WO2008089220A2 - Colorfast fabrics and garments of olefin block compositions - Google Patents

Colorfast fabrics and garments of olefin block compositions Download PDF

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Publication number
WO2008089220A2
WO2008089220A2 PCT/US2008/051142 US2008051142W WO2008089220A2 WO 2008089220 A2 WO2008089220 A2 WO 2008089220A2 US 2008051142 W US2008051142 W US 2008051142W WO 2008089220 A2 WO2008089220 A2 WO 2008089220A2
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WIPO (PCT)
Prior art keywords
fabric
percent
polymer
ethylene
measured
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Application number
PCT/US2008/051142
Other languages
French (fr)
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WO2008089220A9 (en
WO2008089220A3 (en
Inventor
Fabio D'ottaviano
Jerry Chien Ting Wang
Rhonda N. Neel
Debbie Y. Chiu
Traci Li Zhi Zhang
Shih-Yaw Lai
Alberto Lora Lamia
Hongyu Chen
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Dow Global Technologies Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by Dow Global Technologies Inc. filed Critical Dow Global Technologies Inc.
Priority to EP08705940A priority Critical patent/EP2102396B1/en
Priority to AU2008206336A priority patent/AU2008206336A1/en
Priority to CA002674597A priority patent/CA2674597A1/en
Priority to DE602008006667T priority patent/DE602008006667D1/en
Priority to BRPI0806226-9A priority patent/BRPI0806226A2/en
Priority to JP2009546488A priority patent/JP2010516909A/en
Priority to AT08705940T priority patent/ATE508217T1/en
Publication of WO2008089220A2 publication Critical patent/WO2008089220A2/en
Publication of WO2008089220A3 publication Critical patent/WO2008089220A3/en
Publication of WO2008089220A9 publication Critical patent/WO2008089220A9/en

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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/79Polyolefins
    • D06P3/794Polyolefins using dispersed dyes
    • DTEXTILES; PAPER
    • D03WEAVING
    • D03DWOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/20Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
    • D03D15/283Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads synthetic polymer-based, e.g. polyamide or polyester fibres
    • DTEXTILES; PAPER
    • D03WEAVING
    • D03DWOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/50Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads
    • D03D15/56Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads elastic
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/20Physical treatments affecting dyeing, e.g. ultrasonic or electric
    • D06P5/2066Thermic treatments of textile materials
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2201/00Cellulose-based fibres, e.g. vegetable fibres
    • D10B2201/01Natural vegetable fibres
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2201/00Cellulose-based fibres, e.g. vegetable fibres
    • D10B2201/01Natural vegetable fibres
    • D10B2201/02Cotton
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2201/00Cellulose-based fibres, e.g. vegetable fibres
    • D10B2201/01Natural vegetable fibres
    • D10B2201/04Linen
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2201/00Cellulose-based fibres, e.g. vegetable fibres
    • D10B2201/01Natural vegetable fibres
    • D10B2201/08Ramie
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2201/00Cellulose-based fibres, e.g. vegetable fibres
    • D10B2201/01Natural vegetable fibres
    • D10B2201/10Bamboo
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2211/00Protein-based fibres, e.g. animal fibres
    • D10B2211/01Natural animal fibres, e.g. keratin fibres
    • D10B2211/02Wool
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2211/00Protein-based fibres, e.g. animal fibres
    • D10B2211/01Natural animal fibres, e.g. keratin fibres
    • D10B2211/04Silk
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2321/00Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D10B2321/02Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins
    • D10B2321/021Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins polyethylene
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/02Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/04Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00Physical properties
    • D10B2401/06Load-responsive characteristics
    • D10B2401/061Load-responsive characteristics elastic
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00Physical properties
    • D10B2401/06Load-responsive characteristics
    • D10B2401/063Load-responsive characteristics high strength
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00Physical properties
    • D10B2401/14Dyeability
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2501/00Wearing apparel

Definitions

  • This invention relates to dyed fabrics that are coiorfast.
  • the fabric of the present invention is typically a knit or woven fabric comprising elastic fibers.
  • Such knit fabrics include, for example, polyesters like microfiber poh esters.
  • the elastic fibers often comprise the reaction product of at least one ethylene block polymer and at least one crosslinking agent. The fibers are characterized by an amount of crosslinking such that the fabric has the desired properties.
  • the ethylene block poh met is usually
  • ⁇ T > 48°C for ⁇ H greater than 130 J'g .
  • the CRYST ⁇ F peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the pohmer has an identifiable CRYS I AF peak, then the CRYS f AF temperature is 30 0 C; or
  • (6) a molecular fraction which elutes between 40°C and 130"C when fractionated using FRl f . characterized in that the fraction has a molar eemonorner content of at least 5 percent higher than that of a comparable random ethylene interpohmer fraction elutmg between the s.anic temperature, wherein said comparable random ethy lene interpohmer has lhe same comonomer(s) and has a melt index, density, and molar comononier content (based on the whole polymer) within 10 percent of that of the ethylene/ ⁇ - olefin inte ⁇ olymer; or
  • the ethylene/ ⁇ -olefin interpolymer characteristics (1) through (7) above are given with respect to the cthylene/ ⁇ -olcfin interpolymer before any significant crosslinking, i.e.. before crosslinking.
  • the ethylene/ ⁇ -olefin inte ⁇ oiymers useful in the present invention are usually crosslinked to a degree to obtain the desired properties.
  • characteristics (1 ⁇ through (7) as measured before crosslinking is not meant to suggest that the inte ⁇ olymer is not required to be crosslinked - only that the characteristic is measured with respect to the interpolymer without significant crosslinking.
  • Crosslinking may or may not change each of these properties depending upon the specific polymer and degree of crosslinking.
  • the dyed fabrics of the present invention may often be characterized by a color change of greater than or equal to about 3.0 according to AATCC evaluation after a first wash by AATCC 61 -2003- 2A,
  • the dyed fabrics of the present invention may often be characterized by a color strength after dying of greater than or equal to about 600 as measured with a spectrum photometer.
  • Figure 2 show s plots of delta DSC-C RYST ⁇ F as a function of DSC Melt
  • the diamonds represent random ethylene, octene copolymers: the squares represent polymer examples 1 -4: the triangles represent polymer examples 5-9: and the circles represent polymer examples 10-19.
  • the "X " symbols represent polymer examples A + -F*.
  • Figure 3 shows the effect of density on elastic recovery for unoriented films made from inventive inte ⁇ oly mers( represented by the squares and circles) and traditional u poly mers (repicsc ⁇ ted b ⁇ lhe triangles which are v arious M-FINI l ⁇ l Vl polymers (av ailable from The Dow Chemical Company )).
  • the squares represent inventive ethy lene/butene copolymers; and the circles represent in ⁇ r enti ⁇ e ethylene 'octene copolymers.
  • Figure 4 is a plot of octene content of TRKF fractionated ethylene/ 1 -octene copolymer fractions versus TREF elution temperature of the fraction for the polymer of
  • Example 5 represented by the circles
  • eomparati ⁇ e polymers E and F represented by the
  • Figure 5 is a plot of octene content of TREF fractionated ethylene * 1 -octene copolymer fractions versus T REF elution temperature of the fraction for the polymer of
  • Example 5 (curve 1) and for comparative F (curve 2).
  • the squares represent Example F*: and the triangles represent Example 5.
  • Figure 6 is a graph of the log of storage modulus as a function of temperature for comparative ethylene/ 1 -octene copolymer (curve 2) and propylene/ ethylene- copolymer
  • Figure 7 shows a plot of TMA (1 mm) versus flex modulus for some imentive polymers (represented by the diamonds), as compared to some known polymers.
  • the triangles represent various Dow VERSIFY' M polymers( available from The Dow Chemical
  • Figure 8 shows photos of a lab dyeing machine.
  • Hgure 9 shows a dyeing and reduction wash process.
  • '"Fiber means a material in the length to diameter ratio is greater than about 10.
  • Fiber is typically classified according to its diameter.
  • Filament fiber is generally defined as having an individual fiber diameter greater than about 15 denier, usually greater than about 30 denier per filament.
  • Fine denier fiber generally refers to a fiber hav ing a diameter less than about 15 denier per filament.
  • Microdenier fiber is generally defined as fiber ha ⁇ ipg a diameter les 1 - than about !0() microns denier per filament f ⁇ l ⁇ ] * i ilament Il be-" or "monofilament fiber " mean*> a continuous strand of m ⁇ te ⁇ ai o! indefinite ⁇ c . net predetermined j length, a, opposed lo a "staple fiber *" which is a discontinuous strand of material of definite length (i.e.. a strand which has been cut or otherwise divided into segments of a predetermined length).
  • Elastic means that a fiber will recover at least about 50 percent of its stretched length after the first pull and after the fourth to 100% strain (doubled the length). Elasticity can also be described by the "permanent set” of the fiber. Permanent set is the comerse of elasticity. A fiber is stretched to a certain point and subsequent!) released to the original position before stretch, and then stretched again. The point at which the fiber begins to pull a load is designated as the percent permanent set. "Elastic materials " are also referred to in the art as “elastomers'' and "elastomeric”.
  • Elastic material (sometimes referred to as an elastic article) includes the copolymer itself as well as, but not limited to, the copolymer in the form of a fiber, film, strip, tape, ribbon, sheet, coating, molding and the like.
  • the preferred elastic material is fiber.
  • the elastic material can be either cured or uncured. radiated or un-radiated, and/or crosslinked or uncrosslinked.
  • Nonlastic material means a material, e.g., a fiber, that is not elastic as defined above.
  • Homofil fiber means a fiber that has a single polymer region or domain, and that does not ha ⁇ e any other distinct polymer regions (as do bicomponent fibers).
  • Bicomponent fiber means a fiber that has two or more distinct polymer regions or domains. Bicomponent fibers are also know as conjugated or multicomponent fibers. The polymers are usually different from each other although two or more components may comprise the same polymer. 1 he polymers are arranged in substantially distinct /ones across the cross-section of the bicomponent fiber, and usually extend continuously along the length of the bicomponent fiber.
  • bicomponent fiber can be, for example, a sheath/core arrangement (in which one polymer is surrounded by another), a side by side arrangement, a pie arrangement or an "islands-in-the sea” arrangement.
  • Bicomponent fibers are further described in L.S. Patents No. 6.225.243. 6.140.442. 5,382.400. 5.336.552 and 5,108.820.
  • “Melfblown fibers” are fibers formed by extruding a molten thermoplastic polymer composition through a plurality of fine, usually circular, die capillaries as molten threads or filaments into converging high velocity gas streams ⁇ e.g air) which function to attenuate ihe threads or filament-, to reduced diameters. I he filaments or threads are carried and deposited on ⁇ collecting surface to form a we ⁇ o( iandomh dispersed fibers with average diameters geneially ⁇ mailer than I u microns. [0022] "Mcltspun fibers” are fibers formed by melting at least one polymer and then drawing the fiber in the melt to a diameter (or other cross-section shape) less than the diameter (or other cross-section shape) of the die.
  • ""Spunbond fibers" are fibers formed by extruding a molten thermoplastic pohmer composition as filaments through a plurality of fine, usually circular, die capillaries of a spinneret. The diameter of the extruded filaments is rapidly reduced, and then the filaments are deposited onto a collecting surface to form a web of randomly dispersed fibers with average diameters generally between about 7 and about 30 microns.
  • "Nonwoven" means a web or fabric having a structure of individual fibers or threads which are randomly interlaid, but not in an identifiable manner as is the case of a knitted fabric.
  • the elastic fiber in accordance with embodiments of the invention can be employed to prepare nonwoven structures as well as composite structures of elastic nonwoven fabric in combination with nonelastic materials.
  • Yarn means a continuous length of twisted or otherwise entangled filaments which can be used in the manufacture of woven or knitted fabrics and other articles. Yarn can be covered or uncovered. Covered yarn is yarn at least partially wrapped within an outer covering of another fiber or material, typically a natural fiber such as cotton or wool.
  • Polymer means a polymeric compound prepared by polymerizing monomers, whether of the same or a different type, ⁇ he generic term “polymer " embraces the terms “homopolymer,” “copolymer. " “terpolymcr” as well as “inierpolymer.
  • interpolymcr means a polymer prepared by the polymerization of at least two different types oi monomers.
  • inierpolymer includes the term “copolymer” (which is usually employed to refer to a polymer prepared from two different monomers) as well as the term “terpolymer” (which is usually employed to refer to a polymer prepared from three different types of monomers). It also encompasses polymers made by polymerizing four or more types of monomers.
  • ethylene ⁇ -olefin interpoly mer generally refers to polymers comprising ethy lene and an ⁇ -olefin having 3 or more carbon atoms.
  • ethylene comprises the majority mole fraction of the whole polymer, i e.. ethylene comprises at least about 50 mole percent of the whole polymer.
  • ethy lene comprises at least about 60 mole percent, at least about 70 mole percent, or at least about 80 mole percent, with the substantial rern ameer ol ihe nholt131ymtr cump ⁇ sing admir1 leavi one other tor ⁇ on ⁇ 'per thai is preferably an ⁇ -olefin mg 3 or more carbon at ⁇ rr ⁇ ! ⁇ or many ethy lent, octene copolymers, the preferred composition comprises an ethy lene content greater than about 80 mole percent of the whole polymer and an octene content of from about 10 to about 15. preferably from about 15 to about 20 mole percent of the whole pohmer.
  • the ethylene/ ⁇ -o Ie fin interpolymers do not include those produced in low yields or in a minor amount or as a by-product of a chemical process. While the ethylene' ⁇ - olefin interpolymers can be blended with one or more polymers, the as-produced ethylene ' ⁇ - olefin interpolymers are substantially pure and often comprise a major component of the reaction product of a polymerization process.
  • the ethylene/ ⁇ -olcfln interpolymers comprise ethy lene and one or more copoiymerizabie ⁇ -olefm comonomers in polymerized form, characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical or physical properties. That is, the ethvlene/ ⁇ -olefin interpolymers are block interpolymers, preferably multi-block interpolymers or copolymers.
  • the terms "interpolymer” and "copolymer 1" are used interchangeably herein.
  • the multi-block copolymer can be represented by the following formula:
  • n is at least 1, preferably an integer greater than I . such as 2. 3. 4, 5, 10, 15, 20. 30. 40, 50. 60, 70. 80. 90, 100, or higher, " ⁇ " represents a hard block or segment and "B " " represents a soft block or segment.
  • ⁇ s and Bs are linked in a substantially linear fashion, as opposed to a substantially branched or substantially star-shaped fashion.
  • a blocks and B blocks are randomly distributed along the polymer chain.
  • the block copolymers usually do not have a structure as follows.
  • the block copolymers do not usually have a third type of block, which comprises different comonomer(s).
  • each of block A and block B has monomers or comonomers substantially randomly distributed within the block.
  • neither block A nor block B comprises two or more sub-segments (or sub-blocks) of distinct composition, such as a tip segment, which has a substantially different composition than the rest of the block.
  • the multi-block polymers typically comprise ⁇ arious amounts of "hard” and “soft " segments.
  • Hard “ segments refer to blocks of poly mer ⁇ /ed units in which ethy lene is present in an amount greater than about 95 weight percent, and preferably greater than about 98 weight pel cent based on the weight of the polymer.
  • the eomorsomer content ⁇ content of monomers other than ethy lene; in the hard segments is less than Jbout 5 weight percent, and preferably iess than about 2 weight percent ba&ed on the weight of the polymer.
  • the hard segments comprises all or substantially all ethylene.
  • Soft segments refer to blocks of pol> merited units in which the comonomer content (content of monomers other than ethylene) is greater than about 5 weight percent, preferably greater than about 8 weight percent, greater than about 10 weight percent, or greater than about 15 weight percent based on the weight of the polymer.
  • the comonomer content in the soft segments can be greater than about 20 weight percent, greater than about 25 weight percent, greater than about 30 weight percent, greater than about 35 weight percent, greater than about 40 weight percent, greater than about 45 weight percent, greater than about 50 weight percent, or greater than about 60 weight percent.
  • the soft segments can often be present in a block interpolymer from about 1 weight percent to about 99 weight percent of the total weight of the block interpolymer, preferably from about 5 weight percent to about 95 weight percent, from about 10 weight percent to about 90 weight percent, from about 15 weight percent to about 85 weight percent, from about 20 weight percent to about 80 weight percent, from about 25 weight percent to about 75 weight percent, from about 30 weight percent to about 70 weight percent, from about 35 weight percent to about 65 weight percent, from about 40 weight percent to about 60 weight percent, or from about 45 weight percent to about 55 weight percent of the total weight of the block interpolymer.
  • the hard segments can be present in similar ranges.
  • the soft segment weight percentage and the hard segment weight percentage can be calculated based on data obtained from DSC or NMR, Such methods and calculations are disclosed in a concurrently filed U.S. Patent Application Serial No. 1 1/376,835.
  • crystalline refers to a polymer that possesses a first order transition or crystalline melting point (Tm) as determined by differential scanning calorimetry (DSC) or equivalent technique.
  • Tm first order transition or crystalline melting point
  • DSC differential scanning calorimetry
  • amorphous refers to a poly mer lacking a cry stalline melting point as determined by differential scanning eaiorimetry (DSC) or equivalent technique.
  • the blocks differ in the amount or type of comonomer incorporated therein, the density, the amount of crystallinity. the crystallite size attributable to a polymer of such composition, the type or degree of tacticity (isotactic or syndiotactic). regio-regularity or regio-irregularity . the amount of branching, including long chain branching or hyper-branching, the homogeneity, or any other chemical or physical property.
  • the multi-block copolymers are characterized by unique distributions of both polydispersity index (PDI or Mw/ Mn), block length distribution, and/or block number distribution due to the unique process making of the copolymers. More specifically, when produced in a continuous process, the polymers desirably possess PDI from 1.7 to 2.9, preferably from 1.8 to 2.5, more preferably from 1.8 to 2.2, and most preferably from 1.8 to 2.1. When produced in a batch or semi-batch process, the polymers possess PDI from LO to 2.9, preferably from 1.3 to 2.5, more preferably from 1.4 to 2.0, and most preferably from 1.4 to 1.8.
  • PDI polydispersity index
  • he olefin block polymers e.g. ethylene ⁇ -olefin interpolymers, used in embodiments of the invention (also referred to as "inventive interpohmer " or polymer " ) comprise ethylene and one or more copoiymerizabie ⁇ -olefin comonomers in pohmeri/ed form, characterized by muitipie blocks or segments of two or more poh meri/ed monomer u ⁇ ib differing in chemical or phy sical properties (block interpoiynicr). preferably a multi-block copolymer.
  • the ethy lene ⁇ -olefin interpol ⁇ mcrs used in embodiments of the invention have a M v y'M n from about 1.7 to about 3.5 and at least one melting point, T m . in degrees Celsius and density, d. in grams/cubic centimeter, wherein the numerical values of the variables correspond to the relationship;
  • T 111 > -2002.9 - 4538.5(d) - 2422.2(d) 2 , and preferably
  • T m > 858.91 - 1825.3(d) t- 1 112.8(d) 2 .
  • Such melting point/density relationship is illustrated in Figure 1.
  • the inventive interpolymers represented by diamonds
  • the melting point of such polymers are in the range of about 1 10 0 C to about 130 0 C when densit ⁇ ranges from 0.875 g'cc to about 0.945 g/cc.
  • the melting point of Mich polymers are in the range of about 1 15 0 C to about 125 0 C when densit) ranges from 0.875 g,cc to about 0.945 g'cc.
  • the ethylene ; ⁇ -olefm interpol) mcrs comprise, in polymerized form, ethylene and one or more ⁇ -olefins and are characterized by a ⁇ T, in degree Celsius, defined as the temperature for the tallest Differential Scanning Calorimetry ("DSC " ) peak minus the temperature for the tallest Crystallization Anal) sis Fractionation (“CRYS I AF”) peak and a heat of fusion in J g. ⁇ H, and ⁇ T and ⁇ H satisfy the following relationships: ⁇ T > -0.1299( ⁇ H) + 62.8 L and preferably
  • the CRYS TAF peak is determined using at least 5 percent of the cumulative polymer (that is. the peak must represent at least 5 percent of the cumulative polymer), and if iess than 5 percent of the polymer has an identifiable CRYS TAF peak, then the CRYSTAF temperature is 30 0 C, and ⁇ H is the numerical value of the heat or fusion m J g. More preferabh . die highest C RYS I Al peak contains at least 10 percent of the c poly r ⁇ er. Hgure 2 shows plotted data for mvenme polymers as well a ⁇ - com par at he
  • Integrated peak areas and peak temperatures are calculated b ⁇ the computerized drawing program supplied by the instrument maker, lhe diagonal line shown for the random ethylene octene comparative pohmers corresponds to the equation ⁇ T ⁇ -0.1299 (AH) - 62.81.
  • the ethylene' ⁇ -olefm interpohmers ha ⁇ e a molecular fraction which elutes between 40 0 C and 13O 0 C when fractionated using Temperature Rising Elution Fractionation ("TREF " ). characterized in that said fraction has a molar comonomer content higher, preferably at least 5 percent higher, more preferably at least 10 percent higher, than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, wherein the comparable random ethylene interpolymer contains the same comonomer(s). and has a melt index, density, and molar comonomer content (based on the whole polymer) within 10 percent of that of the block interpolymer.
  • TEZ Temperature Rising Elution Fractionation
  • the Mw/Mn of the comparable interpolymer is also within 10 percent of that of the block interpolymer and/or the comparable interpolymer has a total comonomer content within 10 weight percent of that of the block interpolymer.
  • the ethylene/ ⁇ -olcfin interpoKmers are characterized by an elastic reco ⁇ ery, Re, in percent at 300 percent strain and 1 cycle measured on a compression- molded film of an ethylene ' ⁇ -olcfin interpol>mcr, and has a density, d. in grams, cubic centimeter, wherein the numerical values of Re and d satisfy the following relationship when ethylene ' ⁇ -olefin interpolymer is substantially free of a cross-linked phase: Re >1481-1629(d); and preferably
  • the ethylene/ ⁇ -olefm interpolymers have ⁇ 1 ⁇ a storage modulus ratio, G " (25°C>G * ( ⁇ OO°C), of from 1 to 50. preferably from 1 to 20. more preferably from 1 to 10; and or (2) a 7O 0 C compression set of less than 80 percent, preferably less than 70 percent, especially less than 60 percent, less than 50 percent, or less than 40 percent, down to a compression set of 0 percent.
  • G " 25°C>G * ( ⁇ OO°C)
  • the ethylene/ ⁇ -olefm interpolymers have a 7O 0 C compression set of less than 80 percent, less than 70 percent, less than 60 percent, or less than 50 percent.
  • the 70 0 C compression set of the interpolymers is less than 40 percent, less than 30 percent, less than 20 percent, and may go down to about 0 percent.
  • the ethyl ene/ ⁇ -ole fin interpolymers have a heat of fusion of less than 85 J/'g and/or a pellet blocking strength of equal to or less than 100 pounds/foot (4800 Pa), preferably equal to or less than 50 lbs/ft 2 (2400 Pa), especially equal to or less than 5 lbs/ft 2 (240 Pa), and as low as 0 lbs/ft 2 (0 Pa).
  • the ethylene/ ⁇ -olefm interpol ⁇ mers comprise, in polymerized form, at least 50 mole percent ethylene and have a 7O 0 C compression set of less than 80 percent, preferably less than 70 percent or less than 60 percent, most preferably less than 40 to 50 percent and down to close to zero percent,
  • the multi-block copolymers possess a PDI fitting a Schultz-Flory distribution rather than a Poisson distribution.
  • the copolymers are further characterized as having both a polydisperse block distribution and a poivdisperse distribution of block si/es and possessing a most probable distribution of block lengths.
  • Preferred multi- block copolymers are those containing 4 or more blocks or segments including terminal blocks. More preferably, the copolymers include at least 5. 10 or 20 blocks or segments including terminal blocks.
  • Comonomer content may be measured using any suitable technique, with techniques bas.ed on nuclear magnetic resonance ("XMR " ) spectroscopy preferred.
  • the polymer desirably is first fractionated using TREF into fractions each hav ing an cJuted tern perai are range of 10°C or less. That is. each eluted fraction has a collection temperature umdovt of HfC or Ie ⁇ s.
  • the incentive polymer is an olefin interpoly mcr, preferably comprising ethylene and one or more copolymeri/able comonomers in polymerized form, characterized by multiple blocks (i.e.. at least two blocks) or segments of two or more polymerized monomer units differing in chemical or physical properties (blocked interpolymer).
  • a multi-block copolymer said block interpolymer having a peak (but not just a molecular fraction) which elutes between 40 0 C and 13O 0 C (but without collecting and/or isolating individual fractions), characterized in that said peak, has a comonomer content estimated by infra-red spectroscopy when expanded using a full width 'half maximum (FWHM) area calculation, has an average molar comonomer content higher, preferably at least 5 percent higher, more preferably at least 10 percent higher, than that of a comparable random ethylene interpolymer peak at the same elution temperature and expanded using a full width/h a!
  • FWHM full width 'half maximum
  • said comparable random ethylene interpolymer has the same comonomer(s) and has a melt index, density, and molar comonomer content (based on the whole polymer) within 10 percent of that of the blocked interpolymer.
  • the MwMn of the comparable interpolymer is also within 10 percent of that of the blocked interpolymer and/or the comparable interpolymer has a total comonomer content within 10 weight percent of that of the blocked interpolymer.
  • the full width/half maximum (FWIlM) calculation is based on the ratio of methyl to methylene response area ICH 3 /CH 2 ] from the ⁇ 'IREF infra-red detector, wherein the tallest (highest) peak is identified from the base line, and then the FWIIM area is determined.
  • the FWHM area is defined as the area under the curve between Ti and T 2 , where T
  • ⁇ calibration curve for comonomer content is made using random ethylene ' ⁇ -olef ⁇ n copolymers, plotting comonomer content from NMR versus FWIIM area ratio of the TREF peak.
  • the calibration curv e is generated for the same comonomer type of interest.
  • the comonomer content of ⁇ REF peak of the inventiv e polymer can be determined by referencing this calibration curve using its FWHM methyl : methylene area ratio [CHi CH 2 ] of the TREF peak.
  • Comonomer content may be measured using any suitable technique, with techniques based on nuclear magnetic iesonanee (WIRi spectroscopy preferred. I sing th ⁇ technique, said blocked mterpohmer ha ⁇ higher molar comonomer content than a corresponding comparable interpoiyrner.
  • WIRi spectroscopy preferred. I sing th ⁇ technique, said blocked mterpohmer ha ⁇ higher molar comonomer content than a corresponding comparable interpoiyrner.
  • the block interpolymer has a comonomer content of the TREF fraction eluting between 40 and 130 Q C greater than or equal to the quantity ⁇ - 0.2013) T + 20.07, more preferably greater than or equal to the quantity (-0.2013) T ⁇ 21.07, where T is the numerical ⁇ alue of the peak elution temperature of the TREF fraction being compared, measured in 0 C.
  • Figure 4 graphically depicts an embodiment of the block interpolymers of ethylene and 1-octene where a plot of the comonomer content versus TREF elution temperature for se ⁇ eral comparable ethylene'l-octene interpolymers (random copolymers) are fit to a line representing (-0.2013) T - ⁇ - 20.07 (solid line). The line for the equation (- 0.2013) T -+- 21.07 is depicted by a dotted line. Also depicted are the comonomer contents for fractions of several block ethylene/1 -octene interpolymers of the invention (multi-block copolymers).
  • FIG. 5 graphically displays the TREF curve and comonomer contents of polymer fractions for Example 5 and Comparative F discussed below.
  • the peak eluting from 40 to 13O 0 C. preferably from 6O 0 C to 95 0 C for both polymers is fractionated into three parts, each part eluting over a temperature range of less than 10 0 C. Actual data for Example 5 is represented by triangles.
  • an appropriate calibration curve may be constructed for inierpolymers containing different comonomers and a line used as a comparison fitted to the TREb values obtained from comparative interpolymers of the same monomers, preferably random copolymers made using a metallocene or other homogeneous catalyst composition.
  • Inventive interpolymers are characterized by a molar comonomer content greater than the value determined from the calibration curve at the same TREF elution temperature, preferably at least 5 percent greater, more preferably at least 10 percent greater.
  • the inventive polymers can be characterized by one or more additional characteristics.
  • the inventive polymer is an olefin interpolymer, preferably comprising ethy lene and one or more eopohmeri/ahle comonomers in polymerized form, characterized by multiple blocks or segments of two or more pohmeri/ed monomer units- JtfJerhig in chemical or physical properties f blocked interpolymer).
  • said block inte ⁇ x ⁇ vmer rut ins a molecular fraction which el ⁇ tcs between 4O 0 C " and 130X " , when
  • said fraction has a molar comoBomer content higher, preferably at least 5 percent higher, more preferabK at least 10. 15, 20 or 25 percent higher, than that of a comparable random ethylene interpoK mer fraction eluting between the same temperatures, wherein said comparable random ethylene interpolymer comprises the same comonorner(s). preferabK it is the same comonomer(s), and a melt index, density . and molar comonomer content ⁇ based on the whole polymer) within 10 percent of that of the blocked interpolymer.
  • the Mw Mn of the comparable interpolymer is also within 10 percent of that of the blocked interpoly rner and or the comparable interpolymer has a total comonomer content within 10 weight percent of that of the blocked interpolymer.
  • the interpolymers are interpolymers of ethylene and at least one ⁇ -olef ⁇ n, especially those interpolymers having a whole polymer density from about 0.855 to about 0.935 g/cm ⁇ and more especially for polymers having more than about 1 mole percent comonomer, the blocked interpolymer has a comonomer content of the 1 REF fraction eluting between 40 and 13O 0 C greater than or equal to the quantity (-0.1356) F + 13.89.
  • T is the numerical value of the peak ATREF elution temperature of the TREF fraction being compared, measured m 0 C.
  • T is the numerical value of the peak ATREF elution temperature of the TREF fraction being compared, measured m 0 C.
  • the blocked interpolymer has a comonomer content of the TRFF fraction eluting between 40 and 130°C greater than or equal to the quantity (- 0.2013) T -- 20.07, more preferably greater than or equal to the quantity (-0.2013) 1+ 21.07.
  • F is the numerical value of the peak elution temperature of the ⁇ REF fraction being compared, measured in 0 C.
  • the im entive polymer is an olefin interpolymer.
  • preferabK comprising ethylene and one or more copoKmerizable comonomers in polymerized form, characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical or phy sical properties (blocked interpoK mer).
  • a multi- block copolymer said block interpolymer having a molecular fraction which elutes between Mf '( and 130T. when fractionated using 1 RE-I- increments, chatacte ⁇ /ed m that every ing a comonomer content cl at 'cast atx>ut 6 mole percent fias.
  • Tm > (-5.5926)(mole percent comonomer in the fraction) + 135.90.
  • the inventhe polymer is an olefin interpolymer, preferably comprising ethylene and one or more copolymerizable comonomers in poly merized form, characterized by multiple blocks or segments of two or more polymeri/ed monomer units differing in chemical or physical properties (blocked interpolymer), most preferably a multi- block copolymer, said block interpolymer having a molecular fraction which elutes between 40 0 C and BO 0 C. when fractionated using TREF increments, characterized in that every fraction that has an ATREF elution temperature greater than or equal to about 7 ⁇ °C, has a melt enthalpy (heat of fusion) as measured by DSC. corresponding to the equation:
  • the inventive block interpolymers have a molecular fraction which elutes between 4O 0 C and 13O 0 C, when fractionated using TRHF increments, characterized in that every fraction that has an ATREF elution temperature between 40 0 C and less than about 76°C. has a melt enthalpy (heat of fusion) as measured by DSC, corresponding to the equation:
  • the "composition mode" of the detector is equipped with a measurement sensor (CH 2 ) and composition sensor (CFIj) that are fixed narrow band infra-red filters in the region of 2800-3000 cm “1 .
  • the measurement sensor detects the methylene (CHa) carbons on the polymer (which directly relates to the polymer concentration in solution) while the composition sensor detects the methyl (CH-,) groups of the polymer.
  • the mathematical ratio of the composition signal (CH ? ) dhided by the measurement signal (CH;) is sensitive to the comonomer content of the measured polymer in solution and its response is calibrated with known ethylene aipha-olefm copolymer "standards.
  • a polymer specific calibration can be created by measuring the area ratio of the CII3 to CH 2 for polymers with known comonomer content (preferably measured b> NMR).
  • the comonomer content of an ATREF peak of a pohmer can be estimated by applying a the reference calibration of the ratio of the areas for the individual CH 3 and CH 2 response (i.e. area ratio CH 3 /CH 2 ⁇ ersus comonomer content),
  • the area of the peaks can be calculated using a full width/ half maximum (FWHM) calculation after applying the appropriate baselines to integrate the individual signal responses from the FREF chromatogram.
  • the full width/half maximum calculation is based on the ratio of methyl to methylene response area [CH 3 /CH 2 J from the ATREF infrared detector, wherein the tallest (highest) peak is identified from the base line, and then the FWHM area is determined.
  • the FWHM area is defined as the area under the curve between Tl and F2. where Tl and T2 are points determined, to the left and right of the ATREF peak, by dividing the peak height by two, and then drawing a line horizontal to the base line, that intersects the left and right portions of the ATREF curve.
  • infra-red spectroscopy to measure the comonomer content of polymers in this ATREF-infra-red method is, in principle, similar to that of GPC/FT1R systems as described in the following references: Markovich, Ronald P.; Ilazlitt. Lonnie G.; Smith, Linley; "Development of gel-permeation chromatography -Fourier transform infrared spectroscopy for characterization of ethyiene-based poly olefin copolymers " . Polymeric Materials Science and Engineering ( 1991), 65. c >8-100.: and Deslauriers, P. J.; Rohlfmg, D. C: Shieh, E.
  • the inventive ethylenes-olefin interpolymer is characterized by an av erage block index.
  • ABL which is greater than /ero and up to about 1.0 and a molecular weight distribution.
  • ABI is the weight average of the block index ("Bf") for each of the pohmer fractions obtained in preparative TREF from 20 0 C and 1 10 0 C. with an increment of 5 0 C:
  • BI 1 is the block index for the ith fraction of the incentive ethylene ⁇ -olelln interpolymer obtained in preparative 1 REF.
  • w s is the weight percentage of the ith fraction.
  • Bl is defined by one of the two following equations (both of which give the same Bl value):
  • T ⁇ is the preparative ATREF elution temperature for the ith fraction (preferably expressed in Kelvin)
  • Px is the ethylene mole fraction for the ith fraction, which can be measured b> NMR or IR as described above.
  • P ⁇ B is the ethylene mole fraction of the whole ethylene ⁇ -olefin interpoSymer (before fractionation), which also can be measured by NMR or IR.
  • T ⁇ and P A are the ATRHF elution temperature and the ethylene mole fraction for pure "hard segments" (which refer to the crystalline segments of the interpolymer).
  • the T v and P ⁇ values are set to those for high density polyethylene homopoiymer. if the actual values for the "hard segments' " are not available.
  • T ⁇ is 372°K
  • P ⁇ is 1.
  • f VB is the AT RLF temperature for a random copolymer of the same composition and having an ethylene mole fraction of P ⁇ ⁇ .
  • T ⁇ B can be calculated from the following equation:
  • ⁇ and ⁇ are two constants which can be determined by calibration using a number of known random ethylene copolymers. It should be noted that ⁇ and ⁇ may van from instrument to instrument. Moreover, one would need to create their own calibration curve with the polymer composition of interest and also in a similar molecular weight range as the fractions. Lhere is a slight molecular weight effect. If the calibration curv e is obtained from similar molecular weight ranges, such effect would be essentially negligible.
  • random ethylene copoly mers satisfy the following relationship
  • the weight average block index, ABI. for the whole polymer can be calculated.
  • ABI is greater than zero but less than about 0.3 or from about 0.1 to about 0.3. ⁇ n other embodiments.
  • ABl is greater than about 0.3 and up to about 1.0.
  • ABI should be in the range of from about 0,4 to about 0.7. from about 0.5 to about 0.7, or from about 0.6 to about 0.9. In some embodiments.
  • ABl is in the range of from about 0.3 to about 0.9, from about 0.3 to about 0.8, or from about 0.3 to about 0.7, from about 0.3 to about 0.6, from about 0.3 to about 0.5, or from about 0.3 to about 0.4. In other embodiments. ABl is in the range of from about 0.4 to about 1.0. from about 0.5 to about 1.0- or from about 0.6 to about 1.0, from about 0.7 to about 1.0, from about 0.8 to about 1.0, or from about 0.9 to about 1.0.
  • inventive ethvlene' ⁇ -olefm interpolymer comprises at least one polymer fraction which can be obtained by preparative TREF 5 wherein the fraction has a block index greater than about 0.1 and up to about 1.0 and a molecular weight distribution, Mw 1 M n . greater than about 1.3. ⁇ n some embodiments, the polymer fraction has a block index greater than about 0.6 and up to about 1.0. greater than about 0.7 and up to about 1.0, greater than about 0.8 and up to about 1.0, or greater than about 0.9 and up to about 1.0.
  • the polymer fraction has a block index greater than about 0.1 and up to about 1.0. greater than about 0.2 and up to about 1.0, greater than about 0.3 and up to about 1.0, greater than about 0.4 and up to about 1.0, or greater than about 0.4 and up to about 1.0. In still other embodiments, the polymer fraction has a block index greater than about 0.1 and up to about 0.5, greater than about 0,2 and up to about 0.5. greater than about 0.3 and up to about 0.5. or greater than about 0.4 and up to about 0.5. In yet other embodiments, the polv mer fraction has a block index greater than about 0.2 and up to about 0.9.
  • the inventive pohmers preferably possess (D a PDI of at least 1.3. more preferabh at least 1.5. at least 1.7. or at least 2.0. and most preferably at least 2 6. up to a maximum value of 5.0. more piefcrahh ap to a maximum of 3.5. and especial!) up to a maximum of 2. 7 : (2) a heat of fusion uf 8 ⁇ J g or less: ( ?) an
  • inventive polymers can have, alone or in combination with any other properties disclosed herein, a storage modulus, G", such that log (G ' ) is greater than or equal to 400 kPa. preferably greater than or equal to 1.0 MPa. at a temperature of 100 0 C.
  • inventive polymers possess a relatively flat storage modulus as a function of temperature in the range from 0 to 100 0 C (illustrated in Figure 6) that is characteristic of block copolymers, and heretofore unknown for an olefin copolymer, especially a copolymer of ethylene and one or more Cj -S aliphatic ⁇ -olefms.
  • olefin copolymer especially a copolymer of ethylene and one or more Cj -S aliphatic ⁇ -olefms.
  • the inventive interpolymers may be further characterized by a thermomechanical analysis penetration depth of 1 mm at a temperature of at least 9O 0 C as well as a flexural modulus of from 3 kpsi (20 MPa) to 13 kpsi (90 MPa).
  • the inventive interpolymers can ha ⁇ e a thermomechanical analysis penetration depth of 1 mm at a temperature of at least 104 0 C as well as a flexural modulus of at least 3 kpsi (20 MPa). They may be characterized as having an abrasion resistance (or volume loss) of less than 90 mm J .
  • Figure 7 shows the TMA (1 mm) versus flex modulus for the inventive polymers, as compared to other known polymers.
  • the inventive polymers have significantly better flexibility-heat resistance balance than the other polymers.
  • the ethy !ene/ ⁇ -olefin interpolymers can have a melt index. I 2 . from 0.01 to 2000 g/ 10 minutes, preferably from 0.01 to 1000 g'10 minutes, more preferably from 0.01 to 500 g/10 minutes, and especially from 0.01 to 100 g/10 minutes.
  • the ethy lene/ ⁇ -olefin interpolymers have a melt index, h. from 0.01 to 10 g/ 10 minutes, from 0.5 to 50 g/10 minutes, from 1 to 30 g/10 minutes, from 1 to 6 g 10 minutes or from 0.3 to 10 g, 10 minutes.
  • the melt index for the ethylenc ⁇ -olefm polvmers is Ig/ 10 minutes. 3 g'10 minutes or 5 gi O minutes.
  • the polymers can have molecular weights, M w . from 1 ,000 g mole to 5,000.000 g, mole. preferably from 1000 g mole to 1 ,000,000, more preferably from 10.000 g mole to 500,000 g/mole, and especially from 10,000 g mole to 300,000 g mole.
  • the density of the inventive polvmers can be from 0.80 to 0.99 g'cr ⁇ * and preferably for ethy lene containing polymers from 0,85 g cm ' to ') 97 g era ' .
  • the density el the ethy lene ⁇ -oiefin polymers ranges from 0.860 to 0.925 g em ' or 0.867 to 0.910 g eai ⁇
  • Catalyst ( ⁇ 1 ) is [N-(2, ⁇ -di( 1 -niethyleths 1 )pheny l)amido)(2-isoprop> lpheny 1 )( ⁇ - naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium dimethyl, prepared according to the teachings of WO 03'4019S. 2003US0204017. USSN 10/429.024. filed May 2. 2003, and WO
  • Catalyst (A3) is bis[N.N - " ' -(2,4,6- trifmethylpheny l)amido)ethylenediamine]hafhium dibenzyl.
  • Catalyst ( ⁇ 4) is bis((2-oxoyl-3-(diben/o-lH-pvrroic-l- ⁇ l)-5-(meth> l)phenyl)-2- pheno ⁇ ymethyl)c ⁇ clohexane-l,2-di ⁇ l zirconium (IV) diben/vl. prepared substantialh according to the teachings of LS-A-2004'0010103.
  • Catalyst (B2) is L2-bis-(3,5-di-t-butylphenylene)(l-(N-(2-meth ⁇ lcycIohex>l)- immino)methyl)(2-oxoyl) zirconium dibenzvl
  • Catalyst (C l ) is (t-but>Iamido)dimcth> l(3-N-p>rrol>l-1.2.3,3a,7a- ⁇ -indcn-l - >I)silanctitanium dimethyl prepared substantiall ⁇ according to the techniques of USP 6,268,444:
  • Catahst (C2) is (t-but ⁇ l- L2.3.3a,7a- ⁇ -inden- according to the teachings of L S-A- 2003 004286:
  • Catalyst (D 1 ) is bis(dimcth> ldisiloxane)(indcnc- 1 -yl)zirconium dichloridc available from Sigma- ⁇ ldrich:
  • shuttling agents employed include lzine. di(i- but ⁇ l)zinc, trieth> taluminum. triocty laluminum. triethv IgaUium, i- i-b ⁇ t> laluminum bis(di(trimeth> lsil> l)amide). n-octvialuminum bis ⁇ n-ociadec> hi-bun laluminum. i- laluminum bB( ⁇ t( !armde ⁇ .
  • ethylzinc (2,6-diphenyiphenox ⁇ de) and ethy Izinc (t-butoxide).
  • the foregoing process takes the form of a continuous solution process for forming block copolymers, especially multi-block copolymers, preferably linear multi- block copolymers of two or more monomers, more especially ethylene and a C ⁇ o olefin or cycloolefm, and most especially ethylene and a C 4 . 20 ⁇ -olefm. using multiple catalysts that are incapable of intercon version. That is, the catalysts are chemically distinct.
  • the process is ideally suited for polymerization of mixtures of monomers at high monomer conversions. Under these polymerization conditions, shuttling from the chain shuttling agent to the catalyst becomes ad ⁇ antaged compared to chain growth, and multi-block copolymers, especially linear multi- block copolymers are formed in high efficiency.
  • the inventive interpolymers may be differentiated from conventional, random copolymers, physical blends of polymers, and block copolymers prepared via sequential monomer addition, fluxional catalysts, anionic or cationic living polymerization techniques.
  • the inventive interpolymers compared to a random copolymer of the same monomers and monomer content at equivalent cry stallintty or modulus, the inventive interpolymers have better (higher) heat resistance as measured by melting point, higher TMA penetration temperature, higher high- temperature tensile strength, and/ or higher high-temperature torsion storage modulus as determined by dynamic mechanical analysis.
  • the inventive interpoiymers have lower compression set. particularly at elevated temperatures, lower stress relaxation, higher creep resistance, higher tear strength, higher blocking resistance, faster setup due to higher crystallization (solidification) temperature, higher recovery (particularly at elevated temperatures), better abrasion resistance, higher retractive force, and better oil and filler acceptance.
  • the inventiv e interpolymers have a relatively large difference between the tallest peak temperature measured using CRYS TAF and DSC as a function of heat of fusion, especially as compared to random copolymers containing the same monomeis and monomer level or phy sical blciidb of poh niers. such a*, a blend of a high density polymer and a lower density eopoh met", at equivalent en era! 1 density .
  • the in ⁇ enti ⁇ e interpolvmers may comprise alternating blocks of differing comonomer content (including homopolymer blocks).
  • the in ⁇ enti ⁇ e interpolvmers may also comprise a distribution in number and/or block size of polymer blocks of differing density or comonomer content, which is a Schultz-Flory type of distribution.
  • inventive interpolvmers also have a unique peak melting point and crystallization temperature profile that is substantially independent of polymer density, modulus, and morphology,
  • the microcrystalline order of the polvmers demonstrates characteristic spherulites and lamellae that are distinguishable from random or block copolymers, even at PDl ⁇ alues that are less than 1.7. or even less than 1.5. down to less than 1.3.
  • inventive interpolymers may be prepared using techniques to influence the degree or level of blockiness. That is the amount of comonomer and length of each polymer block or segment can be altered by controlling the ratio and type of catalysts and shuttling agent as well as the temperature of the polymerization, and other polymerization variables.
  • a surprising benefit of this phenomenon is the discovery that as the degree of blockiness is increased, the optical properties, tear strength, and high temperature recovery properties of the resulting polymer are improved. In particular, haze decreases while clarity, tear strength, and high temperature recovery properties increase as the average number of blocks in the polvmer increases.
  • shuttling agents and catalyst combinations having the desired chain transferring ability high rates of shuttling with low levels of chain termination
  • other forms of polvmer termination are effective! ⁇ suppressed. Accordingly, little if any ⁇ -hydride elimination is observed in the polymerization of ethylene/ ⁇ -oiefin comonomer mixtures according to embodiments of the invention, and the resulting crystalline blocks are highly, or substantially completely, linear, possessing little or no long chain branching.
  • Pol>mers with highly crystalline chain ends can be selectively prepared in accordance with embodiments of the invention.
  • reducing the relative quantity of polvmer that terminates with an amorphous block reduces the i ⁇ termolecuiar d ⁇ utive effect on ervstalline regions. This result can be obtained by choosing chain shuttling agents and eatahsts hav ing an appropriate response to hydrogen or other chain terminating agents.
  • the ethy !ene ⁇ -oletln interpolymers used in the embodiments of the ⁇ n ⁇ ention are preferably interpolymers of ethylene with at least one C3-C2O ⁇ -olefm. Copolymers of ethylene and a C3-C20 ⁇ -olef ⁇ n are especially preferred.
  • the interpolymers may further comprise C4-C] 8 diolefm and/or alkenylbenzene.
  • Suitable unsaturated comonomers useful for polymerizing with ethylene include, for example. eth>lenically unsaturated monomers, conjugated or nonconjugated dienes. polyenes, alkenylbenzenes, etc.
  • Examples of such comonomers include C3-C20 ⁇ -olefins such as propy lene, isobutylene, 1-butene, 1-hexene, l-pentene, 4-methyl-l-pentene, 1-heptene. 1-octene, 1-nonene, 1 -decene, and the like. 1- butene and 1-octene are especially preferred.
  • Other suitable monomers include styrene. halo- or alkyi-substituted styrenes, vinylbcn/ocyclobutane. 1 ,4-hexadiene, L7-octadiene.
  • ethylene/ ⁇ -olefm interpolymers are preferred polymers, other ethylene/olefin polymers may also be used.
  • Olefins as used herein refer to a family of unsaturated hydrocarbon-based compounds with at lea ⁇ t one carbon-carbon double bond. Depending on the selection of catalysts, any olefin may be used in embodiments of the invention.
  • suitable olefins are C3-C20 aliphatic and aromatic compounds containing viny Hc unsaturation. as well as cyclic compounds, such as cyclobutene, cyclopentene.
  • dicyclopentadiene and norbornene, including but not limited to. norbornene substituted in the 5 and 6 position with Ci-C20 hydrocarbyl or cyclohydrocarby 1 groups. Also included are mixtures of such olefins as well as mixtures of such olefins with C4-C40 diolefm compounds.
  • olefin monomers include, but are not limited to propy lene. isobutylene. 1-butene, l-pentene, 1-hexene. 1-heptene, 1-octene. 1 -no ⁇ ene. 1 -decene, and 1 ⁇ dodecene. 1 -tetradecetie, 1-hexadeeene. 1 -oetadeeene. I -eicosene. 3 -methy l- 1-butene. 3- ni €tK I- 1 -penleiie. 4-r ⁇ eth> 1- 1 -per. 1 ene. 4.6- Jimethy 1- 1 -heptene.
  • the ⁇ -olefin is propylene.1 -butene. 1 ⁇ pentene,l-hexene. 1-octene or a combination thereof.
  • hydrocarbon containing a vinyl group potentially may be used in embodiments of the i mention, practical issues such as monomer a ⁇ ailability, cost, and the ability to conveniently remove unreacted monomer from the resulting polymer may become more problematic as the molecular weight of the monomer becomes too high.
  • polystyrcne mono ⁇ inylidene aromatic monomers including styrcne, 0- methyl styrene. p-methyl styrene, t-butylstyrene, and the like.
  • interpolymcrs comprising ethylene and styrene can be prepared by following the teachings herein.
  • copolymers comprising ethylene, styrene and a C3-C20 alpha olefin, optionally comprising a C4-C20 diene, having improved properties can be prepared.
  • Suitable non-conjugated diene monomers can be a straight chain, branched chain or cyclic hydrocarbon diene having from 6 to 15 carbon atoms.
  • suitable non- conjugated dienes include, but are not limited to. straight chain acyclic dienes. such as 1 ,4- hexadiene, 1.6-octadiene, 1 ,7-octadiene.
  • 1,9-decadiene branched chain acyclic dienes, such as 5-methyl-l ,4-hexadiene; 3.7-dimethyl-l, ⁇ -octadiene; 3,7-dimethyl-1.7-octadiene and mixed isomers of dihydromyricene and dihydroocinene, single ring alicyclic dienes. such as 1,3-cyclopentadiene; 1,4-cyclohexadiene; 1.5-cyclooctadiene and 1.5-cyclododecadiene. and multi-ring alicyclic fused and bridged ring dienes. such as tetrahydroindene.
  • the particularly preferred dienes are 1 ,4-hexadiene (HD).
  • the especially preferred dienes are 5- ethylidene-2-norbornene (ENB) and 1.4-hexadiene (HD).
  • JOlOO] One class of desirable polymers that can be made in accordance with embodiments of the invention are cia ⁇ tomeric inierpolymers of ethy lene, a C3-C20 u-oleiin.
  • cvpe ⁇ alh prop ⁇ Icne. and optionally one or more diene ⁇ - ⁇ lcilns for use in this, embodiment of the presera im ention are designated hy the formula C I ⁇ CHR + .
  • R* is a linear or branched alkyl group of from 1 lo 12 carbon atoms.
  • suitable ⁇ -olefms include, but are not limited to, propy lene. isobutylene. 1 -butene, 1 -pentene, 1-hexene, 4-methyl-l -pentene. and 1-oc ⁇ .ene. ⁇ particularly preferred ⁇ -olefin is propylene.
  • the propylene based polymers are generally referred to in the art as EP or EPDM polymers.
  • Suitable dienes for use in preparing such polymers, especially multi-block EPDM type polymers include conjugated or non-conjugated, straight or branched chain-, cyclic- or poly cyclic- dienes comprising from 4 to 20 carbons.
  • Preferred dienes include 1.4-pentadiene, 1 ,4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, cyclohexadiene. and 5- butyli.dene-2-norbomene, A particularly preferred diene is 5-ethylidene-2-norbornene.
  • the diene containing polymers comprise alternating segments or blocks containing greater or lesser quantities of the diene (including none) and ⁇ -olefin (including none), the total quantity of diene and ⁇ -olef In may be reduced without loss of subsequent polymer properties. That is. because the diene and ⁇ -olefin monomers are preferentially incorporated into one type of block of the polymer rather than uniformly or randomly throughout the polymer, they are more efficiently utilized and subsequently the crosslink density of the polymer can be better controlled. Such crosslinkable elastomers and the cured products have advantaged properties, including higher tensile strength and better elastic recovery.
  • the inventive interpolymers made with two catalysts incorporating differing quantities of comonomer have a weight ratio of blocks formed thereby from 95:5 to 5:95.
  • the elastomeric polymers desirably have an ethylene content of from 20 to 90 percent, a diene content of from 0.1 to 10 percent, and an ⁇ -olefin content of from 10 to 80 percent, based on the total weight of the polymer.
  • the multi-block elastomeric polymers have an ethylene content of from 60 to 90 percent, a diene content of from 0.1 to 10 percent, and an ⁇ -olefm content of from 10 to 40 percent, based on the total weight of the poi>mer.
  • Preferred polymers are high molecular weight polymers, ha ⁇ ing a weight average molecular weight (Mw) from 10.000 to about 2.500.000. preferably from 20,000 to 500.000, more preferably from 20.000 to 350.000, and a polydispersity less than 3.5. more preferably less than 3.0. and a Mooney ⁇ iscosity (ML ( 1 -4) 125°C.) from 1 to 250. More preferably, such polymers have an ethy lene content from 65 to 75 percent, a diene content from 0 to 6 percent, and an ⁇ - ⁇ lefin content from 20 to 35 percent.
  • Mw weight average molecular weight
  • the ethylene ⁇ -olelm interpoK mcrs can be iunetionaii/eu by incorporating at least one functional group in ⁇ U polymer structure.
  • exemplary functional groups may include, for example, ethyienieu ⁇ k unsaturated mono- and di-functional carboxylic acid ⁇ . ethylenically unsaturated mono- and di ⁇ functional carboxylic acid anhydrides, salts thereof and esters thereof.
  • Such functional groups may be grafted to an ethylene/ ⁇ -olefin interpolymer. or it may be copolymerized with ethylene and an optional additional comonomer to form an interpolymer of ethylene, the functional comonomer and optionally other comonomer(s).
  • the amount of the functional group present in the functional interpolymer can vary.
  • the functional group can typically be present in a copolymer- type functional i zed interpolymer in an amount of at least about 1.0 weight percent, preferably at least about 5 weight percent, and more preferably at least about 7 weight percent.
  • the functional group will typically be present in a copolymer-type functionalized interpolymer in an amount less than about 40 weight percent, preferably less than about 30 weight percent, and more preferably less than about 25 weight percent.
  • An automated liquid-handling robot equipped with a heated needle set to 160 0 C is used to add enough 1 ,2,4-trichlorobenzene stabilized with 300 ppm ionol to each dried polymer sample to a final concentration of 30 mg/mL.
  • a small glass stir rod is placed into each tube and the samples are heated to 160 0 C for 2 hours on a heated, orbital -shaker rotating at 250 rpm.
  • the concentrated polymer solution is then diluted to 1 mg/ml using the automated liquid-handling robot and the heated needle set to 16O 0 C.
  • a Symyx Rapid GPC system is used to determine the molecular weight data for each sample.
  • a Gilson 350 pump set at 2.0 mimin flow rate is used to pump helium-purged 1.2-dichlorobenzenc stabilized with 300 ppm Ionol as the mobile phase through three Plgel 10 micrometer ⁇ m) Mixed B 300mm x 7.5mm columns placed in series and heated to 160 c C.
  • a PoK mer Labs ELS 1000 Detector is used with the E ⁇ aporator set to 25O 0 C. the Nebuii/er set to I65 C C. and the nitrogen flow rate set to 1 ,8 SLM at a pressure of 60-80 p ⁇ (4UO-600 kPa) N:.
  • the polymer samples are heated to 160 0 C and each sample injected into a 250 ⁇ l loop u ⁇ ing the liquid-handling robot and a heated needle.
  • [0108J Branching distributions are determined by crystallization analysis fractionation (CRYST ⁇ F) using a CRYSTAF 200 unit commercially available from PolymcrChar. Valencia, Spain.
  • the samples are dissolved in 1 ,2,4 trichlorobenzene at 160 0 C (0.66 mg/niL) for 1 hour and stabilized at 95°C for 45 minutes.
  • the sampling temperatures range from 95 to 30 0 C at a cooling rate of 0.2 0 C 7 ITaIn.
  • An infrared detector is used to measure the polymer solution concentrations.
  • the cumulative soluble concentration is measured as the polymer crystallizes while the temperature is decreased.
  • the analytical derivative of the cumulative profile reflects the short chain branching distribution of the polymer.
  • the CRYST ⁇ F peak temperature and area are identified by the peak anal y sis module included in the CRYSTAF Software (Version 200 l .b, PoiymerChar, Valencia, Spain).
  • the CRYS FAF peak finding routine identifies a peak temperature as a maximum in the dW/dT curve and the area between the largest positive inflections on either side of the identified peak in the derivative curve.
  • the preferred processing parameters are with a temperature limit of 7O 0 C and with smoothing parameters above the temperature limit of 0.1. and below the temperature limit of 0.3.
  • the DSC melting peak is measured as the maximum in heat flow rate (W/g) with respect to the linear baseline drawn between -30 & C and end of melting.
  • the heat of fusion is measured as the area under the melting curve between -3O 0 C and the end of melting using a linear baseline.
  • the gel permeation chromatographic system consists of either a Polymer Laboratories Model PL-210 or a Polymer Laboratories Model PL-22G instrument.
  • the column and carousel compartments are operated at HO 0 C.
  • Three Polymer Laboratories 10- micron Mixed-B columns are used.
  • the solvent is 1,2,4 trichlorobenzene.
  • the samples are prepared at a concentration of O. t grams of polymer in 50 milliliters of solvent containing 200 ppm of butylated hydroxytoluene (BHT). Samples are prepared by agitating lightly for 2 hours at 16O 0 C.
  • the injection volume used is 100 microliters and the flow rate is 1.0 ml/minute.
  • Calibration of the GPC column set is performed with 21 narrow molecular weight distribution polystyrene standards with molecular weights ranging from 580 to 8,400,000, arranged in 6 ""cocktail" mixtures with at least a decade of separation between individual molecular weights.
  • the standards are purchased from Polymer Laboratories (Shropshire, UK).
  • the polystyrene standards are prepared at 0.025 grams in 50 milliliters of solvent for molecular weights equal to or greater than 1.000.000. and 0.05 grains in 50 milliliters of solvent for molecular weights less than 1 ,000.000.
  • the polystyrene standards are dissolved at 80 0 C with gentle agitation for 30 minutes.
  • the narrow standards mixtures are run first and in order of decreasing highest molecular weight component to minimize degradation.
  • Compression set is measured according to ⁇ STM D 395.
  • the sample is prepared by stacking 25.4 mm diameter round discs of 3.2 mm, 2.0 mm. and 0.25 mm thickness until a total thickness of 12.7 mm is reached.
  • the discs are eui from 12.7 cm x 12, 7 cm compression molded plaques molded with a hot press under the following conditions: zero pressure for 3 minutes at 190 0 C, followed by 86 MPa for 2 minutes at 19O 0 C. followed by cooling inside the press with co ⁇ d running water at 86 MPa.
  • Samples for density measurement are prepared according to ASTM D 1928. Measurements are made within one hour of sample pressing using ASTM D792. Method B.
  • Samples are compression molded using ASTM D 1928. Flexural and 2 percent secant moduli are measured according to ASTM D-790. Storage modulus is measured according to ASTM D 5026-01 or equivalent technique.
  • the compression molded films are used for optical measurements. tensile behavior, recovery, and stress relaxation.
  • Clarity is measured using BYK Gardner Haze-gard as specified in ASTM D 1746.
  • Procedure A Mineral oil is applied to the film surface to remove surface scratches.
  • ⁇ f is the strain taken for cyclic loading and ⁇ ., is the strain where the load returns to the baseline during the T 1 unloading cycle.
  • L is the load at 50% strain at 0 time and L ) 2 is the load at 50 percent strain after 12 hours.
  • D ⁇ namic Mechanical Analysis is measured on compression molded disks formed in a hot press at 18O 0 C at 10 MPa pressure for 5 minutes and then v ⁇ ater cooled in the press at 90 0 C / min. Testing is conducted using an ARES controlled strain rheometer (TA instruments) equipped with dual cantilever fixtures for torsion testing.
  • TA instruments ARES controlled strain rheometer equipped with dual cantilever fixtures for torsion testing.
  • a 1.5mm plaque is pressed and cut in a bar of dimensions 32x12mm. The sample is clamped at both ends between fixtures separated by 10mm (grip separation ⁇ L) and subjected to successive temperature steps from -100 0 C to 200 0 C (5°C per step). At each temperature the torsion modulus G' is measured at an angular frequency of 10 rad/s, the strain amplitude being maintained between 0.1 percent and 4 percent to ensure that the torque is sufficient and that the measurement remains in the linear regime.
  • Meit index, or I 2 . is measured in accordance with AS TVl D 1238, Condition 190X72.16 kg. Melt index, or Iio is also measured in accordance with ASTM D 1238, Condition 190 0 COO kg.
  • a ⁇ ah tical temperature rising elution fractionation (A I RhF) anal) sis is conducted according to the method described in U.S. Patent No. 4.798.081 and Wilde, L.; Rj Ie, f.R.; Knobeloch. D. C: Peat. I.R.: Determination of Branching Distributions in Polyethylene and Ethylene Copolymers. J. PoKm. ScL 20, 441-455 ( 1982), which are incorporated b> reference herein in their entire! ⁇ .
  • composition to be analvzed is dissohed in t ⁇ ehSorobe ⁇ /e ⁇ e and allowed to cnstalh/e in a column containing an inert bupport (>tamle ⁇ steel shot* b ⁇ slowh reducing the temperature to 2lP € at a cooling rate of O. TC min. the column h equipped with an infrared detector.
  • An ⁇ I RFF ehromatograin curve is then generated by eluting the crystallized poljmer sample from the column slowly increasing the temperature of the eluting solvent (trichloroben/ene) from 20 to 12O 0 C at a rate of 1.5 0 C/min.
  • the samples are prepared by adding approximately 3g of a 50'5O mixture of telrachioroethane-d" orthodichlorobenzene to 0.4 g sample in a 10 mm NMR tube.
  • the samples are dissolved and homogenized by heating the tube and its contents to 150 0 C.
  • the data are collected using a JEOL EclipseTM 400MHz spectrometer or a Varian Unity PlusTM 400MHz spectrometer, corresponding to a 13 C resonance frequency of 100.5 MHz.
  • the data are acquired using 4000 transients per data file with a 6 second pulse repetition delay. To achieve minimum signal-to-noise for quantitative analysis, multiple data files are added together.
  • the spectral width is 25,000 Hz with a minimum file size of 32K data points.
  • the samples are analyzed at 130 0 C in a 10 mm broad band probe.
  • the comonomer incorporation is determined using Randall's triad method (Randall, J. C; JMS-Rev. Macromol. C hem. Phys., C29, 201-317 (1989), which is incorporated bv reference herein in its entirety.
  • TREF fractionation is carried by dissolving 15-20 g of polymer in 2 liters of 1.2,4-trichlorobenzene (TCB)by stirring for 4 hours at 160 0 C.
  • the pol>mer solution is forced b> 15 psig ( 100 kPa) nitrogen onto a 3 inch by 4 fool (7.6 cm x 12 cm) steel column packed with a 60:40 (v:v) mix of 30-40 mesh (600-425 ⁇ m) spherical, technical qual ⁇ t) glass beads (available from Potters Industries, HC 30 Box 20, Brownwood, IX, 76801) and stainless steel, 0.028" (0.7mm) diameter cut wire shot (available from Pellets. Inc.
  • the pohmer is concentrated in each fraction using a rotan evaporator until about 50 to 100 ml of the poKmer solution remains, I he concentrated HiiUttons are allowed io •-t ⁇ nd overnight before adding excess methanol, filtering, and rinsmg (jpprox. 3CO-50O ml of methanol including the final rinse i. f he filtration step is performed on A 3 position vacuum assisted filtering station using 5.0 ⁇ m polytetrafluoroethviene coated filter paper (available from Osmonics Inc.. Cat ⁇ Z50WP04750). The filtrated fractions are dried overnight in a ⁇ acuum ov en at 60 c C and weighed on an analytical balance before further testing.
  • Melt Strength is measured by using a capillary rheometer fitted with a 2.1 mm diameter, 20: 1 die with an entrance angle of approximate ⁇ 45 degrees. After equilibrating the samples at 190 0 C for 10 minutes, the piston is run at a speed of 1 inch/minute (2.54 cm/minute). The standard test temperature is 190 0 C. The sample is drawn uniaxially to a set of accelerating nips located 100 mm below the die with an acceleration of 2.4 mm/sec 2 . The required tensile force is recorded as a function of the take-up speed of the nip rolls. The maximum tensile force attained during the test is defined as the melt strength. ⁇ n the case of polymer melt exhibiting draw resonance, the tensile force before the onset of draw resonance was taken as melt strength. The melt strength is recorded in centiNewtons ("cN").
  • MMAO refers to modified a triisohutylaluminum modified methj lalumoxane available commercially from Akzo-Noble Corporation.
  • T he preparation of catalyst (Bl) is conducted as follows. a) (3.00 g) is added to 10 mL of isopropviamine. The solution rapidly turns bright After stirring at ambient temperature lor 3 hours. are removed under v acuum Io ⁇ ieid a bright cry stalline solid (97 percent ⁇ ieldj.
  • shuttling Agents I he shuttling agents empiovcd include diothv i/ ⁇ c ,,DF/. SA 1 1. ⁇ FFA. SA-tj,
  • i-butylaluminum bis(di(tritnethylsilyl)amide) S A8), n-octylaluminum di(pvridinc-2-methoxide) (SA9), bis(n-octadecyl)i-but ⁇ lalurainum (SAlO), i-butylaluminum bis(di(n-pentyl)atnide) (SAl 1), n-octylaluminum bis(2,6-di-t-butylphenoxide) (SA12), n- octylaluminum di(ethyl(l ⁇ naphthyl)amide) (SA 13), ethylalumii ⁇ im bis(t- butyldimethylsiloxide) (SAl 4), ethylaluminum di(bis(trimethylsilyl)amide) (SA15), ethylaluminum bis(2.3»6,7-di
  • Polymerizations are conducted using a high throughput, parallel polymerization reactor (PPR) available from Symyx Technologies, Inc. and operated substantially according to US Patents No. 6.248,540. 6.030,917. 6,362,309. 6.306.658, and 6,316,663.
  • PPR parallel polymerization reactor
  • Ethylene copolymerizations are conducted at 130 0 C and 200 psi (1.4 MPa) with ethylene on demand using 1 ,2 equivalents of cocatalyst 1 based on total catalyst used (1.1 equivalents v ⁇ hen MMAO is present).
  • a series of polymerizations are conducted in a parallel pressure reactor (PPR) contained of 48 individual reactor cells in a 6 x 8 array that are fitted with a pre- weighed glass tube.
  • each reactor cell The working volume in each reactor cell is 6000 ⁇ L.
  • Each ceil is temperature and pressure controlled with stirring provided by individual stirring paddles.
  • the monomer gas and quench gas are plumbed directly into the PPR unit and controlled by automatic valves.
  • Liquid reagents are robotically added to each reactor cell by syringes and the reservoir solvent is mixed alkanes. The order of addition is mixed aikanes sohent (4 ml), ethylene, 1-octene comonomer (1 ml), cocatalyst 1 or cocatalyst KMM AO mixture, shuttling agent, and catalyst or cataly st mixture.
  • Examples 1-4 demonstrate the s ⁇ nthesis of linear block copolymers by the present invention as evidenced by the formation of a very narrow MWD. essentially monomodal copolymer when DEZ is present and a bimodal. broad molecular weight distribution product (a mixture of separately produced polymers) in the absence of DEZ. Due to the fact that Catalyst (Al ) is known to incorporate more octene than Catalyst (B I ), the different blocks or segments of the resulting copolymers of the invention are distinguishable based on branching or density.
  • the polymers produced according to the invention have a relatively narrow polydispersity (MwMn) and larger block-copoiymer content (irimer, tetramer, or larger) than polymers prepared in the absence of the shuttling agent.
  • MwMn polydispersity
  • block-copoiymer content irimer, tetramer, or larger
  • Further characterizing data for the polymers of Table 1 are determined by reference to the figures. More specifically DSC and ATREF results show the following: [0147J
  • the DSC curve for the polymer of example 1 shows a 1 15.7°C melting point (Tm) with a heat of fusion of 158.1 J g.
  • the corresponding CRYSTAF curve shows the tallest peak at 34.5 0 C with a peak area of 52.9 percent.
  • the difference between the DSC Tm and the rcry staf is 81.2°C.
  • the DSC curs e for the polymer of example 2 shows a peak with a 109.7 0 C melting point (Tm) with a heat of fusion of 214.0 J g.
  • the corresponding CRYSTAF curve shows the tallest peak at 46.2°C with a peak area of 57.0 percent.
  • the difference between the I)SC Fm and the Fcn ⁇ uf is 63.5°C.
  • the DSC cur ⁇ e for the polymer of example 3 shows a peak with a 120.7 0 C melting point (Tm) with a heat of fusion of 160.1 J/g.
  • the corresponding CRYSTAF curve shows the tallest peak at 66.1°C with a peak area of 71.8 percent.
  • the difference between the DSC Tm and the Tcrystaf is 54.6°C.
  • the DSC curve for the polymer of example 4 shows a peak with a 104.5 0 C melting point (Tm) with a heat of fusion of 170.7 J/g.
  • the corresponding CRYSTAF curve shows the tallest peak at 30 0 C with a peak area of 18.2 percent.
  • the DSC curve for comparative A shows a 90.0 0 C melting point (Tm) with a heat of fusion of 86.7 J/g.
  • the corresponding CRYST ⁇ F curve shows the tallest peak at 48.5°C with a peak area of 29.4 percent. Both of these values are consistent with a resin that is low in density.
  • the difference between the DSC Tm and the Tcrystaf is 41.8 0 C.
  • the DSC curve for comparative B shows a 129.8°C melting point (Tm) with a heat of fusion of 237.0 J/g.
  • the corresponding CRYSTAF curve shows the tallest peak at 82.4 0 C with a peak area of 83.7 percent.
  • the difference between the DSC Tm and the Tcrystaf is 47.4°C.
  • the DSC curve for comparative C shows a 125.3 Q C melting point (Tm) with a heat of fusion of 143.0 J/g.
  • the corresponding CRYST ⁇ F curve shows the tallest peak at 81.8 0 C with a peak area of 34.7 percent as well as a lower crystalline peak at 52.4 0 C.
  • the separation between the two peaks is consistent with the presence of a high crystalline and a low crystalline polymer.
  • the difference between the DSC Tm and the Tcrystaf is 43.5°C.
  • Continuous solution polymerizations are carried out in a computer controlled autoclave reactor equipped with an internal stirrer.
  • Purified mixed alkanes solvent (Isopar 1 M E available from ExxonMobil Chemical Company ), ethylene at 2.70 ib& hour (1.22 kg/hour).
  • 1-octene. and hydrogen (where used) are supplied to a 3.8 L reactor equipped with a jacket for temperature control and an internal thermocouple.
  • the sohent feed to the reactor is measured by a mass-flow controller.
  • a variable speed diaphragm pump controls the solvent il ⁇ w rate and pressure to the reactor.
  • a side stream is taken to prov ide flush flows for the catalyst and eocatahst I injection lines and the reactor agitator.
  • I hcse flows are measured by Micro-Motion mass flow meters and controlled b> control valves or by the manual adjustment of needle valves.
  • the remaining sohent is combined with l ⁇ octene, ethy iene, and hydrogen (where used) and fed to the reactor.
  • ⁇ mass flow controller is used to deliver hydrogen to the reactor as needed.
  • the temperature of the solvent/monomer solution is controlled by use of a heat exchanger before entering the reactor. This stream enters the bottom of the reactor.
  • the catalyst component solutions are metered using pumps and mass flow meters and are combined with the catalyst flush solvent and introduced into the bottom of the reactor.
  • the reactor is run liquid-full at 500 psig (3.45 MPa) with vigorous stirring.
  • Product is removed through exit lines at the top of the reactor. All exit lines from the reactor are steam traced and insulated.
  • Polymerization is stopped by the addition of a small amount of water into the exit line along with any stabilizers or other additives and passing the mixture through a static mixer.
  • the product stream is then heated by passing through a heat exchanger before devolatilization.
  • the polymer product is recovered by extrusion using a devolatilizing extruder and w r ater cooled pelletizer. Process details and results are contained in Table 2. Selected polymer properties are provided in Table 3.
  • the DSC cur ⁇ e for the pohmer of example 5 shows a peak with a 119.6 0 C melting point (Tm) with a heat of fusion of 60.0 J/g.
  • the corresponding CRYSTAF curve shows the tallest peak at 47.6°C with a peak area of 59.5 percent, f he delta between the DSC
  • Tm and the Tcrystaf is 72.0 0 C.
  • the DSC curve for the polymer of example 6 shows a peak with a 115.2 0 C melting point (Tm) with a heat of fusion of 60.4 J 'g.
  • I he corresponding CRYSTAF curve shows the tallest peak at 44.2°C with a peak area of 62.7 percent.
  • Tm and the Tcrystaf is 71.0 0 C.
  • the DSC curve for the polymer of example 7 shows a peak with a 121.3 0 C melting point with a heat of fusion of 69.1 J''g.
  • the corresponding CRYSlAF curve shows the tallest peak at 49.2°C with a peak area of 29.4 percent.
  • the delta between the DSC Tm and the Tcrystaf is 72.1 0 C.
  • the DSC curve for the polymer of example 8 shows a peak with a 123.5 0 C melting point (Tm) with a heat of fusion of 67.9 J/g.
  • the corresponding CRYSTAF curve shows the tallest peak at 80.1 0 C with a peak area of 12.7 percent.
  • Tm and the Tcrystaf is 43.4°C.
  • the DSC curve for the polymer of example 9 shows a peak with a 124.6 0 C melting point (Tm) with a heat of fusion of 73.5 J/g. 1 he corresponding CRYSTAF curve shows the tallest peak at 80.8 0 C with a peak area of 16.0 percent.
  • Tm 124.6 0 C melting point
  • he corresponding CRYSTAF curve shows the tallest peak at 80.8 0 C with a peak area of 16.0 percent.
  • Tm and the 1 crystal * is 43.8 0 C.
  • Tm and the Tcrystaf is 74.7 0 C.
  • lhe DSC curve for the pohmer of example 1 1 shows a peak with a 1 13.6 0 C melting point (Tm) with a heat of fusion of 70.4 J g.
  • the corresponding CRYS TAF eurv e shows the tallest peak at 39.6°C with a peak area of 25.2 percent, fhe delta between the DSC i m and the Fcry ->tai is 74.1 2 C.
  • the DSC for the polymer of example 14 shows a peak with a 120.8 0 C melting point (Tm) with a heat of fusion of 127.9 J/g.
  • the corresponding CRYSTAF curve shows the tallest peak at 72.9 0 C with a peak area of 92.2 percent.
  • the delta between the DSC Tm and the Tcr>staf is 47.9°C.
  • the DSC curve for the polymer of example 15 shows a peak with a 1 14.3 0 C melting point (Tm) with a heat of fusion of 36.2 J/g
  • the corresponding CRYSTAF curve shows the tallest peak at 32.3 0 C with a peak area of 9.8 percent.
  • the delta between the DSC Tm and the Tcrystaf is 82.0 0 C. fO167
  • the DSC curve for the polymer of example 16 shows a peak with a 1 16.6 °C melting point (Tm) with a heat of fusion of 44.9 J/g
  • the corresponding CRYSTAF curve shows the tallest peak at 48.0 0 C with a peak area of 65.0 percent.
  • the delta between the DSC Tm and the Tcrystaf is 68.6°C.
  • the DSC curve for the polymer of example 17 shows a peak with a 116.0 0 C melting point (Tm) with a heat of fusion of 47.0 J'g,
  • the corresponding CRYSTAF curve shows the tallest peak at 43.1 0 C with a peak area of 56.8 percent.
  • the deita between the DSC Tm and the Tcrystaf is 72.9°C.
  • the DSC curve for the polymer of example 18 shows a peak with a 120.5 0 C melting point ( Fm) with a heat of fusion of 141.8 J,g.
  • the corresponding CRYSTAF curve shows the tallest peak at 70.0 0 C with a peak area of 94.0 percent.
  • the delta between the DSC Tm and the Tcrystaf is 50.5 0 C.
  • the DSC curve for the poh mer of example 19 shows a peak with a 124.8 0 C melting point (Tm) with a heat of fusion of 174.8 J g.
  • the corresponding CRYS FAF curve shows the tallest peak at 79.9 0 C with a peak area of 87.9 percent.
  • the delta between the DSC I m and the Fcr> staf is 45.0 0 C.
  • the corresponding CRYSlAt cu ⁇ e shows the tallest peak at 79.3°C with a peak area of 94.6 percent. Both of these ⁇ allies are consistent with a resin that is high in density.
  • the delta between the DSC Tm and the Tcrystaf is 44.6°C.
  • the DSC curve for the polymer of comparative F shows a peak with a 124.8 0 C melting point (Tm) with a heat of fusion of 90.4 Tg.
  • the corresponding CRYSTAF curve shows the tallest peak at 77.6°C with a peak area of 19.5 percent. The separation between the two peaks is consistent with the presence of both a high crystalline and a low crystalline polymer.
  • the delta between the DSC Tm and the Tcrystaf is 47.2°C.
  • Comparative G* is a substantially linear ethylene/ 1-octene copolymer (AFHNI FYD, available from The Dow Chemical Company), Comparative H* is an elastomeric.
  • Comparative 1 is a substantially linear ethylene' 1-octene copolymer (AFFINl IY ⁇ PL1840, available from The Dow Chemical Company)
  • Comparative J is a hydrogenated sty rene, butadiene styrene triblock copolymer (KRATONTM G1652, available from KRA ' ION Polymers).
  • Comparative K is a thermoplastic vulcanizate (TPV. a poly olefin blend containing dispersed therein a cross linked elastomer). Results are presented in I able 4. Table 4 High Temperature Mechanical Properties
  • Comparative F (which is a physical blend of the two po ⁇ >mers resulting from simultaneous polymerizations using catalyst Al and B l) has a 1 mm penetration temperature of about 70 0 C, while Examples 5-9 have a 1 mm penetration temperature of 100 0 C or greater. Further, examples 10-19 all have a 1 mm penetration temperature of greater than 85 0 C, with most having 1 mm TMA temperature of greater than 90 0 C or even greater than 100 0 C. This shows that the novel polymers have better dimensional stability at higher temperatures compared to a physical blend. Comparative J (a commercial SEBS) has a good 1 mm TMA temperature of about 107 0 C.
  • Comparative G of similar density has a storage modulus ratio an order of magnitude greater (89). It is desirable that the storage modulus ratio of a polymer be as close to 1 as possible. Such polymers will be relative! ⁇ unaffected by temperature, and fabricated articles made from such polymers can be usefully empkned over a broad temperature range, 1 his feature of low storage modulus ratio and temperature independence is particularly useful in elastomer applications such as in pressure sensith e adhesive formulations.
  • Example 5 has a pellet blocking strength of 0 MPa, meaning it is free flowing under the conditions tested, compared to Comparathes F and G which show considerable blocking. Blocking strength is important since bulk shipment of polymers having large blocking strengths can result in product clumping or sticking together upon storage or shipping, resulting in poor handling properties.
  • High temperature (70 0 C) compression set for the inventh e polymers is generally good, meaning generally less than about 80 percent, preferably less than about 70 percent and especially less than about 60 percent. In contrast.
  • Comparatives F, G, H and J all have a 70 0 C compression set of 100 percent (the maximum possible value, indicating no recovery). Good high temperature compression set (low numerical values) is especially needed for applications such as gaskets, window profiles, o-rings. and the like.
  • Table 5 shows results for mechanical properties for the new polymers as well as for various comparison polymers at ambient temperatures. It may be seen that the inventive polymers have very good abrasion resistance when tested according to ISO 4649, generally showing a volume loss of less than about 90 mm J . preferably less than about 80 mm', and especially less than about 50 m ⁇ v ⁇ In this test, higher numbers indicate higher volume loss and consequently lower abrasion resistance.
  • Tear strength as measured by tensile notched tear strength of the inventive polymers is generally 1000 mJ or higher, as shown in Table 5. Tear strength for the inventive polymers can be as high as 3000 m J. or even as high as 5000 mJ. Comparative polymers generally have tear strengths no higher than 750 mj.
  • Table 5 also shows that the polymers of the invention have better retractive stress at 150 percent strain (demonstrated by higher retractive stress values) than some of the comparative samples.
  • Comparative Examples F, G and H have retractive stress value at 150 percent strain of 400 kPa or less, while the inventive polymers have retractive stress values at 150 percent strain of 500 kPa (Ex. 1 1 ) to as high as about 1 100 kPa (Ex, 17).
  • Polymers having higher than 150 percent retractive stress values would be quite useful for elastic applications, such as elastic fibers and fabrics, especially nonwoven fabrics. Other applications include diaper, hygiene, and medical garment waistband applications, such as tabs and elastic bands.
  • Table 5 also shows that stress relaxation (at 50 percent strain) is also improved (less) for the inventive polymers as compared to, for example. Comparative Cr. Lower stress relaxation means that the polymer retains its force better in applications such as diapers and other garments where retention of elastic properties over long time periods at body temperatures is desired.
  • optical properties reported in Table 6 are based on compression molded films substantially lacking in orientation. Optical properties of the polymers may be varied over wide ranges, due to variation in crystallite size, resulting from variation in the quantity of chain shuttling agent employed in the polymerization.
  • Any ether remaining in the extractor is returned to the flask, fhe ether in the flask is evaporated under vacuum at ambient temperature, and the resulting solids are purged dry with irirogen. Am residue is transferred to a weighed bottle ttMiig succc ⁇ si' e washes of hexane. The combined hexane washes are then evaporated with another nitrogen purge, and the residue dried under vacuum overnight at 4O 0 C. Any remaining ether in the extractor is. purged dry with nitrogen.
  • a second clean round bottom flask charged with 350 mL of hexane is then connected to the extractor.
  • the hexane is heated to reflux with stirring and maintained at reflux for 24 hours after hexane is first noticed condensing into the thimble. Heating is then stopped and the flask is allowed to cool. Any hexane remaining in the extractor is transferred back to the flask.
  • the hexane is removed b> evaporation under vacuum at ambient temperature, and any residue remaining in the flask is transferred to a weighed bottle using successive hexane washes.
  • the hexane in the flask is evaporated by a nitrogen purge, and the residue is vacuum dried overnight at 40 0 C.
  • the wMct the LaIaI) St 1 and terminates the poh meri/ation reactions 1 he post reactor solution h ihen heated in preparation tor a two-stage devitalization. I he soh ent and unreacted monomers are removed during the de ⁇ olatization process.
  • the polymer melt is pumped to a die for underwater pellet cutting.
  • Continuous solution polymerizations are carried out in a computer controlled autoclave reactor equipped with an internal stirrer.
  • Purified mixed alkanes solvent IsoparTM E available from ExxonMobil Chemical Company
  • ethylene at 2.70 lbs/hour (1.22 kg/hour) 1-octene, and hydrogen (where used) are supplied to a 3.8 L reactor equipped with a jacket for temperature control and an internal thermocouple.
  • the solvent feed to the reactor is measured by a mass-flow controller.
  • a variable speed diaphragm pump controls the solvent flow rate and pressure to the reactor. ⁇ t the discharge of the pump, a side stream is taken to provide flush flows for the catalyst and cocatalyst injection lines and the reactor agitator.
  • the remaining solvent is combined with 1-octene, ethylene, and hydrogen (where used) and fed to the reactor.
  • a mass flow controller is used to deliver hydrogen to the reactor as needed.
  • the temperature of the solvent/monomer solution is controlled by use of a heat exchanger before entering the reactor. This stream enters the bottom of the reactor.
  • the catalyst component solutions are metered using pumps and mass flow meters and are combined with the catalyst Hush solvent and introduced into the bottom of the reactor.
  • the reactor is run liquid-full at 500 psig (3.45 MPa) with v igorous stirring. Product is removed through exit lines at the top of the reactor.
  • All exit lines from the reactor arc steam traced and insulated. Polymerization is stopped by the addition of a small amount of water into the exit line along with any stabilizers or other additives and passing the mixture through a static mixer, The product stream is then heated by passing through a heat exchanger before devolatili/ation. The polymer product is recovered by extrusion using a de volatilizing extruder and water cooled pelletizer.
  • inventive examples 19F and 19G show low immediate set of around 65 70 % strain after 500% elongation.
  • Examples 20 and 21 fO191
  • the interpohmer of Examples 20 and 21 were made In a substantially similar manner as Examples 19A-J above with the polymerization conditions shown in Table 1 1 below.
  • the polymers exhibited the properties shown in Table 10.
  • Table 10 also shows any additives to the polymer.
  • Irganox 1010 is TetrakismethyIene(3.5-di-t-butyl-4- hydroxyh)droeinnarnaie)methane.
  • Irganox 1076 is Octadecyl-3-(3'.5'-di-t-buty ⁇ -4'- hydroxyphenyl)propionate.
  • Irgafos 168 is Tris ⁇ 2,4-di-l-butylphenyl)phosphite.
  • Chimasorb 2020 is 1 ,6-lIexanedia.mine, N,N " -bis(2.2.6,6-tetramethyl ⁇ 4-piperidiny ⁇ )- polj mer with 2J.6-trichloro-1.3.5-iriazine. reaction products with, N -butyl- 1- butanamine and N-butyl-2.2,6,6-tetramethy]-4-piperidinamine.
  • the present in ⁇ ent ⁇ on relates to dyed fabrics suitable for textile articles such as shirts, pants, socks, swimsuits. etc.
  • the fabrics may be made in am manner but typically are either woven or knit.
  • Woven fabrics of the present invention are typically characterized by a stretch of at least about about 10 percent measured according to ASTM D3107 whereas knit fabrics of the present invention are typically characterized by a stretch of at least about 30 percent measured according to ASTM D2594.
  • the dyed fabrics are usually comprised of one or more elastic fibers wherein the elastic fibers comprise the reaction product of at least one ethylene olefin block polymer and at least one suitable crosslinking agent.
  • crosslinking agent is any means which cross-links one or more, preferably a majority, of the fibers.
  • crosslinking agents may be chemical compounds but are not necessarily so.
  • Crosslinking agents as used herein also include eiectron-beam irradiation, beta irradiation, gamma irradiation, corona irradiation, silanes, peroxides, ailyl compounds and L 1 V radiation with or without crosslinking catalyst.
  • U.S. Patents No. 6.803,014 and 6,667.351 disclose electron-beam irradiation methods that can be used in embodiments of the im ention.
  • the percent of cross-linked polvmer is at least about 5 percent, preferably at least about 10, more preferably at least about 15 weight percent to about at most 75, preferably at most 65. preferably at most about 50 percent, more preferably at most about 40 percent as measured by the weight percent of gels formed according to the method described in Example 25.
  • the fibers typical!) a filament elongation to break of greater than about 200 o/ o. preferably greater than about 210%, preferably greater than about 220%. preferahh greater than about 230%, preferably greater than about 240%. preferabh greater than about 250%. preferably greater than about 260%. preferabh greater than about 270%. preferabh greater than about 2$0%. and ma> be as high as 600% according ro AS FM D2653-01 * elongation at first filament break test).
  • the fibers of the present imention are further characterized ing 1 1 I ratio of load at 200%
  • the poiyoiefin may be selected from any suitable ethylene olefin block polymer.
  • a particularly preferable olefin block polymer is an ethylencAx-olefin interpolymer, wherein the ethylenes-olefin interpol ⁇ mer has one or more of the following characteristics before crosslinking:
  • ( 1 ) an average block index greater than zero and up to about 1.0 and a molecular weight distribution, Mw-Mn, greater than about 1.3: or
  • an Mw 7 Mn from about 1.7 to about 3.5. and is characterized by a heat of fusion, ⁇ l in J'g. and a delta quantity, AT. in degrees Celsius defined as the temperature difference between the tallest DSC peak and the tallest CRYS TAF peak, w herein the numerical ⁇ alues of A l and AH have the following relationships:
  • the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSlAF peak, then the CRYSTAF temperature is 3O 0 C; or
  • (6) a molecular fraction which elutes between 4O 0 C and 130 0 C when fractionated using TREF, characterized in that the fraction has a molar comonomer content of at least 5 percent higher than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, wherein said comparable random ethylene interpolymer has the same comonomer(s) and has a melt index, density, and molar comonomer content (based on the whole polymer) within 10 percent of that of the ethylene/ ⁇ -olctln interpolymer; or
  • the fibers may be made into any desirable si?e and cross-sectional shape depending upon the desired application. For many applications approximately round cross-section is desirable due to its reduced friction. However, other shapes such as a trilobal shape, or a flat (i.e.. "ribbon” like) shape can also be employed. Denier is a textile term which is defined as the grams of the fiber per 9000 meters of that fiber's length. Preferred denier si/es depend upon the type of fabric and desired applications. Typically, knit fabrics comprise a majority of the fibers ha ⁇ ing a denier from at least about 1, preferably at least about 20. preferably at least about 50.
  • the fiber take any suitable form including a staple fiber or binder fiber.
  • Typical examples may include a homofil fiber, a bicomponent fiber, a melthlown fiber, a me ⁇ tspun fiber, or a spunbond fiber
  • a bicomponent fiber it may have a sheath-core structure: a sea-island structure; a side-by -side structure: a matrix-fibril structure: or a segmented pie structure.
  • conventional fiber forming processes ma> be employed to make the aforementioned fibers. Such processes include those described in, for example. U.S. Patents No. 4.340,563; 4.663,220; 4,668.566; 4,322,027: and 4,413,1 10).
  • the fibers may be made to facilitate processing and unwind the same as or better from a spool than other fibers.
  • Ordinary fibers when in round cross section often fail to provide satisfactory unwinding performance due to their base polymer excessive stress relaxation. This stress relaxation is proportional to the age of the spool and causes filaments located at the very surface of the spool to lose grip on the surface, becoming loose filament strands. Later, when such a spool containing conventional fibers is placed over the roils of positive feeders, i.e. Memminger-IRO, and starts to rotate to industrial speeds, i.e. 100 to 300 rotations'minutc.
  • Another advantage of the fibers is that defects such as fabric faults and elastic filament or fiber breakage may be equivalent or reduced as compared to conventional fibers. That is, use of the above fibers may reduce buildup of fiber fragments on a needle bed - a problem that often occurs in circular knit machines when polymer residue adheres to the needle surface. Thus, the fibers maj reduce the corresponding fabric breaks caused by the residue when the fibers are being made into. e.g. fabrics on a circular knitting machine.
  • the fibers may be knitted in circular machines where the elastic guides that drive the filament all the vun from -pool to the ncx-dks are stationary such as ceramic and meulfk In contrast, some come ⁇ tiona!
  • ⁇ V elastic olefin fibers require that these guides be made of rotating elements such as pullejs as to minimize friction as machine parts, such as evelets. are heated up so that machine stops or filament breaks could be avoided during the circular knitting process. That is. the friction against the guiding elements of the machine is reduced by using the inventive fibers. Further information concerning circular knitting is found in. for example, Bamberg Meisenbach. "Circular Knitting: Technology 1 Process, Structures, Yarns, Quality ", 1995. incorporated herein by reference in its entirety. Additives
  • Antioxidants e.g., IRGAFOS® 168, IRGANOX® 1010, IRGANOXf) 3790. and C ⁇ IIMASSORB® 944 made by Ciba Geigy Corp., may be added to the ethylene polymer to protect against undo degradation during shaping or fabrication operation and/or to better control the extent of grafting or crosslmking (i.e., inhibit excessive gelation).
  • In-process additives e.g. calcium stearate, water, fluoropolymers, etc., may also be used for purposes such as for the deactivation of residual catalyst and/or improved processability.
  • TINUVIN % 770 (from Ciba-Geigy) can be used as a light stabilizer.
  • the copolymer can be filled or unfilled. If filled, then the amount of filler present should not exceed an amount that would adversely affect either heat- resistance or elasticity at an elevated temperature. If present, typically the amount of filler is between 0.01 and 80 wt % based on the total weight of the copoly mer (or if a blend of a copolymer and one or more other polymers, then the total weight of the blend).
  • Representative fillers include kaolin clay, magnesium hydroxide, zinc oxide, silica and calcium carbonate.
  • the filler is coated with a material that will pre ⁇ ent or retard any tendency that the filler might otherwise have to interfere with the crosslinking reactions. Stearic acid is illustrative of such a filler coating.
  • spin finish formulations can be used, such as metallic soaps dispersed in textile oils (see for example U.S. Patent No. 3.039.895 or L ' . S. Patent No. 6.652.599), surfactants in a base oil (sec for example L " S publication 20U 1 0024052 ⁇ and poh alkv Kiloxanct f -.ec for example I .S. Patent ⁇ o, 3.296.063 or U.S. Patent ⁇ o, 4 ⁇ ) 99J 20 >.
  • I " .S. Patent Application Xo. 10/933.721 discloses spin finish compositions that can also be used.
  • the present invention is directed to improved. dyed textile articles comprising an olefin block copolymer.
  • textile articles includes fabric as well as articles, i.e., garments, made from the fabric including, for example, clothing and other items in need of coloring.
  • Bv knitting it is meant intertwining yarn or thread in a series of connected loops either by hand, with knitting needles, or on a machine.
  • the present in ⁇ ention may be applicable to any type of knitting including, for example, warp or weft knitting, flat knitting, and circular knitting. Particularly preferred warp knits include tricot and raschel while preferred weft knits include circular, flat, and seamless.
  • the invention is particularly advantageous when employed in circular knitting, i.e., knitting in the round, in which a circular needle is employed.
  • the present invention may also be applicable to any type of woven fabric.
  • the dyed fabrics of the present invention preferably comprise one or more elastic fibers wherein the elastic fibers comprise the reaction product of at least one ethylene olefin block polymer and at least one crosslinking agent wherein the ethylene olefin block polymer is an ethy lenes-olefin interpolymer, wherein the ethylene/ ⁇ - olefin interpolymer has one or more of the following characteristics prior to crosslinking:
  • the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 3O 0 C; or
  • an elastic recovery, Re in percent at 300 percent strain and 1 cycle measured with a compression-molded film of the eth>lene/ ⁇ -o ⁇ efin interpolymer, and has a density, d, in grams/cubic centimeter, wherein the numerical values of Re and d satisfy the following relationship when ethylene/ ⁇ -olefm interpohmer is substantially free of a cross-linked phase:
  • (6) a molecular fraction which elutes between 40 0 C and 130 0 C when fractionated using TREF, characterized in that the fraction has a molar comonomer content of at least 5 percent higher than that of a comparable random ethylene interpolymer fraction eiuting between the same temperatures, wherein said comparable random ethylene interpolymer has the same comonomer(s) and has a melt index, density, and molar comonomer content (based on the whole polymer) within 10 percent of that of the ethylene, ⁇ -olefin interpolymer; or
  • the ethylene/a-olefm interpolymer may be in the form of a fiber and may be blended with another suitable polymer, e.g. polyolefins such as random ethylene copolymers.
  • polyolefins such as random ethylene copolymers.
  • HDPE high density polyethylene
  • LLDPE low density polyethylene
  • LDPE low density polyethylene
  • ULDPE polypropylene homopolymers. copolymers, plastomers and elastomers, lastol, a polyamide. etc.
  • the ethyiene/ ⁇ -olefin interpol>mer of the fabric may have any density but is usually at least about 0.85 and preferably at least about 0.865 g ⁇ cm 3 (ASTM D 792). Correspondingly, the density is usually less than about 0.93, preferably less than about 0.92 g/cm 3 (ASTM D 792).
  • the ethylene/ ⁇ -olefin interpolymer of the fabric is characterized by an uncrosslinked melt index of from about 0.1 to about 10 g/10 minutes. If crosslinking is desired, then the percent of cross-linked polymer is often at least 10 percent, preferably at least about 20, more preferably at least about 25 weight percent to about at most 90, preferably at most about 75, as measured by the weight percent of gels formed.
  • the fabrics often comprise another material selected from the group consisting of rayon, nylon, viscose, polyester such as microfiber polyester, polyamide. polypropylene, cellulose, cotton, flax, ramie, hemp, wool, silk, linen, bamboo, tencel, mohair, other natural libers, other svthetic fibers, and mixtures thereof.
  • the other material comprises the majority of the fabric. In such case it is preferred that the other material comprise from at least about 50, preferably at least about 60. preferably at least about 70, preferably at least about 80, sometimes as much as 90-95. percent by weight of the fabric.
  • the ethylene/ ⁇ -olefin interpolymer. the other material or both may be in the form of a fiber.
  • Preferred sizes include a denier from at least about 1. preferably at least about 20. preferably at least about 50. to at most about 180. preferably at most about 150, preferably at most about 100. preferably at most about 80 denier.
  • Particularly preferred circular knit fabrics comprise eth ⁇ lene, ⁇ -olefm interpolymer in the form of a fiber in an amount of from about 5 to about 20 percent (by weight) of the fabric.
  • Particular! ⁇ preferred warp knit fabrics comprise cthUene si-oleiln Inierpolymer in trie form of a fiber in an amount of from about 10 to about 30 percent (by weight) of the fabric in the form of a fiber.
  • Such warp knit and circular knit fabrics also comprise polyester or micro fiber polyester.
  • the fabric, particularly knit fabrics often less than about 5, preferably less than 4, preferably less than 3. preferably less than 2. preferably less than 1, preferably less than 0.5, preferably less than 0.25. percent shrinkage after wash according to AATCC 135 in either the horizontal direction, the vertical direction, or both. More specifically, the fabric (after heat setting) often has a dimensional stability of from about 7% to about +7%.
  • the fabrics often have less shrinkage after wash according to AATCC 135 IVAi than a comparable fabric of elastic fibers with a higher amount of crosslinking.
  • Knit fabrics can be made to stretch in two dimensions if desired by controlling the type and amount of ethyl enc/ ⁇ -ole fin interpolymer and other materials. Knit fabrics may sometimes be characterized by a stretch of at least about 30 percent measured according to ASTM D2594. Similarly, the fabric can be made such that the growth in the lengthwise and widthwise directions is less than about 7. preferably less than about 5. preferably less than about 4, preferably less than about 3, preferably less than about 2, preferably less than about 1. to as little as 0.5 percent according to ASTM D 2594. Using the same test (ASTM D 2594) the lengthwise growth at 60 seconds can be less than about 15. preferably less than about 12, preferably less than about 10, preferably less than about 8%.
  • the vvidthwise growth at 60 seconds can be less than about 20. preferably less than about 18, preferably less than about 16. preferably less than about 13%.
  • the widthwise growth can be less than about 10. preferably less than about 9, preferably less than about 8. preferably less than about 6% while the lengthwise growth at 60 minutes can be less than about 8. preferably less than about 7, preferably less than about 6, preferably less than about 5%. fhe lower growth described above allows the fabrics of the imention to be heat set at temperatures from less than about 180. preferably less than about 170. preferably less than about 160. preferably !cbs than about ⁇ 5 ⁇ ' C while still controlling
  • woven fabrics may be characterized by a stretch of at least about 10 percent measured according to ASTM D3107.
  • knit fabrics of the present invention can be made without a substantia! number of breaks and using a knitting machine comprising an eyelet feeder system, a pulley system, or a combination thereof.
  • a knitting machine comprising an eyelet feeder system, a pulley system, or a combination thereof.
  • the circular knitted stretch fabrics having improved moldability while having acceptable dimensional stability (lengthwise and widthwise), acceptable growth and shrinkage, the ability to be heat set at low temperatures while controlling size, low moisture regain can be made without significant breaks, with high throughput, and without derailing in a wide variety of circular knitting machines.
  • the dyed fabrics of the present invention may be made by virtually any dyeing process. For example, many useful techniques are described in Fundamentals of Dyeing and Printing, by Garry Mock, North Carolina State University 2002, ISBN 9780000033871.
  • One advantage of the fabrics of the present invention is that they may often be contacted with the dye at a temperature of at least about 130 0 C to produce a dyed fabric wherein the fabric exhibits a growth to stretch ratio of less than 0.5, preferably less than 0.4, preferably less than 0.35, preferably less than 0.3, preferably less than 0.25, preferably less than 0.2, preferably less than 0.15. preferably less than 0.1. preferably less than 0.05.
  • the resulting dyed fabrics of the present invention are often characterized by a color change of greater than or equal to about 3.0, preferably greater than or equal to about 3.5, more preferably greater than or equal to about 4.0 according to AATCC evaluation after a first wash by AATCC61-2003-2 A.
  • Another advantage is that the fabrics of the present invention may sometimes exhibit a color change of greater than or equal to about 2.5. preferably greater than or equal to about 3.0. more preferably greater than or equal to about 3.5 according to AATCC evaluation after a second wash by AA TCC61-2003-2 A. in essence this means that the dyed fabrics of the present invention may exhibit less fading when subjected to laundering than conventional dyed fabrics.
  • the dyed fabrics of the present invention are also characterized an advantageous color strength atter dy eing, i.e.. the fabrics arc darker ⁇ -ur example, the d ⁇ ed fabrics mav often be characterized bv a color -itremith after ⁇ x mu of greater than
  • the color is substantially retained e ⁇ en after a first and second wash.
  • the dyed fabrics may be characterized by a color strength after a first wash by AATCC61-2003-2 ⁇ that is at least about 90, preferably at least about 95, more preferabh at least about 97 percent of the color strength after dying wherein each color strength is measured with a spectrum photometer.
  • the dyed fabrics may sometimes also be characterized by a color strength after a second wash by A ⁇ TCC61-2003-2 ⁇ that is at least about 90. preferably at least about 92.5. more preferably at least about 94 percent of the color strength after dying wherein each color strength is measured with a spectrum photometer.
  • the reason the dyed fabrics of the present invention dye darker is due to the fibers of the olefin block polymer. That is the olefin block polymer fibers dye to a lesser extent allowing the other material to get darker. Also, a higher dyeing temperature can be employed with less fiber breakage when olefin block polymers are used as the fibers. In a similar manner it is believed that the reason the dyed fabrics fade less upon laundering is that the olefin block polymer fibers are not dyed to as great of an extent as fibers made with other polymers, ⁇ n this manner, the olefin block polymers cannot fade or bleed as much.
  • Example 22 Fibers of elastic ethylene/ ⁇ -olefin interpolymer
  • Example 23 Hard yarns of fibers jO219
  • One comparative example hard yarn employed 40 denier fibers of a random ethylene-octene copolymer made with a line speed of 450 m/min and the same 150 denier. 288 filament polyester fibers.
  • the random ethylene-octene copolymer had an average melt index of 3.0 g/1 Omin, a density of 0.875 g/cm3 and was crosslinked with a dosage of of 166.4 kGy irradiation as the crosslinking agent.
  • the second comparative example hard yarn was made with multi-filament fibers of Lycra rM 162 C polymer and the same 150 denier, 288 filament polyester fibers.
  • Clariant dyestuff Foron Black S-WF was used to d>e the fibers and fabrics into black.
  • the Lycra based fibers were dyed at 125 C C since this elastic fiber may undergo severe damage at higher temperatures.
  • the other two types of fibers were dyed at 135 °C.
  • the specimens of after dyeing, after 1 si reduction wash and after 2 nd reduction wash were collected for evaluation.
  • a lower grade indicates a bigger color change and therefore less colorfastness.
  • the specimens after dyeing, after l s! reduction wash and after 2 nd reduction wash were washed by AATCC 61 -2003-2 A and the color change before and after was measured.
  • Color staining is also based on the tesl of AATCC 61-20G3-2A.
  • a multi- fiber test fabric that consists of acetate, cotton, polyamide, acrylic and wool fiber, is attached to the specimen to wash.
  • the test grades 1 ⁇ 5 and a lower grade means heavier color staining. Textile industry practice is to use the grade result of poly amide as an indication of color staining.
  • the random cthvlene-oclene copolymer and olefin block polymer fiber shows lighter color staining.
  • the specimens are very similar after dyeing, after 1 st reduction wash and after 2 n ⁇ reduction wash.
  • the olefin block polymer fiber shows less dvestuff uptake that helps better colorfastness in micro fiber polyester fabric colorfastness.
  • TJ [0224] 7 able 13 shows the color strength (K/S) ⁇ aiue of micro fiber polyester fabric.
  • the higher value of K/ S represented darker color.
  • Witness micropoK ester fabrics with random ethy lene-octene copolymer and olefin block polymer fibers showed darker black compared with Lycra. While not wishing to be bound to any theory it is believed that this result is due to the higher dyeing temperature employed. There were no significant differences among the samples after dyeing, after F 1 reduction wash and after 2 nd reduction wash. However, the microfiber polyester of olefin block polymer can reach a darker color. Table 13 Color strength(K/S) value of fabrics
  • Table 14 shows the color change ⁇ alue of micro fiber polyester after dveing, after 1 st reduction wash and after 2" ⁇ reduction wash. The higher v alue means lighter color change. All specimens show good color change results. Table 14 Result of color change of micro polyester
  • Three single jersey knits are use in this test. They are micro fiber polyester hard jam knitted with 40 denier Lycra, 40 denier random ethylcne-octene copolymer and 40 denier olefin block polymer fiber. The knitting speed, elastic draft and the fabric weight of greige are given in Table 16.
  • Random ethy Iene-octene copolymer and olefin block polymer greige are scoured at 85 C C for 20 minutes, dried at 135 C C for 45 minutes, tensionless dryed at 130C for 60 minutes, set at 165 3 C for 120 seconds (15 yards per minute) at 20% overfeed, and finished.
  • the dyeing and reduction conditions are gh en in Figure 9 for random eih> Iene-octene eopoh mer and olefin block poly mer containing fabric I he s yera greige ⁇ d>ec a ⁇ 125 J and heat >et dl 185 C ' e * ' -'k ⁇ , u h hand i- ,,s. >'v_ Table 17 Fabric weight of various elastic fiber contented fabric
  • Table 18 shows the test result of AATCC 61 -2003-2 ⁇ .
  • random ethy lene- octene copolymer and olefin block polymer both have excellent performance in color change compared with Lycra 162 before or after heat setting. The reason is random ethylene-octene copolymer and olefin block polymer fiber were dyed at 135 ' C - the disperse dyestut ⁇ has better reaction in this temperature. In the dye lot of micro-fiber polyester/ Ly era, there is un-reacted disperse dyestuff because of low dyeing temperature that stained on fabric and bleeds out that makes specimen color fading during testing. Random ethylene-octene copolymer and OBC both has good color fastness to polyamide compared with Lycra. Lycra shows poor color fastness after heat setting. The reason is the disperse dyes migrated during 185 C high temperature heat setting.
  • Example 25 Varying Amounts of Fiber CrossHnking
  • the elastic ethylene/ ⁇ -olefin inlerpolymcr of Example 20 was used to make monofilament fibers of 40 denier having an approximately round cross-section. Before the fiber was made the following additives were added to the polymer: 7000 ppm PDMSO (polydimethyl siloxane). 3000 ppm CYANOX 1790 (1.3,5-tris-(4-t- butyl-3-hydroxv-2.6-dimethylbenzyl)-l,3,5-triazine-2.4,6-(l H,3H,5H)-trione.
  • the gel content versus the amount of irradiation is shown in Figure 1 1.
  • the gel content was determined by weighing out an approximately 25 mg fiber sample to 4 significant figure accuracy.
  • the sample is then combined with 7 ml xylene in a capped 2-dram vial.
  • the vial is heated 90 minutes at 125 0 C to 135°C. with inversion mixing (i.e. turning vial upside down) every 15 minutes, to extract essentially all the non-crosslinked polymer.
  • the xylene is decanted from the gel.
  • the gel is rinsed in the vial with a small portion of fresh xylenes.
  • the rinsed gel is transferred to a tared aluminum weighing pan.
  • the tared dish with gel is ⁇ acuum dried at 125 C C for 30 minutes to remo ⁇ e the xylene by evaporation.
  • the pan with dried gel is weighed on an analytical balance.
  • the gel content is calculated based on the extracted gel weight and original fiber weight.
  • Figure 1 i shows that as the e-beam dosage increases, lhe amount of ercss ⁇ king ( gel content ⁇ increases.
  • the precise relationship between the amount ofcrosslinking and e-beam dosage may be affected by a given polymer ' s properties, e.g.. molecular weight or melt index.

Abstract

Dyed fabric compositions have now been discovered that often have a balanced combination of desirable properties. The dyed fabric comprises one or more elastic fibers wherein the elastic fibers comprise the reaction product of at least one ethylene olefin block polymer and at least one crosslinking agent. Often the fabrics are characterized by a color change of greater than or equal to about 3.0 according to AATCC evaluation after a first wash by AATCC61-2003-2A.

Description

COLORFAST FABRICS AND GARMENTS OF OLEFIN BLOCK COMPOSITIONS
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001 j For purposes of United States patent practice, the contents of CS. Pro\ isional Application No. 60/885.202, filed January 16, 2007, is herein incorporated by reference in its entirety.
FIELD OF THE INVENTION
[0002 j This invention relates to dyed fabrics that are coiorfast.
BACKGROUND AND SUMMARY OF THE INVENTION
[0003] Many different materials have been used in making dyed fabrics for use in, for example, garments. It is often desirable that such fabrics have a combination of properties including one or more of the following: dimensional stability, heat-set properties, capability to be made stretchable in one or both dimensions, chemical, heat, and abrasion resistant, tenacity, etc. In addition, it is also often important that such dyed fabrics be able to hold color, e.g.. dve, longer and darker when subjected to laundering without significantly degrading one or more of the aforementioned properties. Further, increased throughput with reduced defects, e.g., fiber breakage, is somtimes desirable if the dyed fabric is, for example, a knitted fabric.
JG004J improved fabrics have now been discovered which often have a balanced combination of desirable properties including being able to be able to be colored darker and hold color, i.e.. coiorfast, with laundering. These compositions may also allow for improved processability in some applications. The fabric of the present invention is typically a knit or woven fabric comprising elastic fibers. Such knit fabrics include, for example, polyesters like microfiber poh esters. The elastic fibers often comprise the reaction product of at least one ethylene block polymer and at least one crosslinking agent. The fibers are characterized by an amount of crosslinking such that the fabric has the desired properties. The ethylene block poh met is usually
(A) an elhylene-'α-ϋlefm interpohmer. wherein the ethy lene α-oleiϊn interpohmer has one or more of the following characteristics:
„ ? . ( 1 ) an a\ erage block index greater than ^ero and up to about 1.0 and a molecular weight distribution. Mw, Mn. greater than about 1,3; or
(2) at least one molecular fraction which elutes between 4O0C and 130°C when fractionated using TREF, characterized in that the fraction has a block index of at least 0.5 and up to about 1 ; or
(3) an Mw 'Mn from about 1.7 to about 3.5. at least one melting point. Tm. in degrees Celsius, and a density, d, in grams/cubic centimeter, wherein the numerical values of Tm and d correspond to the relationship:
Tm > -2002.9 + 4538.5(d) - 2422.2(d)2; or
(4) an Mw7Mn from about 1.7 to about 3.5, and is characterized by a heat of fusion, ΔH in J/g, and a delta quantity, ΔT. in degrees Celsius defined as the temperature difference between the tallest DSC peak and the tallest CRYSTΛF peak, wherein the numerical values of ΔT and ΔH have the following relationships:
ΔT > -0.1299(ΔH) + 62.81 for ΔH greater than zero and up to 130 J/g,
ΔT > 48°C for ΔH greater than 130 J'g .
wherein the CRYSTΛF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the pohmer has an identifiable CRYS I AF peak, then the CRYS f AF temperature is 300C; or
(5) an elastic recovery, Re, in percent at 300 percent strain and 1 cycle measured with a compression-molded film of the ethylene α-oiefm interpolymer. and has a density, d, in grams cubic centimeter, wherein the numerical \atues of Re and d satisfy the following relationship when ethylene α-oiefin interpolymer is substantially free of a cross- linked phase:
Re >1481-1629(d): or
(6) a molecular fraction which elutes between 40°C and 130"C when fractionated using FRl f . characterized in that the fraction has a molar eemonorner content of at least 5 percent higher than that of a comparable random ethylene interpohmer fraction elutmg between the s.anic temperature, wherein said comparable random ethy lene interpohmer has lhe same comonomer(s) and has a melt index, density, and molar comononier content (based on the whole polymer) within 10 percent of that of the ethylene/α- olefin inteφolymer; or
(7) a storage modulus at 25 0C. G'(25 0C), and a storage modulus at 100 0C. G'OOO 0C), wherein the ratio of G*(25 0C) to G'{ 100 0C) is in the range of about 1 :1 to about 9:1.
[0005] The ethylene/ α-olefin interpolymer characteristics (1) through (7) above are given with respect to the cthylene/α-olcfin interpolymer before any significant crosslinking, i.e.. before crosslinking. The ethylene/α-olefin inteφoiymers useful in the present invention are usually crosslinked to a degree to obtain the desired properties. By using characteristics (1 } through (7) as measured before crosslinking is not meant to suggest that the inteφolymer is not required to be crosslinked - only that the characteristic is measured with respect to the interpolymer without significant crosslinking. Crosslinking may or may not change each of these properties depending upon the specific polymer and degree of crosslinking. The dyed fabrics of the present invention may often be characterized by a color change of greater than or equal to about 3.0 according to AATCC evaluation after a first wash by AATCC 61 -2003- 2A, The dyed fabrics of the present invention may often be characterized by a color strength after dying of greater than or equal to about 600 as measured with a spectrum photometer.
BRIEF DESCRIPTION OF THE DRAWINGS
|0006j Figure 1 shows the melting point/density relationship for the inventive polymers
(represented by diamonds) as compared to traditional random copolymers (represented by circles) and Ziegler-Natta copolymers (represented by triangles).
[0007] Figure 2 show s plots of delta DSC-C RYSTΛF as a function of DSC Melt
Enthalpy for various polymers. The diamonds represent random ethylene, octene copolymers: the squares represent polymer examples 1 -4: the triangles represent polymer examples 5-9: and the circles represent polymer examples 10-19. The "X" symbols represent polymer examples A+-F*.
10008] Figure 3 shows the effect of density on elastic recovery for unoriented films made from inventive inteφoly mers( represented by the squares and circles) and traditional u poly mers (repicscπted b\ lhe triangles which are v arious M-FINI l \ l Vl polymers (av ailable from The Dow Chemical Company )). The squares represent inventive ethy lene/butene copolymers; and the circles represent in\renti\e ethylene 'octene copolymers.
100091 Figure 4 is a plot of octene content of TRKF fractionated ethylene/ 1 -octene copolymer fractions versus TREF elution temperature of the fraction for the polymer of
Example 5 (represented by the circles) and eomparati\e polymers E and F (represented by the
"X" symbols). The diamonds represent traditional random ethylene octene copolymers. jϋϋlO] Figure 5 is a plot of octene content of TREF fractionated ethylene* 1 -octene copolymer fractions versus T REF elution temperature of the fraction for the polymer of
Example 5 (curve 1) and for comparative F (curve 2). The squares represent Example F*: and the triangles represent Example 5.
[0011] Figure 6 is a graph of the log of storage modulus as a function of temperature for comparative ethylene/ 1 -octene copolymer (curve 2) and propylene/ ethylene- copolymer
(curve 3) and for two ethylene/1 -octene block copolymers of the invention made with differing quantities of chain shuttling agent (curves 1).
[0012] Figure 7 shows a plot of TMA (1 mm) versus flex modulus for some imentive polymers (represented by the diamonds), as compared to some known polymers. The triangles represent various Dow VERSIFY'M polymers( available from The Dow Chemical
Company); the circles represent various random ethylene, sty rene copolymers; and the squares represent various Dow AFFINITY™ polymers(avaiiable from The Dow Chemical
Company).
[0013] Figure 8 shows photos of a lab dyeing machine.
[0014] Hgure 9 shows a dyeing and reduction wash process.
DETAILED DESCRIP TION OF THE INVENTION
General Definitions
[0015] '"Fiber" means a material in
Figure imgf000006_0001
the length to diameter ratio is greater than about 10. Fiber is typically classified according to its diameter. Filament fiber is generally defined as having an individual fiber diameter greater than about 15 denier, usually greater than about 30 denier per filament. Fine denier fiber generally refers to a fiber hav ing a diameter less than about 15 denier per filament. Microdenier fiber is generally defined as fiber ha\ ipg a diameter les1- than about !0() microns denier per filament fθβlό] *i ilament Il be-" or "monofilament fiber" mean*> a continuous strand of mαteπai o! indefinite ύ c . net predetermined j length, a, opposed lo a "staple fiber*" which is a discontinuous strand of material of definite length (i.e.. a strand which has been cut or otherwise divided into segments of a predetermined length).
[0017] "Elastic" means that a fiber will recover at least about 50 percent of its stretched length after the first pull and after the fourth to 100% strain (doubled the length). Elasticity can also be described by the "permanent set" of the fiber. Permanent set is the comerse of elasticity. A fiber is stretched to a certain point and subsequent!) released to the original position before stretch, and then stretched again. The point at which the fiber begins to pull a load is designated as the percent permanent set. "Elastic materials" are also referred to in the art as "elastomers'' and "elastomeric". Elastic material (sometimes referred to as an elastic article) includes the copolymer itself as well as, but not limited to, the copolymer in the form of a fiber, film, strip, tape, ribbon, sheet, coating, molding and the like. The preferred elastic material is fiber. The elastic material can be either cured or uncured. radiated or un-radiated, and/or crosslinked or uncrosslinked.
[0018] "Nonelastic material"" means a material, e.g., a fiber, that is not elastic as defined above.
[0019] "Homofil fiber" means a fiber that has a single polymer region or domain, and that does not ha\e any other distinct polymer regions (as do bicomponent fibers). [0020] "Bicomponent fiber" means a fiber that has two or more distinct polymer regions or domains. Bicomponent fibers are also know as conjugated or multicomponent fibers. The polymers are usually different from each other although two or more components may comprise the same polymer. 1 he polymers are arranged in substantially distinct /ones across the cross-section of the bicomponent fiber, and usually extend continuously along the length of the bicomponent fiber. The configuration of a bicomponent fiber can be, for example, a sheath/core arrangement (in which one polymer is surrounded by another), a side by side arrangement, a pie arrangement or an "islands-in-the sea" arrangement. Bicomponent fibers are further described in L.S. Patents No. 6.225.243. 6.140.442. 5,382.400. 5.336.552 and 5,108.820.
[0021] "Melfblown fibers" are fibers formed by extruding a molten thermoplastic polymer composition through a plurality of fine, usually circular, die capillaries as molten threads or filaments into converging high velocity gas streams {e.g air) which function to attenuate ihe threads or filament-, to reduced diameters. I he filaments or threads are carried
Figure imgf000007_0001
and deposited on α collecting surface to form a weϋ o( iandomh dispersed fibers with average diameters geneially ^mailer than I u microns. [0022] "Mcltspun fibers" are fibers formed by melting at least one polymer and then drawing the fiber in the melt to a diameter (or other cross-section shape) less than the diameter (or other cross-section shape) of the die.
{0023] ""Spunbond fibers" are fibers formed by extruding a molten thermoplastic pohmer composition as filaments through a plurality of fine, usually circular, die capillaries of a spinneret. The diameter of the extruded filaments is rapidly reduced, and then the filaments are deposited onto a collecting surface to form a web of randomly dispersed fibers with average diameters generally between about 7 and about 30 microns. [0024] "Nonwoven" means a web or fabric having a structure of individual fibers or threads which are randomly interlaid, but not in an identifiable manner as is the case of a knitted fabric. The elastic fiber in accordance with embodiments of the invention can be employed to prepare nonwoven structures as well as composite structures of elastic nonwoven fabric in combination with nonelastic materials.
[0025] "Yarn" means a continuous length of twisted or otherwise entangled filaments which can be used in the manufacture of woven or knitted fabrics and other articles. Yarn can be covered or uncovered. Covered yarn is yarn at least partially wrapped within an outer covering of another fiber or material, typically a natural fiber such as cotton or wool. [0026] "Polymer" means a polymeric compound prepared by polymerizing monomers, whether of the same or a different type, ϊ he generic term "polymer" embraces the terms "homopolymer," "copolymer." "terpolymcr" as well as "inierpolymer." [0027] "interpolymcr" means a polymer prepared by the polymerization of at least two different types oi monomers. I he generic term "inierpolymer" includes the term "copolymer" (which is usually employed to refer to a polymer prepared from two different monomers) as well as the term "terpolymer" (which is usually employed to refer to a polymer prepared from three different types of monomers). It also encompasses polymers made by polymerizing four or more types of monomers.
[0028] 1 he term "ethylene α-olefin interpoly mer" generally refers to polymers comprising ethy lene and an α -olefin having 3 or more carbon atoms. Preferably, ethylene comprises the majority mole fraction of the whole polymer, i e.. ethylene comprises at least about 50 mole percent of the whole polymer. More preferably ethy lene comprises at least about 60 mole percent, at least about 70 mole percent, or at least about 80 mole percent, with the substantial rern ameer ol ihe nholt puiymtr cumpπsing „1 leavi one other torπonυ'per thai is preferably an α-olefin
Figure imgf000008_0001
mg 3 or more carbon atυrrΛ ! or many ethy lent, octene copolymers, the preferred composition comprises an ethy lene content greater than about 80 mole percent of the whole polymer and an octene content of from about 10 to about 15. preferably from about 15 to about 20 mole percent of the whole pohmer. in some embodiments, the ethylene/ α-o Ie fin interpolymers do not include those produced in low yields or in a minor amount or as a by-product of a chemical process. While the ethylene'α- olefin interpolymers can be blended with one or more polymers, the as-produced ethylene 'α- olefin interpolymers are substantially pure and often comprise a major component of the reaction product of a polymerization process.
[0029] The ethylene/α-olcfln interpolymers comprise ethy lene and one or more copoiymerizabie α-olefm comonomers in polymerized form, characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical or physical properties. That is, the ethvlene/α-olefin interpolymers are block interpolymers, preferably multi-block interpolymers or copolymers. The terms "interpolymer" and "copolymer1" are used interchangeably herein. In some embodiments, the multi-block copolymer can be represented by the following formula:
(AB)n where n is at least 1, preferably an integer greater than I . such as 2. 3. 4, 5, 10, 15, 20. 30. 40, 50. 60, 70. 80. 90, 100, or higher, "Λ" represents a hard block or segment and "B"" represents a soft block or segment. Preferably , Λs and Bs are linked in a substantially linear fashion, as opposed to a substantially branched or substantially star-shaped fashion. In other embodiments, A blocks and B blocks are randomly distributed along the polymer chain. In other words, the block copolymers usually do not have a structure as follows.
AAA—ΛA-BBB— BB
[0030] In still other embodiments, the block copolymers do not usually have a third type of block, which comprises different comonomer(s). In yet other embodiments, each of block A and block B has monomers or comonomers substantially randomly distributed within the block. In other words, neither block A nor block B comprises two or more sub-segments (or sub-blocks) of distinct composition, such as a tip segment, which has a substantially different composition than the rest of the block.
[0031] The multi-block polymers typically comprise \ arious amounts of "hard" and "soft" segments. "Hard" segments refer to blocks of poly merϊ/ed units in which ethy lene is present in an amount greater than about 95 weight percent, and preferably greater than about 98 weight pel cent based on the weight of the polymer. In other Λardx the eomorsomer content {content of monomers other than ethy lene; in the hard segments is less than Jbout 5 weight percent, and preferably iess than about 2 weight percent ba&ed on the weight of the polymer. In some embodiments, the hard segments comprises all or substantially all ethylene. "Soft" segments, on the other hand, refer to blocks of pol> merited units in which the comonomer content (content of monomers other than ethylene) is greater than about 5 weight percent, preferably greater than about 8 weight percent, greater than about 10 weight percent, or greater than about 15 weight percent based on the weight of the polymer. In some embodiments, the comonomer content in the soft segments can be greater than about 20 weight percent, greater than about 25 weight percent, greater than about 30 weight percent, greater than about 35 weight percent, greater than about 40 weight percent, greater than about 45 weight percent, greater than about 50 weight percent, or greater than about 60 weight percent.
[0032] The soft segments can often be present in a block interpolymer from about 1 weight percent to about 99 weight percent of the total weight of the block interpolymer, preferably from about 5 weight percent to about 95 weight percent, from about 10 weight percent to about 90 weight percent, from about 15 weight percent to about 85 weight percent, from about 20 weight percent to about 80 weight percent, from about 25 weight percent to about 75 weight percent, from about 30 weight percent to about 70 weight percent, from about 35 weight percent to about 65 weight percent, from about 40 weight percent to about 60 weight percent, or from about 45 weight percent to about 55 weight percent of the total weight of the block interpolymer. Conversely, the hard segments can be present in similar ranges. The soft segment weight percentage and the hard segment weight percentage can be calculated based on data obtained from DSC or NMR, Such methods and calculations are disclosed in a concurrently filed U.S. Patent Application Serial No. 1 1/376,835. Attorney Docket No. 385063999558. entitled "Eth> lene/α-Olefms Block ϊnterpolymers", filed on March 15. 2006, in the name of Colin L.P. Shan, Lonnie Ha/litt, et. al. and assigned to Dow- Global Technologies Inc., the disclosure of which is incorporated by reference herein in its entirety.
(0033) The term "crystalline" if employed, refers to a polymer that possesses a first order transition or crystalline melting point (Tm) as determined by differential scanning calorimetry (DSC) or equivalent technique. The term may be used interchangeably with the term "semicrv stalline". The term "amorphous" refers to a poly mer lacking a cry stalline melting point as determined by differential scanning eaiorimetry (DSC) or equivalent technique. (§034 j 1 he term ""multi-block eopoiy mer" or "segmented copoly mer" refers to a poh mer comprising two or more chemical!} distinct regions or segments (referred to as "blocks"*)
-H- preferably joined in a linear manner, that is. a polymer comprising chemically differentiated units which are joined end-to-end with respect to polymerized ethylenic functionality, rather than in pendent or grafted fashion. In a preferred embodiment, the blocks differ in the amount or type of comonomer incorporated therein, the density, the amount of crystallinity. the crystallite size attributable to a polymer of such composition, the type or degree of tacticity (isotactic or syndiotactic). regio-regularity or regio-irregularity . the amount of branching, including long chain branching or hyper-branching, the homogeneity, or any other chemical or physical property. The multi-block copolymers are characterized by unique distributions of both polydispersity index (PDI or Mw/ Mn), block length distribution, and/or block number distribution due to the unique process making of the copolymers. More specifically, when produced in a continuous process, the polymers desirably possess PDI from 1.7 to 2.9, preferably from 1.8 to 2.5, more preferably from 1.8 to 2.2, and most preferably from 1.8 to 2.1. When produced in a batch or semi-batch process, the polymers possess PDI from LO to 2.9, preferably from 1.3 to 2.5, more preferably from 1.4 to 2.0, and most preferably from 1.4 to 1.8.
[0035] In the following description, all numbers disclosed herein arc approximate values, regardless whether the word "about" or "approximate" is used in connection therewith. They may vary by 1 percent. 2 percent, 5 percent, or, sometimes. 10 to 20 percent. Whenever a numerical range with a lower limit, R1 and an upper limit, R1 , is disclosed, any number falling within the range is specifically disclosed. In particular, the following numbers within the range are specifically disclosed: R=-R! -rk^R1 -R1 ). wherein k is a variable ranging from 1 percent to 100 percent with a 1 percent increment, i.e.. k is 1 percent, 2 percent, 3 percent, 4 percent. 5 percent...., 50 percent. 51 percent. 52 percent,..., 95 percent, 96 percent, 97 percent, 98 percent. 99 percent, or 100 percent. Moreover, any numerical range defined by two R numbers as defined in the above is also specifically disclosed.
Figure imgf000011_0001
Interpolymers
[0036 j 1 he olefin block polymers, e.g. ethylene α -olefin interpolymers, used in embodiments of the invention (also referred to as "inventive interpohmer" or
Figure imgf000011_0002
polymer") comprise ethylene and one or more copoiymerizabie α-olefin comonomers in pohmeri/ed form, characterized by muitipie blocks or segments of two or more poh meri/ed monomer uπib differing in chemical or phy sical properties (block interpoiynicr). preferably a multi-block copolymer. 1 he ethy lene α-olefin interpoSyiners are characterized by one or more of the aspects described as fυlkmv [0037] In one aspect, the ethy lene<α-olefin interpol} mcrs used in embodiments of the invention have a Mvy'Mn from about 1.7 to about 3.5 and at least one melting point, Tm. in degrees Celsius and density, d. in grams/cubic centimeter, wherein the numerical values of the variables correspond to the relationship;
T111 > -2002.9 - 4538.5(d) - 2422.2(d)2, and preferably
Tm > -6288.1 -1- 13141(d) - 6720.3(d)2. and more preferabl>
Tm > 858.91 - 1825.3(d) t- 1 112.8(d)2.
[0038] Such melting point/density relationship is illustrated in Figure 1. Unlike the traditional random copolymers of ethylene/α-oleflns whose melting points decrease with decreasing densities, the inventive interpolymers (represented by diamonds) exhibit melting points substantially independent of the density, particularly when density is between about 0.87 g/cc to about 0.95 g'cc. For example, the melting point of such polymers are in the range of about 1 10 0C to about 130 0C when densit} ranges from 0.875 g'cc to about 0.945 g/cc. fn some embodiments, the melting point of Mich polymers are in the range of about 1 15 0C to about 125 0C when densit) ranges from 0.875 g,cc to about 0.945 g'cc. [0039} In another aspect, the ethylene;α-olefm interpol) mcrs comprise, in polymerized form, ethylene and one or more α-olefins and are characterized by a ΔT, in degree Celsius, defined as the temperature for the tallest Differential Scanning Calorimetry ("DSC") peak minus the temperature for the tallest Crystallization Anal) sis Fractionation ("CRYS I AF") peak and a heat of fusion in J g. ΔH, and ΔT and ΔH satisfy the following relationships: ΛT > -0.1299(ΛH) + 62.8 L and preferably
AT > -0.1299(ΔH) -L 64.38. and more preferabt)
ΔT > -0.1299(AH) - 65.95.
for ΔH up to 130 J, g. Moreover. A 1 is equal to or greater than 48 ϋC for ΔH greater than 130 J g. The CRYS TAF peak is determined using at least 5 percent of the cumulative polymer (that is. the peak must represent at least 5 percent of the cumulative polymer), and if iess than 5 percent of the polymer has an identifiable CRYS TAF peak, then the CRYSTAF temperature is 300C, and \H is the numerical value of the heat or fusion m J g. More preferabh . die highest C RYS I Al peak contains at least 10 percent of the c poly rπer. Hgure 2 shows plotted data for mvenme polymers as well a<- com par at he
-H)- examples. Integrated peak areas and peak temperatures are calculated b\ the computerized drawing program supplied by the instrument maker, lhe diagonal line shown for the random ethylene octene comparative pohmers corresponds to the equation ΔT ~ -0.1299 (AH) - 62.81.
[0040] In vet another aspect, the ethylene'α-olefm interpohmers ha\e a molecular fraction which elutes between 400C and 13O0C when fractionated using Temperature Rising Elution Fractionation ("TREF"). characterized in that said fraction has a molar comonomer content higher, preferably at least 5 percent higher, more preferably at least 10 percent higher, than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, wherein the comparable random ethylene interpolymer contains the same comonomer(s). and has a melt index, density, and molar comonomer content (based on the whole polymer) within 10 percent of that of the block interpolymer. Preferably, the Mw/Mn of the comparable interpolymer is also within 10 percent of that of the block interpolymer and/or the comparable interpolymer has a total comonomer content within 10 weight percent of that of the block interpolymer.
10041] ϊn still another aspect, the ethylene/α-olcfin interpoKmers are characterized by an elastic reco\ery, Re, in percent at 300 percent strain and 1 cycle measured on a compression- molded film of an ethylene 'α-olcfin interpol>mcr, and has a density, d. in grams, cubic centimeter, wherein the numerical values of Re and d satisfy the following relationship when ethylene 'α-olefin interpolymer is substantially free of a cross-linked phase: Re >1481-1629(d); and preferably
Re >1491-1629(d); and more preferably
Re >1501-1629(d); and e\en more preferably
Re >151 Mό29(d).
|0042| Figure 3 shows the effect of density on elastic recovery, for unoriented films made from certain inventive interpohmers and traditional random copoh mers. For the same densitv. the inventive interpoKmers ha\ e substantial!} higher elastic reco\ erics. (0043) Ia some embodiments, the ethy lene α-olefin interpoKmers hav e a tensile strength above 10 MPa. preferabH a tensile strength 2 1 1 MPa. more preferaH; a tensile strength - P MPu and or an elongation ai break of at least d00 percent, more prefei<ibly at least ~H)U percent, highly preferably at least 800 percent, and most highh preferably at least 900 percent at a crosshead separation rate of 1 1 cm. 'minute.
[0044] In other embodiments, the ethylene/α-olefm interpolymers have { 1 } a storage modulus ratio, G"(25°C>G*(Ϊ OO°C), of from 1 to 50. preferably from 1 to 20. more preferably from 1 to 10; and or (2) a 7O0C compression set of less than 80 percent, preferably less than 70 percent, especially less than 60 percent, less than 50 percent, or less than 40 percent, down to a compression set of 0 percent.
[0045] In still other embodiments, the ethylene/α-olefm interpolymers have a 7O0C compression set of less than 80 percent, less than 70 percent, less than 60 percent, or less than 50 percent. Preferably, the 700C compression set of the interpolymers is less than 40 percent, less than 30 percent, less than 20 percent, and may go down to about 0 percent. [0046J In some embodiments, the ethyl ene/α-ole fin interpolymers have a heat of fusion of less than 85 J/'g and/or a pellet blocking strength of equal to or less than 100 pounds/foot (4800 Pa), preferably equal to or less than 50 lbs/ft2 (2400 Pa), especially equal to or less than 5 lbs/ft2 (240 Pa), and as low as 0 lbs/ft2 (0 Pa).
[0047] In other embodiments, the ethylene/α-olefm interpol} mers comprise, in polymerized form, at least 50 mole percent ethylene and have a 7O0C compression set of less than 80 percent, preferably less than 70 percent or less than 60 percent, most preferably less than 40 to 50 percent and down to close to zero percent,
[0048] In some embodiments, the multi-block copolymers possess a PDI fitting a Schultz-Flory distribution rather than a Poisson distribution. The copolymers are further characterized as having both a polydisperse block distribution and a poivdisperse distribution of block si/es and possessing a most probable distribution of block lengths. Preferred multi- block copolymers are those containing 4 or more blocks or segments including terminal blocks. More preferably, the copolymers include at least 5. 10 or 20 blocks or segments including terminal blocks.
[0049| Comonomer content may be measured using any suitable technique, with techniques bas.ed on nuclear magnetic resonance ("XMR") spectroscopy preferred. Moreover, for polymers or blends of polymers hav ing relatively broad TRhF curves, the polymer desirably is first fractionated using TREF into fractions each hav ing an cJuted tern perai are range of 10°C or less. That is. each eluted fraction has a collection temperature umdovt of HfC or Ie^s. i sing ihK technique, ^aid bϊock interpohmer^ have at least one such fraction hav ing a higher nioLr eomcnomer content than a corresponding fraction uf the comparable interpoly mer. [0050] In another aspect, the incentive polymer is an olefin interpoly mcr, preferably comprising ethylene and one or more copolymeri/able comonomers in polymerized form, characterized by multiple blocks (i.e.. at least two blocks) or segments of two or more polymerized monomer units differing in chemical or physical properties (blocked interpolymer). most preferably a multi-block copolymer, said block interpolymer having a peak (but not just a molecular fraction) which elutes between 400C and 13O0C (but without collecting and/or isolating individual fractions), characterized in that said peak, has a comonomer content estimated by infra-red spectroscopy when expanded using a full width 'half maximum (FWHM) area calculation, has an average molar comonomer content higher, preferably at least 5 percent higher, more preferably at least 10 percent higher, than that of a comparable random ethylene interpolymer peak at the same elution temperature and expanded using a full width/h a! f maximum (FWHM) area calculation, wherein said comparable random ethylene interpolymer has the same comonomer(s) and has a melt index, density, and molar comonomer content (based on the whole polymer) within 10 percent of that of the blocked interpolymer. Preferably, the MwMn of the comparable interpolymer is also within 10 percent of that of the blocked interpolymer and/or the comparable interpolymer has a total comonomer content within 10 weight percent of that of the blocked interpolymer. The full width/half maximum (FWIlM) calculation is based on the ratio of methyl to methylene response area ICH3/CH2] from the Λ'IREF infra-red detector, wherein the tallest (highest) peak is identified from the base line, and then the FWIIM area is determined. For a distribution measured using an A 1 RJLF peak, the FWHM area is defined as the area under the curve between Ti and T2, where T| and F2 are points determined, to lhe left and right of the ATREF peak, by dividing the peak height by two. and then drawing a line horizontal to the base line, that intersects the left and right portions of the ATRLF curve. Λ calibration curve for comonomer content is made using random ethylene 'α-olefϊn copolymers, plotting comonomer content from NMR versus FWIIM area ratio of the TREF peak. For this infra-red method, the calibration curv e is generated for the same comonomer type of interest. The comonomer content of ϊ REF peak of the inventiv e polymer can be determined by referencing this calibration curve using its FWHM methyl : methylene area ratio [CHi CH2] of the TREF peak.
[0051] Comonomer content may be measured using any suitable technique, with techniques based on nuclear magnetic iesonanee (WIRi spectroscopy preferred. I sing th^ technique, said blocked mterpohmer ha^ higher molar comonomer content than a corresponding comparable interpoiyrner. [0052] Preferably, for interpolymers of ethylene and 1-octene, the block interpolymer has a comonomer content of the TREF fraction eluting between 40 and 130QC greater than or equal to the quantity {- 0.2013) T + 20.07, more preferably greater than or equal to the quantity (-0.2013) T~ 21.07, where T is the numerical \alue of the peak elution temperature of the TREF fraction being compared, measured in 0C.
[0053] Figure 4 graphically depicts an embodiment of the block interpolymers of ethylene and 1-octene where a plot of the comonomer content versus TREF elution temperature for se\eral comparable ethylene'l-octene interpolymers (random copolymers) are fit to a line representing (-0.2013) T -- 20.07 (solid line). The line for the equation (- 0.2013) T -+- 21.07 is depicted by a dotted line. Also depicted are the comonomer contents for fractions of several block ethylene/1 -octene interpolymers of the invention (multi-block copolymers). All of the block interpolymer fractions have significantly higher 1-octene content than either line at equivalent elution temperatures. This result is characteristic of the inventive interpolymer and is believed to be due to the presence of differentiated blocks within the polymer chains, having both crystalline and amorphous nature. [0054| Figure 5 graphically displays the TREF curve and comonomer contents of polymer fractions for Example 5 and Comparative F discussed below. The peak eluting from 40 to 13O0C. preferably from 6O0C to 950C for both polymers is fractionated into three parts, each part eluting over a temperature range of less than 100C. Actual data for Example 5 is represented by triangles. The skilled artisan can appreciate that an appropriate calibration curve may be constructed for inierpolymers containing different comonomers and a line used as a comparison fitted to the TREb values obtained from comparative interpolymers of the same monomers, preferably random copolymers made using a metallocene or other homogeneous catalyst composition. Inventive interpolymers are characterized by a molar comonomer content greater than the value determined from the calibration curve at the same TREF elution temperature, preferably at least 5 percent greater, more preferably at least 10 percent greater.
[0055] in addition to the abo\e aspects and properties described herein, the inventive polymers can be characterized by one or more additional characteristics. In one aspect, the inventive polymer is an olefin interpolymer, preferably comprising ethy lene and one or more eopohmeri/ahle comonomers in polymerized form, characterized by multiple blocks or segments of two or more pohmeri/ed monomer units- JtfJerhig in chemical or physical properties f blocked interpolymer). most preferably a multi-block copolymer, said block inteπxήvmer rut ins a molecular fraction which elυtcs between 4O0C" and 130X", when
- ! -+- fractionated u^ing TREF increments, characterized in that said fraction has a molar comoBomer content higher, preferably at least 5 percent higher, more preferabK at least 10. 15, 20 or 25 percent higher, than that of a comparable random ethylene interpoK mer fraction eluting between the same temperatures, wherein said comparable random ethylene interpolymer comprises the same comonorner(s). preferabK it is the same comonomer(s), and a melt index, density . and molar comonomer content {based on the whole polymer) within 10 percent of that of the blocked interpolymer. Preferably the Mw Mn of the comparable interpolymer is also within 10 percent of that of the blocked interpoly rner and or the comparable interpolymer has a total comonomer content within 10 weight percent of that of the blocked interpolymer.
[0056 j Preferably, the
Figure imgf000017_0001
interpolymers are interpolymers of ethylene and at least one α-olefϊn, especially those interpolymers having a whole polymer density from about 0.855 to about 0.935 g/cm\ and more especially for polymers having more than about 1 mole percent comonomer, the blocked interpolymer has a comonomer content of the 1 REF fraction eluting between 40 and 13O0C greater than or equal to the quantity (-0.1356) F + 13.89. more preferably greater than or equal to the quantity (-0.1356) T4- 14.93, and most preferably greater than or equal to the quantity (-0.2013)T - 21.07, where T is the numerical value of the peak ATREF elution temperature of the TREF fraction being compared, measured m 0C. [0057] Preferably, for the above interpolymers of ethylene and at least one alpha-olefin especially those interpolymers having a whole polymer density from about 0.855 to about 0.935 g/cm5. and more especially for polymers having more than about 1 mole percent comonomer, the blocked interpolymer has a comonomer content of the TRFF fraction eluting between 40 and 130°C greater than or equal to the quantity (- 0.2013) T -- 20.07, more preferably greater than or equal to the quantity (-0.2013) 1+ 21.07. where F is the numerical value of the peak elution temperature of the ϊ REF fraction being compared, measured in 0C. [0058] In still another aspect, the im entive polymer is an olefin interpolymer. preferabK comprising ethylene and one or more copoKmerizable comonomers in polymerized form, characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical or phy sical properties (blocked interpoK mer). most preferably a multi- block copolymer, said block interpolymer having a molecular fraction which elutes between Mf '( and 130T. when fractionated using 1 RE-I- increments, chatacteπ/ed m that every ing a comonomer content cl at 'cast atx>ut 6 mole percent fias. a rπehi% pent creater than about I bCrC I or those fi actions, hav ing α eormmomef content from about ? mole percent to about 6 mole pet cent, every fraction lias ^ DSC melting pomt of aooui 1 IOC or higher. More preferably, said polymer fractions. ing at least 1 mole percent comonomer, has a DSC melting point that corresponds to the equation:
Tm > (-5.5926)(mole percent comonomer in the fraction) + 135.90.
[0059] In yet another aspect, the inventhe polymer is an olefin interpolymer, preferably comprising ethylene and one or more copolymerizable comonomers in poly merized form, characterized by multiple blocks or segments of two or more polymeri/ed monomer units differing in chemical or physical properties (blocked interpolymer), most preferably a multi- block copolymer, said block interpolymer having a molecular fraction which elutes between 400C and BO0C. when fractionated using TREF increments, characterized in that every fraction that has an ATREF elution temperature greater than or equal to about 7ό°C, has a melt enthalpy (heat of fusion) as measured by DSC. corresponding to the equation:
Heat of fusion (J/gm) < (3.1718)( ATREF elution temperature in Celsius) - 136.58,
[0060] The inventive block interpolymers have a molecular fraction which elutes between 4O0C and 13O0C, when fractionated using TRHF increments, characterized in that every fraction that has an ATREF elution temperature between 400C and less than about 76°C. has a melt enthalpy (heat of fusion) as measured by DSC, corresponding to the equation:
I ϊcat of fusion (J 'gm) < ( 1.1312)( ATREF elution temperature in Celsius) -r 22.97.
ATREF Peak Coraonomer Composition Measurement by Ϊnfra-Red Detector
[0061 j 1 he comonomer composition of the 1 RF. F peak can be measured using an 1R4 infra-red detector available from Polymer Char, Valencia, Spain (http: 'w w w. pohmerehar.com ).
J 0062] The "composition mode" of the detector is equipped with a measurement sensor (CH2) and composition sensor (CFIj) that are fixed narrow band infra-red filters in the region of 2800-3000 cm"1. The measurement sensor detects the methylene (CHa) carbons on the polymer (which directly relates to the polymer concentration in solution) while the composition sensor detects the methyl (CH-,) groups of the polymer. The mathematical ratio of the composition signal (CH?) dhided by the measurement signal (CH;) is sensitive to the comonomer content of the measured polymer in solution and its response is calibrated with known ethylene aipha-olefm copolymer "standards.
(0063] 1 fie detector when used with an
Figure imgf000018_0001
lde^ both a concentration i CI M and composition (C H-*) signal response of the eluted polymer during tnc i Hl I process. A polymer specific calibration can be created by measuring the area ratio of the CII3 to CH2 for polymers with known comonomer content (preferably measured b> NMR). The comonomer content of an ATREF peak of a pohmer can be estimated by applying a the reference calibration of the ratio of the areas for the individual CH3 and CH2 response (i.e. area ratio CH3/CH2 \ersus comonomer content),
[0064] The area of the peaks can be calculated using a full width/ half maximum (FWHM) calculation after applying the appropriate baselines to integrate the individual signal responses from the FREF chromatogram. The full width/half maximum calculation is based on the ratio of methyl to methylene response area [CH3/CH2J from the ATREF infrared detector, wherein the tallest (highest) peak is identified from the base line, and then the FWHM area is determined. For a distribution measured using an ATREF peak, the FWHM area is defined as the area under the curve between Tl and F2. where Tl and T2 are points determined, to the left and right of the ATREF peak, by dividing the peak height by two, and then drawing a line horizontal to the base line, that intersects the left and right portions of the ATREF curve.
[0065] The application of infra-red spectroscopy to measure the comonomer content of polymers in this ATREF-infra-red method is, in principle, similar to that of GPC/FT1R systems as described in the following references: Markovich, Ronald P.; Ilazlitt. Lonnie G.; Smith, Linley; "Development of gel-permeation chromatography -Fourier transform infrared spectroscopy for characterization of ethyiene-based poly olefin copolymers". Polymeric Materials Science and Engineering ( 1991), 65. c>8-100.: and Deslauriers, P. J.; Rohlfmg, D. C: Shieh, E. I .: "Quantifying short chain branching microstructures in ethylene- 1 -olefin copolymers using si/e exclusion chromatography and Fourier transform infrared spectroscopy (SEC-FTiR)". Polymer (2002), 43, 59-170., both of which are incorporated by reference herein in their entirety.
[0066] In other embodiments, the inventive ethylenes-olefin interpolymer is characterized by an av erage block index. ABL which is greater than /ero and up to about 1.0 and a molecular weight distribution. Mu Mn. greater than about 1.3. Fhe average block index. ABI, is the weight average of the block index ("Bf") for each of the pohmer fractions obtained in preparative TREF from 200C and 1 100C. with an increment of 50C:
ABI = Y1 (H Bf J
- ! ?- where BI1 is the block index for the ith fraction of the incentive ethylene α-olelln interpolymer obtained in preparative 1 REF. and ws is the weight percentage of the ith fraction.
10067] For each polymer fraction, Bl is defined by one of the two following equations (both of which give the same Bl value):
1 T, - V Ti9 LnPx - LnP1n where T\ is the preparative ATREF elution temperature for the ith fraction (preferably expressed in Kelvin), Px is the ethylene mole fraction for the ith fraction, which can be measured b> NMR or IR as described above. P \B is the ethylene mole fraction of the whole ethylene α-olefin interpoSymer (before fractionation), which also can be measured by NMR or IR. TΛ and PA are the ATRHF elution temperature and the ethylene mole fraction for pure "hard segments" (which refer to the crystalline segments of the interpolymer). As a first order approximation, the T v and P \ values are set to those for high density polyethylene homopoiymer. if the actual values for the "hard segments'" are not available. For calculations performed herein, T \ is 372°K, P \ is 1.
[0068] f VB is the AT RLF temperature for a random copolymer of the same composition and having an ethylene mole fraction of P \\\. T \B can be calculated from the following equation:
Ln P Mi = α, l + β
where α and β are two constants which can be determined by calibration using a number of known random ethylene copolymers. It should be noted that α and β may van from instrument to instrument. Moreover, one would need to create their own calibration curve with the polymer composition of interest and also in a similar molecular weight range as the fractions. Lhere is a slight molecular weight effect. If the calibration curv e is obtained from similar molecular weight ranges, such effect would be essentially negligible. In some embodiments, random ethylene copoly mers satisfy the following relationship
Ln P —237 83 !\i Rn - 0.639
}O(I69| I M SS the \ l R! i 'unpeiαture lor _. random tojx h '<iei of the sa.r>>e composition and mu an
Figure imgf000020_0001
lcne mole fraction oτ P- I sO can be calculated 'rom I nP Λ α I v, - β Conversely, P\o is the ethylene mole fraction for a random copolymer of the same composition and having an ATREF temperature of Tx. which can be calculated from Ln
Figure imgf000021_0001
-= α/Tx *- β.
[00701 Once the block index (BI) for each preparative T REF fraction is obtained, the weight average block index, ABI. for the whole polymer can be calculated. In some embodiments, ABI is greater than zero but less than about 0.3 or from about 0.1 to about 0.3. ϊn other embodiments. ABl is greater than about 0.3 and up to about 1.0. Preferably ABI should be in the range of from about 0,4 to about 0.7. from about 0.5 to about 0.7, or from about 0.6 to about 0.9. In some embodiments. ABl is in the range of from about 0.3 to about 0.9, from about 0.3 to about 0.8, or from about 0.3 to about 0.7, from about 0.3 to about 0.6, from about 0.3 to about 0.5, or from about 0.3 to about 0.4. In other embodiments. ABl is in the range of from about 0.4 to about 1.0. from about 0.5 to about 1.0- or from about 0.6 to about 1.0, from about 0.7 to about 1.0, from about 0.8 to about 1.0, or from about 0.9 to about 1.0.
[0071 J Another characteristic of the inventive ethylene, α-olefin interpoly mer is that the inventive ethvlene'α-olefm interpolymer comprises at least one polymer fraction which can be obtained by preparative TREF5 wherein the fraction has a block index greater than about 0.1 and up to about 1.0 and a molecular weight distribution, Mw1Mn. greater than about 1.3. ϊn some embodiments, the polymer fraction has a block index greater than about 0.6 and up to about 1.0. greater than about 0.7 and up to about 1.0, greater than about 0.8 and up to about 1.0, or greater than about 0.9 and up to about 1.0. In other embodiments, the polymer fraction has a block index greater than about 0.1 and up to about 1.0. greater than about 0.2 and up to about 1.0, greater than about 0.3 and up to about 1.0, greater than about 0.4 and up to about 1.0, or greater than about 0.4 and up to about 1.0. In still other embodiments, the polymer fraction has a block index greater than about 0.1 and up to about 0.5, greater than about 0,2 and up to about 0.5. greater than about 0.3 and up to about 0.5. or greater than about 0.4 and up to about 0.5. In yet other embodiments, the polv mer fraction has a block index greater than about 0.2 and up to about 0.9. greater than about 0.3 and up to about 0.8, greater than about 0.4 and up to about 0.7. or greater than about 0.5 and up to about 0.6. [0072] For copolymers of ethy lene and an α-olefin. the inventive pohmers preferably possess (D a PDI of at least 1.3. more preferabh at least 1.5. at least 1.7. or at least 2.0. and most preferably at least 2 6. up to a maximum value of 5.0. more piefcrahh ap to a maximum of 3.5. and especial!) up to a maximum of 2.7: (2) a heat of fusion uf 8ϋ J g or less: ( ?) an
-; 9- ethylene content of at least 50 weight percent; (4) a glass transition temperature. Tg. of less than -250C, more preferably less than -3O0C: and/or (5) one and only one Tm. [0073] Further, the inventive polymers can have, alone or in combination with any other properties disclosed herein, a storage modulus, G", such that log (G') is greater than or equal to 400 kPa. preferably greater than or equal to 1.0 MPa. at a temperature of 1000C. Moreover, the inventive polymers possess a relatively flat storage modulus as a function of temperature in the range from 0 to 1000C (illustrated in Figure 6) that is characteristic of block copolymers, and heretofore unknown for an olefin copolymer, especially a copolymer of ethylene and one or more Cj-S aliphatic α-olefms. (By the term "relatively flat" in this context is meant that log G' (in Pascals) decreases by less than one order of magnitude between 50 and 100°C, preferably between 0 and 1000C).
[0074J The inventive interpolymers may be further characterized by a thermomechanical analysis penetration depth of 1 mm at a temperature of at least 9O0C as well as a flexural modulus of from 3 kpsi (20 MPa) to 13 kpsi (90 MPa). Alternatively, the inventive interpolymers can ha\e a thermomechanical analysis penetration depth of 1 mm at a temperature of at least 1040C as well as a flexural modulus of at least 3 kpsi (20 MPa). They may be characterized as having an abrasion resistance (or volume loss) of less than 90 mmJ. Figure 7 shows the TMA (1 mm) versus flex modulus for the inventive polymers, as compared to other known polymers. The inventive polymers have significantly better flexibility-heat resistance balance than the other polymers.
[0075] Additionally . the ethy !ene/α-olefin interpolymers can have a melt index. I2. from 0.01 to 2000 g/ 10 minutes, preferably from 0.01 to 1000 g'10 minutes, more preferably from 0.01 to 500 g/10 minutes, and especially from 0.01 to 100 g/10 minutes. In certain embodiments, the ethy lene/α-olefin interpolymers have a melt index, h. from 0.01 to 10 g/ 10 minutes, from 0.5 to 50 g/10 minutes, from 1 to 30 g/10 minutes, from 1 to 6 g 10 minutes or from 0.3 to 10 g, 10 minutes. In certain embodiments, the melt index for the ethylencα-olefm polvmers is Ig/ 10 minutes. 3 g'10 minutes or 5 gi O minutes.
[0076| The polymers can have molecular weights, Mw. from 1 ,000 g mole to 5,000.000 g, mole. preferably from 1000 g mole to 1 ,000,000, more preferably from 10.000 g mole to 500,000 g/mole, and especially from 10,000 g mole to 300,000 g mole. The density of the inventive polvmers can be from 0.80 to 0.99 g'crπ* and preferably for ethy lene containing polymers from 0,85 g cm' to ') 97 g era' . In certain embodiments, the density el the ethy lene α-oiefin polymers ranges from 0.860 to 0.925 g em ' or 0.867 to 0.910 g eai\
-Kh [0077] The process of making the polymers has been disclosed in the following patent applications: U.S. Pro\ isional Application No. 60 553,906. filed March 17. 2004; U.S. Application No. 60 662.937. filed March 17, 2005; U.S. Provisional Application No. 60'662,939, filed March 17. 2005; U.S. Pro\isional Application No. 60-662.938. filed March 17. 2005: PCT Application No. PCFUS2005O08916. filed March 17. 2005; PCT Application No. PCT/US2005O08915, filed March 17. 2005; and PCT Application No. PCTVU S2005/008917. filed March 17, 2005. all of which are incorporated by reference herein in their entirety. For example, one such method comprises contacting ethylene and optional!} one or more addition polymerizable monomers other than ethylene under addition polymerization conditions with a catal>st composition comprising: the admixture or reaction product resulting from combining:
(A) a first olefin polymerization catalyst having a high comonomer incorporation index,
(B) a second olefin polymerization catalyst having a comonomer incorporation index less than 90 percent, preferably less than 50 percent, most preferably less than 5 percent of the comonomer incorporation index of catalyst (A), and
(C) a chain shuttling agent.
{0078] Representative catalysts and chain shuttling agent are as follows.
[0079 j Catalyst (Λ 1 ) is [N-(2,ό-di( 1 -niethyleths 1 )pheny l)amido)(2-isoprop> lpheny 1 )( α- naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium dimethyl, prepared according to the teachings of WO 03'4019S. 2003US0204017. USSN 10/429.024. filed May 2. 2003, and WO
04/24740.
Figure imgf000023_0001
|0080| CaidK st f Λ2 j Is j Vf 2 ό-du I -muhx icthy 1
Figure imgf000023_0002
phen}
Figure imgf000023_0003
l)mcthaneN! {hafnium prepared according to the teachings
_o t . of WO 03 40195. 2GQ3LS0204017. USSN 10 429,024, filed May 2. 2003. and W O 04/24740.
Figure imgf000024_0001
[00811 Catalyst (A3) is bis[N.N- " '-(2,4,6- trifmethylpheny l)amido)ethylenediamine]hafhium dibenzyl.
Figure imgf000024_0002
[0082J Catalyst (Λ4) is bis((2-oxoyl-3-(diben/o-lH-pvrroic-l-\l)-5-(meth> l)phenyl)-2- pheno\ymethyl)c\clohexane-l,2-di\l zirconium (IV) diben/vl. prepared substantialh according to the teachings of LS-A-2004'0010103.
Figure imgf000024_0003
[0083J Catalyst (Bl) is
Figure imgf000024_0004
l- methy iethy I iimmino jmethy I M 2-o\oy Ij /irconium 1
Figure imgf000025_0001
[0084] Catalyst (B2) is L2-bis-(3,5-di-t-butylphenylene)(l-(N-(2-meth\lcycIohex>l)- immino)methyl)(2-oxoyl) zirconium dibenzvl
Figure imgf000025_0002
[0085] Catalyst (C l ) is (t-but>Iamido)dimcth> l(3-N-p>rrol>l-1.2.3,3a,7a-η-indcn-l - >I)silanctitanium dimethyl prepared substantiall} according to the techniques of USP 6,268,444:
Figure imgf000025_0003
(0086) Catahst (C2) is (t-but\
Figure imgf000025_0004
l- L2.3.3a,7a-η-inden-
Figure imgf000025_0005
according to the teachings of L S-A- 2003 004286:
Figure imgf000026_0001
(0O87J Catalyst (C3) is (t-butylamido)di(4-methylρheny i)(2-methyl- 1.2.3.3a,8a-η-s- indacen-l -yl)silanetitanium dimethyl prepared substantially according to the teachings of US-
Figure imgf000026_0002
[00881 Catalyst (D 1 ) is bis(dimcth> ldisiloxane)(indcnc- 1 -yl)zirconium dichloridc available from Sigma-Λldrich:
Figure imgf000026_0003
[0089] Shuttling Agents I he shuttling agents employed include
Figure imgf000026_0004
lzine. di(i- but\ l)zinc,
Figure imgf000026_0005
trieth> taluminum. triocty laluminum. triethv IgaUium, i-
Figure imgf000026_0006
i-bυt> laluminum bis(di(trimeth> lsil> l)amide). n-octvialuminum
Figure imgf000026_0007
bis{n-ociadec> hi-bun laluminum. i- laluminum bB(αt(
Figure imgf000026_0009
!)armde}. n-oct> Li!αmmum
Figure imgf000026_0008
n- oct % IaS uminum di' eihv i( i -naphth> I iamide ι.
Figure imgf000026_0010
Idfuminum
Figure imgf000026_0011
l)aiπide). cihvlaluminαm bisi.2,3.6.7-dsben/e-! - azaeydoheptanearmde), n-octylaluminum bis(2.3.6,7-dibenzo-l-azac\clohepianeamide), n- octylaluminum bis(dirnethv l(t-but> l)siloxide. ethylzinc (2,6-diphenyiphenoxϊde), and ethy Izinc (t-butoxide).
[009Oj Preferably, the foregoing process takes the form of a continuous solution process for forming block copolymers, especially multi-block copolymers, preferably linear multi- block copolymers of two or more monomers, more especially ethylene and a C^o olefin or cycloolefm, and most especially ethylene and a C4.20 α-olefm. using multiple catalysts that are incapable of intercon version. That is, the catalysts are chemically distinct. Under continuous solution polymerization conditions, the process is ideally suited for polymerization of mixtures of monomers at high monomer conversions. Under these polymerization conditions, shuttling from the chain shuttling agent to the catalyst becomes ad\antaged compared to chain growth, and multi-block copolymers, especially linear multi- block copolymers are formed in high efficiency.
[0091] The inventive interpolymers may be differentiated from conventional, random copolymers, physical blends of polymers, and block copolymers prepared via sequential monomer addition, fluxional catalysts, anionic or cationic living polymerization techniques. In particular, compared to a random copolymer of the same monomers and monomer content at equivalent cry stallintty or modulus, the inventive interpolymers have better (higher) heat resistance as measured by melting point, higher TMA penetration temperature, higher high- temperature tensile strength, and/ or higher high-temperature torsion storage modulus as determined by dynamic mechanical analysis. Compared to a random copolymer containing the same monomers and monomer content, the inventive interpoiymers have lower compression set. particularly at elevated temperatures, lower stress relaxation, higher creep resistance, higher tear strength, higher blocking resistance, faster setup due to higher crystallization (solidification) temperature, higher recovery (particularly at elevated temperatures), better abrasion resistance, higher retractive force, and better oil and filler acceptance.
|0092| I he inventive interpoiymers also exhibit a unique crystallization and branching distribution relationship. That is. the inventiv e interpolymers have a relatively large difference between the tallest peak temperature measured using CRYS TAF and DSC as a function of heat of fusion, especially as compared to random copolymers containing the same monomeis and monomer level or phy sical blciidb of poh niers. such a*, a blend of a high density polymer and a lower density eopoh met", at equivalent en era! 1 density . It is believ ed that thib unique feature of the inventive intcrpcly mors h due to ihe αnkjiie αisiribution of the conionoraer in blocks within the polymer backbone. In particular, the in\enti\e interpolvmers may comprise alternating blocks of differing comonomer content (including homopolymer blocks). The in\enti\ e interpolvmers may also comprise a distribution in number and/or block size of polymer blocks of differing density or comonomer content, which is a Schultz-Flory type of distribution. In addition, the inventive interpolvmers also have a unique peak melting point and crystallization temperature profile that is substantially independent of polymer density, modulus, and morphology, In a preferred embodiment, the microcrystalline order of the polvmers demonstrates characteristic spherulites and lamellae that are distinguishable from random or block copolymers, even at PDl \alues that are less than 1.7. or even less than 1.5. down to less than 1.3.
[0093] Moreover, the inventive interpolymers may be prepared using techniques to influence the degree or level of blockiness. That is the amount of comonomer and length of each polymer block or segment can be altered by controlling the ratio and type of catalysts and shuttling agent as well as the temperature of the polymerization, and other polymerization variables. A surprising benefit of this phenomenon is the discovery that as the degree of blockiness is increased, the optical properties, tear strength, and high temperature recovery properties of the resulting polymer are improved. In particular, haze decreases while clarity, tear strength, and high temperature recovery properties increase as the average number of blocks in the polvmer increases. By selecting shuttling agents and catalyst combinations having the desired chain transferring ability (high rates of shuttling with low levels of chain termination) other forms of polvmer termination are effective!} suppressed. Accordingly, little if any β-hydride elimination is observed in the polymerization of ethylene/α-oiefin comonomer mixtures according to embodiments of the invention, and the resulting crystalline blocks are highly, or substantially completely, linear, possessing little or no long chain branching.
[0094] Pol>mers with highly crystalline chain ends can be selectively prepared in accordance with embodiments of the invention. In elastomer applications, reducing the relative quantity of polvmer that terminates with an amorphous block reduces the iπtermolecuiar dϋutive effect on ervstalline regions. This result can be obtained by choosing chain shuttling agents and eatahsts hav ing an appropriate response to hydrogen or other chain terminating agents. Specificali} , if the eaiah st which produces htghlv crystalline poiv πier i> more susceptible to chain termination { -.ueh .AS b> u&e el Imlrogetij man the catalvbt responsible lor producing the less cry stalline polvmer segment (such ss through higher eomononier incorporation, regie-error, or atactic polvmer formation), then the highh crystalline polymer segments will preferential!} populate the terminal portions of the polymer. Not only are the resulting terminated groups crystalline, but upon termination, the highly crystalline polymer forming catalyst site is once again a\ailable for reinitiation of polymer formation. The initiall> formed polymer is therefore another highly crystalline polymer segment. Accordingly . both ends of the resulting multi-block copoly mer are preferentially highly crystalline.
[0095] The ethy !ene α-oletln interpolymers used in the embodiments of the ιn\ ention are preferably interpolymers of ethylene with at least one C3-C2O α-olefm. Copolymers of ethylene and a C3-C20 α-olefϊn are especially preferred. The interpolymers may further comprise C4-C] 8 diolefm and/or alkenylbenzene. Suitable unsaturated comonomers useful for polymerizing with ethylene include, for example. eth>lenically unsaturated monomers, conjugated or nonconjugated dienes. polyenes, alkenylbenzenes, etc. Examples of such comonomers include C3-C20 ^-olefins such as propy lene, isobutylene, 1-butene, 1-hexene, l-pentene, 4-methyl-l-pentene, 1-heptene. 1-octene, 1-nonene, 1 -decene, and the like. 1- butene and 1-octene are especially preferred. Other suitable monomers include styrene. halo- or alkyi-substituted styrenes, vinylbcn/ocyclobutane. 1 ,4-hexadiene, L7-octadiene. and naphthenics (e.g., cyclopentene, cyclohexene and cyclooctene). [0096] While ethylene/α-olefm interpolymers are preferred polymers, other ethylene/olefin polymers may also be used. Olefins as used herein refer to a family of unsaturated hydrocarbon-based compounds with at lea^t one carbon-carbon double bond. Depending on the selection of catalysts, any olefin may be used in embodiments of the invention. Preferably, suitable olefins are C3-C20 aliphatic and aromatic compounds containing viny Hc unsaturation. as well as cyclic compounds, such as cyclobutene, cyclopentene. dicyclopentadiene. and norbornene, including but not limited to. norbornene substituted in the 5 and 6 position with Ci-C20 hydrocarbyl or cyclohydrocarby 1 groups. Also included are mixtures of such olefins as well as mixtures of such olefins with C4-C40 diolefm compounds.
[0097] Examples of olefin monomers include, but are not limited to propy lene. isobutylene. 1-butene, l-pentene, 1-hexene. 1-heptene, 1-octene. 1 -noπene. 1 -decene, and 1~ dodecene. 1 -tetradecetie, 1-hexadeeene. 1 -oetadeeene. I -eicosene. 3 -methy l- 1-butene. 3- ni€tK I- 1 -penleiie. 4-rπeth> 1- 1 -per.1 ene. 4.6- Jimethy 1- 1 -heptene. \ inyleyclohevine. norborπadicpe. cthy hdene .lerboratne. cyctop
Figure imgf000029_0001
cntenc, c> dieycicpentadicne, cyctooctene. C4-C4{} dienes. including bui not limited to 1."i-outaJiene
_T7_. 1.3-pentadiene. 1 ,4-hexadiene. 1.5-hexadiene. 1,7-octadiene. 1 ,9-dccadiene. other C4-C40 ot- oiefins. and the like. In certain embodiments, the α-olefin is propylene.1 -butene. 1~ pentene,l-hexene. 1-octene or a combination thereof. Although any hydrocarbon containing a vinyl group potentially may be used in embodiments of the i mention, practical issues such as monomer a\ailability, cost, and the ability to conveniently remove unreacted monomer from the resulting polymer may become more problematic as the molecular weight of the monomer becomes too high.
[0098] The polymerization processes described herein are well suited for the production of olefin polymers comprising mono\inylidene aromatic monomers including styrcne, 0- methyl styrene. p-methyl styrene, t-butylstyrene, and the like. In particular, interpolymcrs comprising ethylene and styrene can be prepared by following the teachings herein. Optionally, copolymers comprising ethylene, styrene and a C3-C20 alpha olefin, optionally comprising a C4-C20 diene, having improved properties can be prepared. (0099] Suitable non-conjugated diene monomers can be a straight chain, branched chain or cyclic hydrocarbon diene having from 6 to 15 carbon atoms. Examples of suitable non- conjugated dienes include, but are not limited to. straight chain acyclic dienes. such as 1 ,4- hexadiene, 1.6-octadiene, 1 ,7-octadiene. 1,9-decadiene, branched chain acyclic dienes, such as 5-methyl-l ,4-hexadiene; 3.7-dimethyl-l,ό-octadiene; 3,7-dimethyl-1.7-octadiene and mixed isomers of dihydromyricene and dihydroocinene, single ring alicyclic dienes. such as 1,3-cyclopentadiene; 1,4-cyclohexadiene; 1.5-cyclooctadiene and 1.5-cyclododecadiene. and multi-ring alicyclic fused and bridged ring dienes. such as tetrahydroindene. methy l tetrahydroindene, dicyclopentadiene, bicyclo-(2.2,l )-hepta-2,5-diene: alkenyl, aikylidene. cycloalkenyl and cycloalkylidene norbornenes, such as 5 -methylene- 2 -norbornene (MNB); 5- propenyl-2-norbornene. 5-isopropylidene-2-norbornene. 5-(4-cyciopenienyl)-2-norbornene. 5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene. and norbornadiene. Of the dienes typically used to prepare EPDMs. the particularly preferred dienes are 1 ,4-hexadiene (HD). 5-ethylidene-2-norbornene (ENB). 5-vinylidene-2-norbornene (VNB), 5-methylene-2- norbornene (VfNB), and dicyclopentadiene (DCPD). The especially preferred dienes are 5- ethylidene-2-norbornene (ENB) and 1.4-hexadiene (HD). JOlOO] One class of desirable polymers that can be made in accordance with embodiments of the invention are cia^tomeric inierpolymers of ethy lene, a C3-C20 u-oleiin. cvpeαalh prop} Icne. and optionally one or more diene
Figure imgf000030_0001
α-υlcilns for use in this, embodiment of the presera im ention are designated hy the formula C I^ CHR+. where R* is a linear or branched alkyl group of from 1 lo 12 carbon atoms. Examples of suitable α-olefms include, but are not limited to, propy lene. isobutylene. 1 -butene, 1 -pentene, 1-hexene, 4-methyl-l -pentene. and 1-ocτ.ene. Λ particularly preferred α-olefin is propylene. The propylene based polymers are generally referred to in the art as EP or EPDM polymers. Suitable dienes for use in preparing such polymers, especially multi-block EPDM type polymers include conjugated or non-conjugated, straight or branched chain-, cyclic- or poly cyclic- dienes comprising from 4 to 20 carbons. Preferred dienes include 1.4-pentadiene, 1 ,4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, cyclohexadiene. and 5- butyli.dene-2-norbomene, A particularly preferred diene is 5-ethylidene-2-norbornene. [0101] Because the diene containing polymers comprise alternating segments or blocks containing greater or lesser quantities of the diene (including none) and α-olefin (including none), the total quantity of diene and α-olef In may be reduced without loss of subsequent polymer properties. That is. because the diene and α-olefin monomers are preferentially incorporated into one type of block of the polymer rather than uniformly or randomly throughout the polymer, they are more efficiently utilized and subsequently the crosslink density of the polymer can be better controlled. Such crosslinkable elastomers and the cured products have advantaged properties, including higher tensile strength and better elastic recovery.
[0102] In some embodiments, the inventive interpolymers made with two catalysts incorporating differing quantities of comonomer have a weight ratio of blocks formed thereby from 95:5 to 5:95. The elastomeric polymers desirably have an ethylene content of from 20 to 90 percent, a diene content of from 0.1 to 10 percent, and an α-olefin content of from 10 to 80 percent, based on the total weight of the polymer. Further preferably, the multi-block elastomeric polymers have an ethylene content of from 60 to 90 percent, a diene content of from 0.1 to 10 percent, and an α-olefm content of from 10 to 40 percent, based on the total weight of the poi>mer. Preferred polymers are high molecular weight polymers, ha\ ing a weight average molecular weight (Mw) from 10.000 to about 2.500.000. preferably from 20,000 to 500.000, more preferably from 20.000 to 350.000, and a polydispersity less than 3.5. more preferably less than 3.0. and a Mooney \iscosity (ML ( 1 -4) 125°C.) from 1 to 250. More preferably, such polymers have an ethy lene content from 65 to 75 percent, a diene content from 0 to 6 percent, and an α-ύlefin content from 20 to 35 percent. (0103J The ethylene α-olelm interpoK mcrs can be iunetionaii/eu by incorporating at least one functional group in \U polymer structure. Exemplary functional groups may include, for example, ethyienieuϊk unsaturated mono- and di-functional carboxylic acid^. ethylenically unsaturated mono- and di~ functional carboxylic acid anhydrides, salts thereof and esters thereof. Such functional groups may be grafted to an ethylene/α -olefin interpolymer. or it may be copolymerized with ethylene and an optional additional comonomer to form an interpolymer of ethylene, the functional comonomer and optionally other comonomer(s). Means for grafting functional groups onto polyethylene are described for example in U.S. Patents Nos. 4,762,890, 4.927,888, and 4.950,541, the disclosures of these patents are incorporated herein by reference in their entirety. One particularly useful functional group is malic anhydride,
[0104] The amount of the functional group present in the functional interpolymer can vary. The functional group can typically be present in a copolymer- type functional i zed interpolymer in an amount of at least about 1.0 weight percent, preferably at least about 5 weight percent, and more preferably at least about 7 weight percent. The functional group will typically be present in a copolymer-type functionalized interpolymer in an amount less than about 40 weight percent, preferably less than about 30 weight percent, and more preferably less than about 25 weight percent.
Testing Methods
[0105] In the examples that follow, the following analytical techniques are employed:
GPC Method for Samples 1-4 and A-C
[0106J An automated liquid-handling robot equipped with a heated needle set to 1600C is used to add enough 1 ,2,4-trichlorobenzene stabilized with 300 ppm ionol to each dried polymer sample to
Figure imgf000032_0001
a final concentration of 30 mg/mL. A small glass stir rod is placed into each tube and the samples are heated to 1600C for 2 hours on a heated, orbital -shaker rotating at 250 rpm. The concentrated polymer solution is then diluted to 1 mg/ml using the automated liquid-handling robot and the heated needle set to 16O0C. [0107] A Symyx Rapid GPC system is used to determine the molecular weight data for each sample. A Gilson 350 pump set at 2.0 mimin flow rate is used to pump helium-purged 1.2-dichlorobenzenc stabilized with 300 ppm Ionol as the mobile phase through three Plgel 10 micrometer <μm) Mixed B 300mm x 7.5mm columns placed in series and heated to 160cC. A PoK mer Labs ELS 1000 Detector is used with the E\aporator set to 25O0C. the Nebuii/er set to I65CC. and the nitrogen flow rate set to 1 ,8 SLM at a pressure of 60-80 pή (4UO-600 kPa) N:. The polymer samples are heated to 1600C and each sample injected into a 250 μl loop u^ing the liquid-handling robot and a heated needle. Serial analysis of the
-?y- polymer samples using two switched loops and overlapping injections are used. The sample data is collected and anal; zed using Symyx Epoch™ software. Peaks are manually integrated and the molecular weight information reported imcorrected against a polv styrene standard calibration cur\e.
Standard CRYSTAF Method
[0108J Branching distributions are determined by crystallization analysis fractionation (CRYSTΛF) using a CRYSTAF 200 unit commercially available from PolymcrChar. Valencia, Spain. The samples are dissolved in 1 ,2,4 trichlorobenzene at 1600C (0.66 mg/niL) for 1 hour and stabilized at 95°C for 45 minutes. The sampling temperatures range from 95 to 300C at a cooling rate of 0.20C7ITaIn. An infrared detector is used to measure the polymer solution concentrations. The cumulative soluble concentration is measured as the polymer crystallizes while the temperature is decreased. The analytical derivative of the cumulative profile reflects the short chain branching distribution of the polymer. [0109| The CRYSTΛF peak temperature and area are identified by the peak anal y sis module included in the CRYSTAF Software (Version 200 l .b, PoiymerChar, Valencia, Spain). The CRYS FAF peak finding routine identifies a peak temperature as a maximum in the dW/dT curve and the area between the largest positive inflections on either side of the identified peak in the derivative curve. To calculate the CRYSfAF curv e, the preferred processing parameters are with a temperature limit of 7O0C and with smoothing parameters above the temperature limit of 0.1. and below the temperature limit of 0.3.
DSC Standard Method (Excluding Samples 1-4 and A-C)
10110] Differential Scanning Calorimetry results are determined using a TAI model QlOOO DSC equipped with an RCS cooling accessory and an autosampler. A nitrogen purge gas flow of 50 ml min is used. The sample is pressed into a thin film and melted in the press at about 175°C and then air-cooled to room temperature (25°C). 3-10 mg of material is then cut into a 6 mm diameter disk, accurately weighed, placed in a light aluminum pan (ca 50 mg). and then crimped shut. 1 he thermal behav ior of the sample is investigated with the following temperature profile. The sample is rapidly heated to 180cC and held isothermal for 3 minutes in order to remove
Figure imgf000033_0001
previous thermal histon.. I he sample is then cooled to - 40"C at ?0X min cooling rate and helα at -40X foi 3 minute1-, f he sample is then heated *o 15(1X at 10 C min. heating rate. I he cooling and second heating curves are recorded. [0111] The DSC melting peak is measured as the maximum in heat flow rate (W/g) with respect to the linear baseline drawn between -30&C and end of melting. The heat of fusion is measured as the area under the melting curve between -3O0C and the end of melting using a linear baseline.
GPC Method (Excluding Samples 1-4 and A-C)
[0112] The gel permeation chromatographic system consists of either a Polymer Laboratories Model PL-210 or a Polymer Laboratories Model PL-22G instrument. The column and carousel compartments are operated at HO0C. Three Polymer Laboratories 10- micron Mixed-B columns are used. The solvent is 1,2,4 trichlorobenzene. The samples are prepared at a concentration of O. t grams of polymer in 50 milliliters of solvent containing 200 ppm of butylated hydroxytoluene (BHT). Samples are prepared by agitating lightly for 2 hours at 16O0C. The injection volume used is 100 microliters and the flow rate is 1.0 ml/minute.
[0113] Calibration of the GPC column set is performed with 21 narrow molecular weight distribution polystyrene standards with molecular weights ranging from 580 to 8,400,000, arranged in 6 ""cocktail" mixtures with at least a decade of separation between individual molecular weights. The standards are purchased from Polymer Laboratories (Shropshire, UK). The polystyrene standards are prepared at 0.025 grams in 50 milliliters of solvent for molecular weights equal to or greater than 1.000.000. and 0.05 grains in 50 milliliters of solvent for molecular weights less than 1 ,000.000. The polystyrene standards are dissolved at 800C with gentle agitation for 30 minutes. The narrow standards mixtures are run first and in order of decreasing highest molecular weight component to minimize degradation. The polystyrene standard peak molecular weights are converted to polyethylene molecular weights using the following equation (as described in Williams and Ward, J. Polvm. ScL PoKm Let., 6, 621 (1968)): Methylene = 0.431 (Mpcl>slKC11e)-
[0114] Polyethylene equivalent molecular weight calculations are performed using Viscotek TriSEC software Version 3.0.
Compression Set
[0115] Compression set is measured according to ΛSTM D 395. The sample is prepared by stacking 25.4 mm diameter round discs of 3.2 mm, 2.0 mm. and 0.25 mm thickness until a total thickness of 12.7 mm is reached. The discs are eui from 12.7 cm x 12,7 cm compression molded plaques molded with a hot press under the following conditions: zero pressure for 3 minutes at 1900C, followed by 86 MPa for 2 minutes at 19O0C. followed by cooling inside the press with coϊd running water at 86 MPa.
Density
[0116] Samples for density measurement are prepared according to ASTM D 1928. Measurements are made within one hour of sample pressing using ASTM D792. Method B.
Flexural/Secant Modulus/ Storage Modulus
[0117] Samples are compression molded using ASTM D 1928. Flexural and 2 percent secant moduli are measured according to ASTM D-790. Storage modulus is measured according to ASTM D 5026-01 or equivalent technique.
Optical properties
[0118] Films of 0.4 mm thickness are compression molded using a hot press (Carver
Model #4095-4PR1001 R). The pellets are placed between polvtetrafluoroethylene sheets. heated at 190 0C at 55 psi (380 kPa) for 3 minutes, followed b> 1.3 MPa for 3 minutes, and then 2.6 MPa for 3 minutes. The film is then cooled in the press with running cold water at
1.3 MPa for 1 minute. The compression molded films are used for optical measurements. tensile behavior, recovery, and stress relaxation.
[0119] Clarity is measured using BYK Gardner Haze-gard as specified in ASTM D 1746.
[0120] 45° gloss is measured using BYK Gardner Glossmeter Microgloss 45° as specified in ASTM D-2457.
[0121] Internal haze is measured using BYK Gardner Haze-gard based on ASTM D 1003
Procedure A. Mineral oil is applied to the film surface to remove surface scratches.
Mechanical Properties - Tensile, Hysteresis, and Tear
[0122] Stress-strain behavior in uniaxial tension is measured using ASTM D 1708 microtensiie specimens. Samples are stretched with an Instron at 500% min~' at 213C. Tensile strength and elongation at break are reported from an average of 5 specimens. J0123] 100% and 300% Hjsteresis is determined from cyclic loading to 100% and 300% strains using ASTM D 1708 microtensiie specimens with an Instron I M instrument. The sample i« loaded and unloaded at 267 % raϊrf ' for 3 cvcles at 21 CC C) cue experiments at 300% and 80c€ arc conducted using an environmental chamber. In the HlK" experiment, trie sample is allowed Co equilibrate for 45 minutes at the test temperature before testing. In the 210C, 300% strain cyclic experiment, the retracth e stress at 150% strain from the first unloading cycle is recorded. Percent recovery for all experiments are calculated from the first unloading cycle using the strain at which the load returned to the base line. The percent recovery is defined as:
% Re cov ery = ™ x 100 ε ,
where εf is the strain taken for cyclic loading and ε., is the strain where the load returns to the baseline during the T1 unloading cycle.
)0124j Stress relaxation is measured at 50 percent strain and 37°C for 12 hours using an ϊnstron™ instrument equipped with an environmental chamber. The gauge geometry was 76 mm x 25 mm x 0.4 mm. After equilibrating at 37°C for 45 min in the environmental chamber, the sample was stretched to 50% strain at 333% min"1. Stress was recorded as a function of time for 12 hours. The percent stress relaxation after 12 hours was calculated using the formula:
I — I
% Stress Relaxation = — — x 100
L J n0
where L,) is the load at 50% strain at 0 time and L) 2 is the load at 50 percent strain after 12 hours.
[0125] Tensile notched tear experiments are carried out on samples having a density of 0.88 g/cc or less using an Instron™ instrument. The geometry consists of a gauge section of 76 mm x 13 mm x 0.4 mm with a 2 mm notch cut into the sample at half the specimen length. The sample is stretched at 508 mm min'1 at 21 0C until it breaks. The tear energy is calculated as the area under the stress-elongation curve up to strain at maximum load. An average of at least 3 specimens are reported.
TMA
[0126] Thermal Mechanical Analysis ^Penetration Temperature) is conducted on 30mm diameter x 3.3 mm thick, compression molded discs, formed at 18O0C and 10 MPa molding prc:>sure for 5 minutes and then air quenched. Flic instrument used is a TMA 7. brand awϋable from Perkin-Hmer. In the test, a probe with 1.5 mm radium tip (P Ts N519-0416) h.-, applied to the surface of the sample disc with 1 \* force. F he temperature is raised at 5T min from 25°C. The probe penetration distance is measured as a function of temperature. The experiment ends when the probe has penetrated 1 mm into the sample.
DMA
JΘ127] D\namic Mechanical Analysis (DMA) is measured on compression molded disks formed in a hot press at 18O0C at 10 MPa pressure for 5 minutes and then v\ater cooled in the press at 900C / min. Testing is conducted using an ARES controlled strain rheometer (TA instruments) equipped with dual cantilever fixtures for torsion testing. [0128] A 1.5mm plaque is pressed and cut in a bar of dimensions 32x12mm. The sample is clamped at both ends between fixtures separated by 10mm (grip separation ΔL) and subjected to successive temperature steps from -1000C to 2000C (5°C per step). At each temperature the torsion modulus G' is measured at an angular frequency of 10 rad/s, the strain amplitude being maintained between 0.1 percent and 4 percent to ensure that the torque is sufficient and that the measurement remains in the linear regime.
10129] An initial static force of 10 g is maintained (auto -tension mode) to prevent slack in the sample when thermal expansion occurs. As a consequence, the grip separation ΔL increases with the temperature, particularly above the melting or softening point of the polymer sample. The test stops at the maximum temperature or when the gap between the ilxtures reaches 65 mm.
Melt Index
[0130] Meit index, or I2. is measured in accordance with AS TVl D 1238, Condition 190X72.16 kg. Melt index, or Iio is also measured in accordance with ASTM D 1238, Condition 1900COO kg.
ATREF
[0131 ] Aπah tical temperature rising elution fractionation (A I RhF) anal) sis is conducted according to the method described in U.S. Patent No. 4.798.081 and Wilde, L.; Rj Ie, f.R.; Knobeloch. D. C: Peat. I.R.: Determination of Branching Distributions in Polyethylene and Ethylene Copolymers. J. PoKm. ScL 20, 441-455 ( 1982), which are incorporated b> reference herein in their entire!} . The composition to be analvzed is dissohed in tπehSorobeπ/eπe and allowed to cnstalh/e in a column containing an inert bupport (>tamle^ steel shot* b\ slowh reducing the temperature to 2lP€ at a cooling rate of O. TC min. the column h equipped with an infrared detector. An Λ I RFF ehromatograin curve is then generated by eluting the crystallized poljmer sample from the column
Figure imgf000038_0001
slowly increasing the temperature of the eluting solvent (trichloroben/ene) from 20 to 12O0C at a rate of 1.50C/min.
13C NMR Analysis
[0132] The samples are prepared by adding approximately 3g of a 50'5O mixture of telrachioroethane-d" orthodichlorobenzene to 0.4 g sample in a 10 mm NMR tube. The samples are dissolved and homogenized by heating the tube and its contents to 1500C. The data are collected using a JEOL Eclipse™ 400MHz spectrometer or a Varian Unity Plus™ 400MHz spectrometer, corresponding to a 13C resonance frequency of 100.5 MHz. The data are acquired using 4000 transients per data file with a 6 second pulse repetition delay. To achieve minimum signal-to-noise for quantitative analysis, multiple data files are added together. The spectral width is 25,000 Hz with a minimum file size of 32K data points. The samples are analyzed at 130 0C in a 10 mm broad band probe. The comonomer incorporation is determined using Randall's triad method (Randall, J. C; JMS-Rev. Macromol. C hem. Phys., C29, 201-317 (1989), which is incorporated bv reference herein in its entirety.
Polymer Fractionation by TREF
|Q133] Large-scale TREF fractionation is carried by dissolving 15-20 g of polymer in 2 liters of 1.2,4-trichlorobenzene (TCB)by stirring for 4 hours at 1600C. The pol>mer solution is forced b> 15 psig ( 100 kPa) nitrogen onto a 3 inch by 4 fool (7.6 cm x 12 cm) steel column packed with a 60:40 (v:v) mix of 30-40 mesh (600-425 μm) spherical, technical qualϊt) glass beads (available from Potters Industries, HC 30 Box 20, Brownwood, IX, 76801) and stainless steel, 0.028" (0.7mm) diameter cut wire shot (available from Pellets. Inc. 63 Industrial Drive, North Tonawanda, NY. 14120). I he column is immersed in a thermally controlled oil jacket set initially to 1600C. The column is first cooled ballistically to 125°C\ then slow cooled to 2O0C at 0.040C per minute and held for one hour. Fresh TCB is introduced at about 65 ml'min while the temperature is increased at 0.1670C per minute. [0134] Approximately 2000 ml portions of eiuant from the preparative ϊ Rh! column are collected in a 16 station, heated fraction collector. The pohmer is concentrated in each fraction using a rotan evaporator until about 50 to 100 ml of the poKmer solution remains, I he concentrated HiiUttons are allowed io •-tαnd overnight before adding excess methanol, filtering, and rinsmg (jpprox. 3CO-50O ml of methanol including the final rinse i. f he filtration step is performed on A 3 position vacuum assisted filtering station using 5.0 μm polytetrafluoroethviene coated filter paper (available from Osmonics Inc.. Cat^ Z50WP04750). The filtrated fractions are dried overnight in a \ acuum ov en at 60cC and weighed on an analytical balance before further testing.
Melt Strength
[0135] Melt Strength (MS) is measured by using a capillary rheometer fitted with a 2.1 mm diameter, 20: 1 die with an entrance angle of approximate^ 45 degrees. After equilibrating the samples at 1900C for 10 minutes, the piston is run at a speed of 1 inch/minute (2.54 cm/minute). The standard test temperature is 1900C. The sample is drawn uniaxially to a set of accelerating nips located 100 mm below the die with an acceleration of 2.4 mm/sec2. The required tensile force is recorded as a function of the take-up speed of the nip rolls. The maximum tensile force attained during the test is defined as the melt strength. ϊn the case of polymer melt exhibiting draw resonance, the tensile force before the onset of draw resonance was taken as melt strength. The melt strength is recorded in centiNewtons ("cN").
Catalysts
[0136] The term "overnight", if used, refers to a time of approximately 16-18 hours, the term "room temperature", refers to a temperature of 20-25 0C. and the term "'mixed alkanes" refers to a commercial^ obtained mixture of CVy aliphatic hydrocarbons available under the trade designation Isopar Eκ, from ExxonMobil Chemical Company. In the event the name of a compound herein does not conform to the structural representation thereof, the structural representation shall control. The s>nthesis of all metal complexes and the preparation of all screening experiments were carried out in a dry nitrogen atmosphere using dry box techniques. AU solvents used were HPLC grade and were dried before their use. [0137] MMAO refers to modified
Figure imgf000039_0001
a triisohutylaluminum modified methj lalumoxane available commercially from Akzo-Noble Corporation. [0138| T. he preparation of catalyst (Bl) is conducted as follows. a)
Figure imgf000039_0002
Figure imgf000039_0003
(3.00 g) is added to 10 mL of isopropviamine. The solution rapidly turns bright
Figure imgf000039_0004
After stirring at ambient temperature lor 3 hours. are removed under v acuum Io }ieid a bright cry stalline solid (97 percent \ ieldj. b) Preparation of 1 ■2-bis-(3,5-di-t-but\ lpheny lene)( 1 -(N-( 1 - methylethyl)immino)meth\l)(2-oxov l) yireonium dibenzyl
A solution of (l-methylethyl)(2-hvdroxy-3.5-di(t-bυtyI)phenyl)imine (605 mg. 2.2 rømol) in 5 mL toluene is slowly added to a solution of Zr(CH2Ph)4 (500 mg, 1.1 mmol) in 50 mL toluene. The resulting dark yellow solution is stirred for 30 minutes. Solvent is removed under reduced pressure to yield the desired product as a reddish-brown solid.
[0139| The preparation of catalyst (B2) is conducted as follows. a)
Figure imgf000040_0001
2-Methylcyciohexylamine (8.44 mL, 64.0 mmol) is dissolved in methanol (90 mL). and di-t-butylsalicaldehydc (10.00 g, 42,67 mmol) is added. The reaction mixture is stirred for three hours and then cooled to -250C for 12 hours. The resulting yellow solid precipitate is collected by filtration and washed with cold methanol (2 x 15 mL), and then dried under reduced pressure. The yield is 1 1.17 g of a yellow solid. 1H NMR is consistent with the desired product as a mixture of isomers.
b) Preparation of bis-(l-(2-methylcyclohexyl)ethy1)(2-oxoy!-3,5-di(t-butyl)phenyl) immino)/irconium dibenzyl
Λ solution of ( 1 -(2-methy lcyclohexyl)ethy l)(2-oxoy l-3.5-di(t-buty l)phenyl)imine (7.63 g, 23.2 mmol) in 200 mL toluene is slovvlv added to a solution of Zr(CH2Ph)4 (5.28 g. 11.6 mmol) in 600 mL toluene. The resulting dark yellow solution is stirred for 3 hour at 25°C. The solution is diluted further with 680 mL toluene to give a solution having a concentration of 0.00783 M.
[0140] Cocatalyst 1 Λ mixture of methy IdI(C μ-is
Figure imgf000040_0002
l)ammonium salts of tetrakis(pentafluorophenyl)borate (here-in-after armeenium borate), prepared by reaction of a long chain
Figure imgf000040_0003
(Λrmeen™ M2HT. available from Akzo-Nobel. Inc.). HCl and Li[B(CnFO4], substantially as disclosed in USP 5,919.9883, Ex. 2. [0141] Cocatalyst 2 Mixed Cj4-1S alkjldimethv lammonium salt of bis(tπs(pentafluorophcn> l )-alυmane)-2-undec\ limida/-oIide, prepared according to L'SP 6.395.671. Kx. 16.
[0142] Shuttling Agents I he shuttling agents empiovcd include diothv i/ϊπc ,,DF/. SA 1 1.
Figure imgf000040_0004
\ FFA. SA-tj,
-?8- trioctylaluminum (S A5). triethylgalϋum (S A6). i-hutylaluminum bis(dimethyi(t- buty I)si1oxane) (SA7). i-butylaluminum bis(di(tritnethylsilyl)amide) (S A8), n-octylaluminum di(pvridinc-2-methoxide) (SA9), bis(n-octadecyl)i-but\lalurainum (SAlO), i-butylaluminum bis(di(n-pentyl)atnide) (SAl 1), n-octylaluminum bis(2,6-di-t-butylphenoxide) (SA12), n- octylaluminum di(ethyl(l~naphthyl)amide) (SA 13), ethylalumiiπim bis(t- butyldimethylsiloxide) (SAl 4), ethylaluminum di(bis(trimethylsilyl)amide) (SA15), ethylaluminum bis(2.3»6,7-diben7o-l -azacycloheptaneamide) (SA36), n-octylaluminum bis(2.3,6,7-dibenzo-ϊ-azacycloheptaneamide) (SAl 7), n-octylaluminum bis(dimethyl(t- butyl)siloxide(SA18), ethylzinc (2,6-diphenylphenoxide) (SA 19), and ethyl zinc (t-butoxide) (SA20).
Examples 1-4, Comparative A-C
General High Throughput Parallel Polymerization Conditions
[0143] Polymerizations are conducted using a high throughput, parallel polymerization reactor (PPR) available from Symyx Technologies, Inc. and operated substantially according to US Patents No. 6.248,540. 6.030,917. 6,362,309. 6.306.658, and 6,316,663. Ethylene copolymerizations are conducted at 1300C and 200 psi (1.4 MPa) with ethylene on demand using 1 ,2 equivalents of cocatalyst 1 based on total catalyst used (1.1 equivalents v\hen MMAO is present). A series of polymerizations are conducted in a parallel pressure reactor (PPR) contained of 48 individual reactor cells in a 6 x 8 array that are fitted with a pre- weighed glass tube. The working volume in each reactor cell is 6000 μL. Each ceil is temperature and pressure controlled with stirring provided by individual stirring paddles. The monomer gas and quench gas are plumbed directly into the PPR unit and controlled by automatic valves. Liquid reagents are robotically added to each reactor cell by syringes and the reservoir solvent is mixed alkanes. The order of addition is mixed aikanes sohent (4 ml), ethylene, 1-octene comonomer (1 ml), cocatalyst 1 or cocatalyst KMM AO mixture, shuttling agent, and catalyst or cataly st mixture. When a mixture of cocatalyst 1 and MMAO or a mixture of two catalysts is used, the reagents are prcmixed in a small vial immediately prior to addition to the reactor. When a reagent is omitted in an experiment, the above order of addition h otherwise maintained. Polymerizations are conducted for approximately 1-2 minutes, until predetermined ethylene consumptions are reached. After quenching with CX). the reaetoFb are cooled and the glass lubes are unloaded. 1 he tubes are transferred io a. centrifuge vacuum drying unit, and dried for 12 hours at 6O0C. The tubes containing dried polymer are weighed and the difference between this weight and the tare weight gives the net >ield of polymer. Results are contained in Table 1. In Table 1 and elsewhere in the application, comparative compounds are indicated b\ an asterisk (*).
[0144] Examples 1-4 demonstrate the s\nthesis of linear block copolymers by the present invention as evidenced by the formation of a very narrow MWD. essentially monomodal copolymer when DEZ is present and a bimodal. broad molecular weight distribution product (a mixture of separately produced polymers) in the absence of DEZ. Due to the fact that Catalyst (Al ) is known to incorporate more octene than Catalyst (B I ), the different blocks or segments of the resulting copolymers of the invention are distinguishable based on branching or density.
Table t
Cat. (Λ I ) Cat (B I ) Cocat MMAO shuttling
Ex. (jimoj) (μmol) (μmol) LujnoTj agent (μmol) Yield (g) Mn MWMn hexyls'
A* 0.06 - 0.066 0.3 - 0.1363 300502 3.32
B* - 0.1 O. i l O 0.5 - 0.1 581 36957 1 .22 2.5
C* 0.06 0.1 0.176 0.8 - 0.2038 45526 5.3O2 5.5
1 0.06 0.1 0.192 - DEZ (8.0) 0.1974 28715 1.19 4.8
2 0.06 0.1 0.192 - DEZ (80.0) 0.1468 2161 1.12 14.4
3 0.06 0.1 0.192 - FKA (S-O) 0.208 22675 1.71 4.6
4 0.06 0.1 0.192 - TEA (80.0) 0.1 879 3338 Ϊ .54 9.4
1 C(, or higher chain content per 1000 carbons
2 Bimodal molecular weight distribution
[0145] It may be seen the polymers produced according to the invention have a relatively narrow polydispersity (MwMn) and larger block-copoiymer content (irimer, tetramer, or larger) than polymers prepared in the absence of the shuttling agent. [0146] Further characterizing data for the polymers of Table 1 are determined by reference to the figures. More specifically DSC and ATREF results show the following: [0147J The DSC curve for the polymer of example 1 shows a 1 15.7°C melting point (Tm) with a heat of fusion of 158.1 J g. The corresponding CRYSTAF curve shows the tallest peak at 34.50C with a peak area of 52.9 percent. The difference between the DSC Tm and the rcry staf is 81.2°C.
[0148] The DSC curs e for the polymer of example 2 shows a peak with a 109.70C melting point (Tm) with a heat of fusion of 214.0 J g. The corresponding CRYSTAF curve shows the tallest peak at 46.2°C with a peak area of 57.0 percent. The difference between the I)SC Fm and the Fcn ^uf is 63.5°C. [0149J The DSC cur\ e for the polymer of example 3 shows a peak with a 120.70C melting point (Tm) with a heat of fusion of 160.1 J/g. The corresponding CRYSTAF curve shows the tallest peak at 66.1°C with a peak area of 71.8 percent. The difference between the DSC Tm and the Tcrystaf is 54.6°C.
[0150] The DSC curve for the polymer of example 4 shows a peak with a 104.50C melting point (Tm) with a heat of fusion of 170.7 J/g. The corresponding CRYSTAF curve shows the tallest peak at 30 0C with a peak area of 18.2 percent. The difference between the DSC Tm and the Tcrystafis 74.5°C.
[0151] The DSC curve for comparative A shows a 90.00C melting point (Tm) with a heat of fusion of 86.7 J/g. The corresponding CRYSTΛF curve shows the tallest peak at 48.5°C with a peak area of 29.4 percent. Both of these values are consistent with a resin that is low in density. The difference between the DSC Tm and the Tcrystaf is 41.80C. [0152] The DSC curve for comparative B shows a 129.8°C melting point (Tm) with a heat of fusion of 237.0 J/g. The corresponding CRYSTAF curve shows the tallest peak at 82.40C with a peak area of 83.7 percent. Both of these values are consistent with a resin that is high in density. The difference between the DSC Tm and the Tcrystaf is 47.4°C. [0153] The DSC curve for comparative C shows a 125.3QC melting point (Tm) with a heat of fusion of 143.0 J/g. The corresponding CRYSTΛF curve shows the tallest peak at 81.8 0C with a peak area of 34.7 percent as well as a lower crystalline peak at 52.4 0C. The separation between the two peaks is consistent with the presence of a high crystalline and a low crystalline polymer. The difference between the DSC Tm and the Tcrystaf is 43.5°C.
Examples 5-19, Comparatives D-F, Continuous Solution Polymerization, Catalyst A1/B2 + DEZ
[0154] Continuous solution polymerizations are carried out in a computer controlled autoclave reactor equipped with an internal stirrer. Purified mixed alkanes solvent (Isopar1 M E available from ExxonMobil Chemical Company ), ethylene at 2.70 ib& hour (1.22 kg/hour). 1-octene. and hydrogen (where used) are supplied to a 3.8 L reactor equipped with a jacket for temperature control and an internal thermocouple. The sohent feed to the reactor is measured by a mass-flow controller. A variable speed diaphragm pump controls the solvent ilυw rate and pressure to the reactor. At the discharge of the pump, a side stream is taken to prov ide flush flows for the catalyst and eocatahst I injection lines and the reactor agitator. I hcse flows are measured by Micro-Motion mass flow meters and controlled b> control valves or by the manual adjustment of needle valves. The remaining sohent is combined with l~octene, ethy iene, and hydrogen (where used) and fed to the reactor. Λ mass flow controller is used to deliver hydrogen to the reactor as needed. The temperature of the solvent/monomer solution is controlled by use of a heat exchanger before entering the reactor. This stream enters the bottom of the reactor. The catalyst component solutions are metered using pumps and mass flow meters and are combined with the catalyst flush solvent and introduced into the bottom of the reactor. The reactor is run liquid-full at 500 psig (3.45 MPa) with vigorous stirring. Product is removed through exit lines at the top of the reactor. All exit lines from the reactor are steam traced and insulated. Polymerization is stopped by the addition of a small amount of water into the exit line along with any stabilizers or other additives and passing the mixture through a static mixer. The product stream is then heated by passing through a heat exchanger before devolatilization. The polymer product is recovered by extrusion using a devolatilizing extruder and wrater cooled pelletizer. Process details and results are contained in Table 2. Selected polymer properties are provided in Table 3.
Figure imgf000045_0001
Figure imgf000046_0001
10155] The resulting polymers are tested by DSC and Al REF as with previous examples.
Results are as follows:
[0156] The DSC cur\e for the pohmer of example 5 shows a peak with a 119.6 0C melting point (Tm) with a heat of fusion of 60.0 J/g. The corresponding CRYSTAF curve shows the tallest peak at 47.6°C with a peak area of 59.5 percent, f he delta between the DSC
Tm and the Tcrystaf is 72.00C.
|0157| The DSC curve for the polymer of example 6 shows a peak with a 115.2 0C melting point (Tm) with a heat of fusion of 60.4 J 'g. I he corresponding CRYSTAF curve shows the tallest peak at 44.2°C with a peak area of 62.7 percent. The delta between the DSC
Tm and the Tcrystaf is 71.00C.
[0158] The DSC curve for the polymer of example 7 shows a peak with a 121.3 0C melting point with a heat of fusion of 69.1 J''g. The corresponding CRYSlAF curve shows the tallest peak at 49.2°C with a peak area of 29.4 percent. The delta between the DSC Tm and the Tcrystaf is 72.10C.
[Θ159] The DSC curve for the polymer of example 8 shows a peak with a 123.5 0C melting point (Tm) with a heat of fusion of 67.9 J/g. The corresponding CRYSTAF curve shows the tallest peak at 80.10C with a peak area of 12.7 percent. The delta between the DSC
Tm and the Tcrystaf is 43.4°C.
10160] The DSC curve for the polymer of example 9 shows a peak with a 124.6 0C melting point (Tm) with a heat of fusion of 73.5 J/g. 1 he corresponding CRYSTAF curve shows the tallest peak at 80.80C with a peak area of 16.0 percent. The delta between the DSC
Tm and the 1 crystal* is 43.80C.
|Θ161] lhe DSC curve for the polymer of example 10 shows a peak with a 1 15.6 0C melting point (Tm) with a heat of fusion of 60.7 J/g. The corresponding CRYSTAF curve shows the tallest peak <st 40.90C with a peak area of 52.4 percent. The delta between the DSC
Tm and the Tcrystaf is 74.70C.
[0162] lhe DSC curve for the pohmer of example 1 1 shows a peak with a 1 13.6 0C melting point (Tm) with a heat of fusion of 70.4 J g. The corresponding CRYS TAF eurv e shows the tallest peak at 39.6°C with a peak area of 25.2 percent, fhe delta between the DSC i m and the Fcry ->tai is 74.1 2C.
JΘ1631 l he DSC cum lor the poh niei oi evampϊe 12
Figure imgf000047_0001
a peak with a 1 I J Z % melting point ( I m } with a heat ef fusion of 48.9 J g I he corresponding CRYS ϊ Aϊ curv e shows no peak equal to or above 30 0C. (Ten staf for purposes of further calculation is therefore set at 3O0C). The delta between the DSC Tm and the Tcr>staf is 83.2°C. (0164f The DSC cur\ e for the polymer of example 13 shows a peak with a 1 14.4 °C melting point (Tm) with a heat of fusion of 49.4 J 'g. The corresponding CRYSTAF curve shows the tallest peak at 33.8 0C with a peak area of 7.7 percent. The delta between the DSC Tm and the Tcrystaf is 84.40C.
J0165] The DSC for the polymer of example 14 shows a peak with a 120.8 0C melting point (Tm) with a heat of fusion of 127.9 J/g. The corresponding CRYSTAF curve shows the tallest peak at 72.9 0C with a peak area of 92.2 percent. The delta between the DSC Tm and the Tcr>staf is 47.9°C.
[0166] The DSC curve for the polymer of example 15 shows a peak with a 1 14.3 0C melting point (Tm) with a heat of fusion of 36.2 J/g, The corresponding CRYSTAF curve shows the tallest peak at 32.3 0C with a peak area of 9.8 percent. The delta between the DSC Tm and the Tcrystaf is 82.00C. fO167| The DSC curve for the polymer of example 16 shows a peak with a 1 16.6 °C melting point (Tm) with a heat of fusion of 44.9 J/g, The corresponding CRYSTAF curve shows the tallest peak at 48.0 0C with a peak area of 65.0 percent. The delta between the DSC Tm and the Tcrystaf is 68.6°C.
[0168] The DSC curve for the polymer of example 17 shows a peak with a 116.0 0C melting point (Tm) with a heat of fusion of 47.0 J'g, The corresponding CRYSTAF curve shows the tallest peak at 43.1 0C with a peak area of 56.8 percent. The deita between the DSC Tm and the Tcrystaf is 72.9°C.
[0169] The DSC curve for the polymer of example 18 shows a peak with a 120.5 0C melting point ( Fm) with a heat of fusion of 141.8 J,g. The corresponding CRYSTAF curve shows the tallest peak at 70.0 0C with a peak area of 94.0 percent. The delta between the DSC Tm and the Tcrystaf is 50.5 0C.
[0170] The DSC curve for the poh mer of example 19 shows a peak with a 124.8 0C melting point (Tm) with a heat of fusion of 174.8 J g. The corresponding CRYS FAF curve shows the tallest peak at 79.9 0C with a peak area of 87.9 percent. The delta between the DSC I m and the Fcr> staf is 45.0 0C.
[0171 J I he DSC cune for the polymer of comparative D shows a peak with a ??,3CC melting point ( Fm f with a heat of fusion oι' 31.6 J g. I he corresponding CRYS FAF can e shows no peak equal to and above 300C. Both of these \ allies are consistent with a resin that is low in density. The delta between the DSC Tm and the lcr>staf is 7.3°C. [0172] The DSC cuπ e for the polymer of comparative E shows a peak with a 124.0 0C melting point (Tm) with a heat of fusion of 179.3 Pg. The corresponding CRYSlAt cuπe shows the tallest peak at 79.3°C with a peak area of 94.6 percent. Both of these \ allies are consistent with a resin that is high in density. The delta between the DSC Tm and the Tcrystaf is 44.6°C.
[0173| The DSC curve for the polymer of comparative F shows a peak with a 124.8 0C melting point (Tm) with a heat of fusion of 90.4 Tg. The corresponding CRYSTAF curve shows the tallest peak at 77.6°C with a peak area of 19.5 percent. The separation between the two peaks is consistent with the presence of both a high crystalline and a low crystalline polymer. The delta between the DSC Tm and the Tcrystaf is 47.2°C.
Physical Property Testing
[0174J Polymer samples are evaluated for physical properties such as high temperature resistance properties, as evidenced by TMA temperature testing, pellet blocking strength, high temperature recovery, high temperature compression set and storage modulus ratio, 0'(250C)OXlOO0C). Several commercially available polymers are included in the tests: Comparative G* is a substantially linear ethylene/ 1-octene copolymer (AFHNI FYD, available from The Dow Chemical Company), Comparative H* is an elastomeric. substantially linear ethylene/ 1-octene copolymer (AFFINITY R LG8100, available from Fhe Dow Chemical Company ), Comparative 1 is a substantially linear ethylene' 1-octene copolymer (AFFINl IY ΦPL1840, available from The Dow Chemical Company), Comparative J is a hydrogenated sty rene, butadiene styrene triblock copolymer (KRATON™ G1652, available from KRA'ION Polymers). Comparative K is a thermoplastic vulcanizate (TPV. a poly olefin blend containing dispersed therein a cross linked elastomer). Results are presented in I able 4. Table 4 High Temperature Mechanical Properties
Figure imgf000050_0002
[0175] In Table 4, Comparative F (which is a physical blend of the two poϊ>mers resulting from simultaneous polymerizations using catalyst Al and B l) has a 1 mm penetration temperature of about 700C, while Examples 5-9 have a 1 mm penetration temperature of 1000C or greater. Further, examples 10-19 all have a 1 mm penetration temperature of greater than 850C, with most having 1 mm TMA temperature of greater than 900C or even greater than 1000C. This shows that the novel polymers have better dimensional stability at higher temperatures compared to a physical blend. Comparative J (a commercial SEBS) has a good 1 mm TMA temperature of about 1070C. but it has very poor (high temperature 7O0C) compression set of about 100 percent and it also failed to
Figure imgf000050_0001
(sample broke) during a high temperature (800C) 300 percent strain reeoxery. Thus the exemplified polymers ha\e a unique combination of properties unavailable e\en in some commercial!} available, high performance thermoplastic elastomers. 10176) Similarly. Tabic 4 shows a low fgoodi storage modulus ratio. (3'(25"C } (H 100"C), for the imenme polymers of 6 or less, whereas a physical blend (Comparathe I" ? has a storage modulus ratio oit and a random eth> icne octeno copolymer
-4? (Comparative G) of similar density has a storage modulus ratio an order of magnitude greater (89). It is desirable that the storage modulus ratio of a polymer be as close to 1 as possible. Such polymers will be relative!} unaffected by temperature, and fabricated articles made from such polymers can be usefully empkned over a broad temperature range, 1 his feature of low storage modulus ratio and temperature independence is particularly useful in elastomer applications such as in pressure sensith e adhesive formulations.
[0177] The data in Table 4 also demonstrate that the polvmers of the invention possess improved pellet blocking strength. In particular, Example 5 has a pellet blocking strength of 0 MPa, meaning it is free flowing under the conditions tested, compared to Comparathes F and G which show considerable blocking. Blocking strength is important since bulk shipment of polymers having large blocking strengths can result in product clumping or sticking together upon storage or shipping, resulting in poor handling properties. [0178| High temperature (700C) compression set for the inventh e polymers is generally good, meaning generally less than about 80 percent, preferably less than about 70 percent and especially less than about 60 percent. In contrast. Comparatives F, G, H and J all have a 700C compression set of 100 percent (the maximum possible value, indicating no recovery). Good high temperature compression set (low numerical values) is especially needed for applications such as gaskets, window profiles, o-rings. and the like.
_4y-
Figure imgf000052_0001
[0179| Table 5 shows results for mechanical properties for the new polymers as well as for various comparison polymers at ambient temperatures. It may be seen that the inventive polymers have very good abrasion resistance when tested according to ISO 4649, generally showing a volume loss of less than about 90 mmJ. preferably less than about 80 mm', and especially less than about 50 mπv\ In this test, higher numbers indicate higher volume loss and consequently lower abrasion resistance.
[0180] Tear strength as measured by tensile notched tear strength of the inventive polymers is generally 1000 mJ or higher, as shown in Table 5. Tear strength for the inventive polymers can be as high as 3000 m J. or even as high as 5000 mJ. Comparative polymers generally have tear strengths no higher than 750 mj.
[0181] Table 5 also shows that the polymers of the invention have better retractive stress at 150 percent strain (demonstrated by higher retractive stress values) than some of the comparative samples. Comparative Examples F, G and H have retractive stress value at 150 percent strain of 400 kPa or less, while the inventive polymers have retractive stress values at 150 percent strain of 500 kPa (Ex. 1 1 ) to as high as about 1 100 kPa (Ex, 17). Polymers having higher than 150 percent retractive stress values would be quite useful for elastic applications, such as elastic fibers and fabrics, especially nonwoven fabrics. Other applications include diaper, hygiene, and medical garment waistband applications, such as tabs and elastic bands.
[0182] Table 5 also shows that stress relaxation (at 50 percent strain) is also improved (less) for the inventive polymers as compared to, for example. Comparative Cr. Lower stress relaxation means that the polymer retains its force better in applications such as diapers and other garments where retention of elastic properties over long time periods at body temperatures is desired.
Optical Testing
Figure imgf000054_0001
[0183] The optical properties reported in Table 6 are based on compression molded films substantially lacking in orientation. Optical properties of the polymers may be varied over wide ranges, due to variation in crystallite size, resulting from variation in the quantity of chain shuttling agent employed in the polymerization.
Extractions of Multi-Block Copolymers
[0184] Extraction studies of the polymers of examples 5. 7 and Comparative E are conducted, in the experiments, the polymer sample is weighed into a glass fritted extraction thimble and fitted into a Kumagavva type extractor. The extractor with sample is purged with nitrogen, and a 50OmL round bottom flask is charged with 350 niL of diethyl ether. The flask is then fitted to the extractor. The ether is heated while being stirred. Time is noted when the ether begins to condense into the thimble, and the extraction is allowed to proceed under nitrogen for 24 hours. Λt this time, heating is stopped and the solution is allowed to cool. Any ether remaining in the extractor is returned to the flask, fhe ether in the flask is evaporated under vacuum at ambient temperature, and the resulting solids are purged dry with irirogen. Am residue is transferred to a weighed bottle ttMiig succc^si' e washes of hexane. The combined hexane washes are then evaporated with another nitrogen purge, and the residue dried under vacuum overnight at 4O0C. Any remaining ether in the extractor is. purged dry with nitrogen.
[01851 A second clean round bottom flask charged with 350 mL of hexane is then connected to the extractor. The hexane is heated to reflux with stirring and maintained at reflux for 24 hours after hexane is first noticed condensing into the thimble. Heating is then stopped and the flask is allowed to cool. Any hexane remaining in the extractor is transferred back to the flask. The hexane is removed b> evaporation under vacuum at ambient temperature, and any residue remaining in the flask is transferred to a weighed bottle using successive hexane washes. The hexane in the flask is evaporated by a nitrogen purge, and the residue is vacuum dried overnight at 400C.
[0186] The polymer sample remaining in the thimble after the extractions is transferred from the thimble to a weighed bottle and vacuum dried overnight at 400C. Results are contained in Table 7. Table 7
Figure imgf000055_0002
Determined b> 11C NMR
Additional Polymer Examples 19 A-J, Continuous Solution Polymerization,, Catalyst A1/B2 + DEZ
For Examples 19A-1
[0187 j Continuous solution polymerizations are carried out in a computer controlled well-mixed reactor. Purified mixed alkanes solvent (Isopar1 M E available from Exxon Mobil. Inc.). ethylene, 1-octene. and h\drogen (where used) are combined and fed to a 27 gallon reactor. The feeds to the reactor are measured b\ mass-flow controllers. The temperature of the feed stream is controlled
Figure imgf000055_0001
use of a glycol cooled heat exchanger before entering the reactor. The catalyst component solutions are rnetered using pumps and mass flow meters. The reactor is run liquid-full at approximately 550 psig pressure. Upon exiting the reactor, water and additive are injected m the poh mer solution. The wMct the LaIaI) St1,. and terminates the poh meri/ation reactions 1 he post reactor solution h ihen heated in preparation tor a two-stage devitalization. I he soh ent and unreacted monomers are removed during the de\olatization process. The polymer melt is pumped to a die for underwater pellet cutting.
For Example 19J
[0188] Continuous solution polymerizations are carried out in a computer controlled autoclave reactor equipped with an internal stirrer. Purified mixed alkanes solvent (Isopar™ E available from ExxonMobil Chemical Company), ethylene at 2.70 lbs/hour (1.22 kg/hour), 1-octene, and hydrogen (where used) are supplied to a 3.8 L reactor equipped with a jacket for temperature control and an internal thermocouple. The solvent feed to the reactor is measured by a mass-flow controller. A variable speed diaphragm pump controls the solvent flow rate and pressure to the reactor. Λt the discharge of the pump, a side stream is taken to provide flush flows for the catalyst and cocatalyst injection lines and the reactor agitator. These flows are measured by Micro-Motion mass flow meters and controlled by control valves or by the manual adjustment of needle valves. The remaining solvent is combined with 1-octene, ethylene, and hydrogen (where used) and fed to the reactor. A mass flow controller is used to deliver hydrogen to the reactor as needed. The temperature of the solvent/monomer solution is controlled by use of a heat exchanger before entering the reactor. This stream enters the bottom of the reactor. The catalyst component solutions are metered using pumps and mass flow meters and are combined with the catalyst Hush solvent and introduced into the bottom of the reactor. The reactor is run liquid-full at 500 psig (3.45 MPa) with v igorous stirring. Product is removed through exit lines at the top of the reactor. All exit lines from the reactor arc steam traced and insulated. Polymerization is stopped by the addition of a small amount of water into the exit line along with any stabilizers or other additives and passing the mixture through a static mixer, The product stream is then heated by passing through a heat exchanger before devolatili/ation. The polymer product is recovered by extrusion using a de volatilizing extruder and water cooled pelletizer.
(0189) Process details and results are contained in Fable 8. Selected polvmer properties are prov ided in Tables 9A-C.
[0190) in Table 9B. inventive examples 19F and 19G show low immediate set of around 65 70 % strain after 500% elongation.
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000059_0002
Examples 20 and 21 fO191| The
Figure imgf000060_0001
interpohmer of Examples 20 and 21 were made In a substantially similar manner as Examples 19A-J above with the polymerization conditions shown in Table 1 1 below. The polymers exhibited the properties shown in Table 10. Table 10 also shows any additives to the polymer. Table Ϊ0 - Properties and Additives of Examples 20-21
Figure imgf000060_0002
[0192 j Irganox 1010 is TetrakismethyIene(3.5-di-t-butyl-4- hydroxyh)droeinnarnaie)methane. Irganox 1076 is Octadecyl-3-(3'.5'-di-t-butyϊ-4'- hydroxyphenyl)propionate. Irgafos 168 is Tris{2,4-di-l-butylphenyl)phosphite. Chimasorb 2020 is 1 ,6-lIexanedia.mine, N,N"-bis(2.2.6,6-tetramethyl~4-piperidinyϊ)- polj mer with 2J.6-trichloro-1.3.5-iriazine. reaction products with, N -butyl- 1- butanamine and N-butyl-2.2,6,6-tetramethy]-4-piperidinamine.
-5S-
Figure imgf000061_0001
Fibers Suitable for the Dyed Fabrics and Textile Articles of the Present Invention
[0193] The present in\ entϊon relates to dyed fabrics suitable for textile articles such as shirts, pants, socks, swimsuits. etc. The fabrics may be made in am manner but typically are either woven or knit. Woven fabrics of the present invention are typically characterized by a stretch of at least about about 10 percent measured according to ASTM D3107 whereas knit fabrics of the present invention are typically characterized by a stretch of at least about 30 percent measured according to ASTM D2594. fO194| The dyed fabrics are usually comprised of one or more elastic fibers wherein the elastic fibers comprise the reaction product of at least one ethylene olefin block polymer and at least one suitable crosslinking agent. As used herein, "'crosslinking agent" is any means which cross-links one or more, preferably a majority, of the fibers. Thus, crosslinking agents may be chemical compounds but are not necessarily so. Crosslinking agents as used herein also include eiectron-beam irradiation, beta irradiation, gamma irradiation, corona irradiation, silanes, peroxides, ailyl compounds and L1V radiation with or without crosslinking catalyst. U.S. Patents No. 6.803,014 and 6,667.351 disclose electron-beam irradiation methods that can be used in embodiments of the im ention. Typically, enough fibers are crosslinked in an amount such that the fabric is capable of being dyed. This amount varies depending upon the specific polymer employed and the desired properties. However, in some embodiments, the percent of cross-linked polvmer is at least about 5 percent, preferably at least about 10, more preferably at least about 15 weight percent to about at most 75, preferably at most 65. preferably at most about 50 percent, more preferably at most about 40 percent as measured by the weight percent of gels formed according to the method described in Example 25.
[0195] The fibers typical!)
Figure imgf000062_0001
a filament elongation to break of greater than about 200o/o. preferably greater than about 210%, preferably greater than about 220%. preferahh greater than about 230%, preferably greater than about 240%. preferabh greater than about 250%. preferably greater than about 260%. preferabh greater than about 270%. preferabh greater than about 2$0%. and ma> be as high as 600% according ro AS FM D2653-01 * elongation at first filament break test). The fibers of the present imention are further characterized ing 1 1 I ratio of load at 200%
-6U- elongation / load at 100% elongation of greater than or equal to about 1.5, preferably greater than or equal to about 1.6. preferably greater than or equal to about 1.7. preferably greater than or equal to about 1.8. preferabh greater than or equal to about 1 ,9. preferably greater than or equal to about 2.0. preferably greater than or equal to about 2.1. preferably greater than or equal to about 2.2. preferably greater than or equal to about 2.3, preferably greater than or equal to about 2.4, and may be as high as 4 according to ASTM D2731 -01 (under force at specified elongation in the finished fiber form).
[0196| The poiyoiefin may be selected from any suitable ethylene olefin block polymer. A particularly preferable olefin block polymer is an ethylencAx-olefin interpolymer, wherein the ethylenes-olefin interpol\mer has one or more of the following characteristics before crosslinking:
( 1 ) an average block index greater than zero and up to about 1.0 and a molecular weight distribution, Mw-Mn, greater than about 1.3: or
(2) at least one molecular fraction which elutes between 40°C and 1300C when fractionated using TREF, characterized in that the fraction has a block index of at least 0.5 and up to about 1 ; or
(3) an Mw/Mn from about 1.7 to about 3.5, at lea^t one melting point, Im, in degrees Celsius, and a density, d, in grams cubic centimeter, wherein the numerical values of Tm and d correspond to the relationship:
rm > -2002.9 - 4538.5(d) - 2422.2{d)2; or
(4) an Mw7Mn from about 1.7 to about 3.5. and is characterized by a heat of fusion, Λϊl in J'g. and a delta quantity, AT. in degrees Celsius defined as the temperature difference between the tallest DSC peak and the tallest CRYS TAF peak, w herein the numerical \alues of A l and AH have the following relationships:
A I > -0, 1299(AH) - 62.81 for AH greater than zero and up to 130 J g.
AT > 480C for AH greater than 130 J g . wherein the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSlAF peak, then the CRYSTAF temperature is 3O0C; or
(5) an elastic reco\ ery, Re. in percent at 300 percent strain and 1 cycle measured with a compression-molded film of the ethylene α-ofefin interpol} mer, and has a density, d, in grams-'cubic centimeter, wherein the numerical values of Re and d satisfy the following relationship when ethylene-'α-oleJIn interpolymer is substantially free of a cross-linked phase:
Re >1481-1629(d): or
(6) a molecular fraction which elutes between 4O0C and 1300C when fractionated using TREF, characterized in that the fraction has a molar comonomer content of at least 5 percent higher than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, wherein said comparable random ethylene interpolymer has the same comonomer(s) and has a melt index, density, and molar comonomer content (based on the whole polymer) within 10 percent of that of the ethylene/α-olctln interpolymer; or
(7) a storage modulus at 25 0C, G" (25 0C). and a storage modulus at 100 0C. G'{ 100 0C), wherein the ratio of G"(25 0C) to G"( 100 °C) is in the range of about 1 :1 to about 9:1.
10197] The fibers may be made into any desirable si?e and cross-sectional shape depending upon the desired application. For many applications approximately round cross-section is desirable due to its reduced friction. However, other shapes such as a trilobal shape, or a flat (i.e.. "ribbon" like) shape can also be employed. Denier is a textile term which is defined as the grams of the fiber per 9000 meters of that fiber's length. Preferred denier si/es depend upon the type of fabric and desired applications. Typically, knit fabrics comprise a majority of the fibers ha\ ing a denier from at least about 1, preferably at least about 20. preferably at least about 50. to at most about 180, preferably at most about 150, preferably at most about 100 denier, preferably Ji most about 80 denier 1A oven fabrics, on the other hand.
Figure imgf000064_0001
comprise a majority of the fibers hav ing a denier that ;s larger trum knits and can be up to MKH) denier.
-t>2- [0198] Depending upon the application the fiber
Figure imgf000065_0001
take any suitable form including a staple fiber or binder fiber. Typical examples may include a homofil fiber, a bicomponent fiber, a melthlown fiber, a meϊtspun fiber, or a spunbond fiber, In the case of a bicomponent fiber it may have a sheath-core structure: a sea-island structure; a side-by -side structure: a matrix-fibril structure: or a segmented pie structure. Adv antageously, conventional fiber forming processes ma> be employed to make the aforementioned fibers. Such processes include those described in, for example. U.S. Patents No. 4.340,563; 4.663,220; 4,668.566; 4,322,027: and 4,413,1 10).
[0199| Depending upon their composition, the fibers may be made to facilitate processing and unwind the same as or better from a spool than other fibers. Ordinary fibers when in round cross section often fail to provide satisfactory unwinding performance due to their base polymer excessive stress relaxation. This stress relaxation is proportional to the age of the spool and causes filaments located at the very surface of the spool to lose grip on the surface, becoming loose filament strands. Later, when such a spool containing conventional fibers is placed over the roils of positive feeders, i.e. Memminger-IRO, and starts to rotate to industrial speeds, i.e. 100 to 300 rotations'minutc. the loose fibers are thrown to the sides of the spool surface and ultimately fall off the edge of the spool. This failure is known as derails which denotes the tendency of conventional fibers to slip off the shoulder or edge of the package which disrupts the unwinding process and ultimately causes machine stops. The above fibers may exhibit derailing to the same or a much less significant degree which possibly allows greater throughput.
[020Oj Another advantage of the fibers is that defects such as fabric faults and elastic filament or fiber breakage may be equivalent or reduced as compared to conventional fibers. That is, use of the above fibers may reduce buildup of fiber fragments on a needle bed - a problem that often occurs in circular knit machines when polymer residue adheres to the needle surface. Thus, the fibers maj reduce the corresponding fabric breaks caused by the residue when the fibers are being made into. e.g. fabrics on a circular knitting machine.
[0201 J Another ad\ arttage is that the fibers may be knitted in circular machines where the elastic guides that drive the filament all the vun from -pool to the ncx-dks are stationary such as ceramic and meulfk In contrast, some comeπtiona!
^ V elastic olefin fibers require that these guides be made of rotating elements such as pullejs as to minimize friction as machine parts, such as evelets. are heated up so that machine stops or filament breaks could be avoided during the circular knitting process. That is. the friction against the guiding elements of the machine is reduced by using the inventive fibers. Further information concerning circular knitting is found in. for example, Bamberg Meisenbach. "Circular Knitting: Technology1 Process, Structures, Yarns, Quality ", 1995. incorporated herein by reference in its entirety. Additives
[0202] Antioxidants, e.g., IRGAFOS® 168, IRGANOX® 1010, IRGANOXf) 3790. and CϊIIMASSORB® 944 made by Ciba Geigy Corp., may be added to the ethylene polymer to protect against undo degradation during shaping or fabrication operation and/or to better control the extent of grafting or crosslmking (i.e., inhibit excessive gelation). In-process additives, e.g. calcium stearate, water, fluoropolymers, etc., may also be used for purposes such as for the deactivation of residual catalyst and/or improved processability. TINUVIN % 770 (from Ciba-Geigy) can be used as a light stabilizer.
J0203J The copolymer can be filled or unfilled. If filled, then the amount of filler present should not exceed an amount that would adversely affect either heat- resistance or elasticity at an elevated temperature. If present, typically the amount of filler is between 0.01 and 80 wt % based on the total weight of the copoly mer (or if a blend of a copolymer and one or more other polymers, then the total weight of the blend). Representative fillers include kaolin clay, magnesium hydroxide, zinc oxide, silica and calcium carbonate. In a preferred embodiment, in which a filler is present, the filler is coated with a material that will pre\ent or retard any tendency that the filler might otherwise have to interfere with the crosslinking reactions. Stearic acid is illustrative of such a filler coating.
[0204] To reduce the friction coefficient of the fibers, various spin finish formulations can be used, such as metallic soaps dispersed in textile oils (see for example U.S. Patent No. 3.039.895 or L'. S. Patent No. 6.652.599), surfactants in a base oil (sec for example L" S publication 20U1 0024052 ϊ and poh alkv Kiloxanct f -.ec for example I .S. Patent \o, 3.296.063 or U.S. Patent \o, 4Λ)99J 20 >. I ".S. Patent Application Xo. 10/933.721 (published as US20050142360) discloses spin finish compositions that can also be used.
Fabrics
[0205] The present invention is directed to improved. dyed textile articles comprising an olefin block copolymer. For purposes of the present invention, "textile articles" includes fabric as well as articles, i.e., garments, made from the fabric including, for example, clothing and other items in need of coloring. Bv knitting it is meant intertwining yarn or thread in a series of connected loops either by hand, with knitting needles, or on a machine. The present in\ ention may be applicable to any type of knitting including, for example, warp or weft knitting, flat knitting, and circular knitting. Particularly preferred warp knits include tricot and raschel while preferred weft knits include circular, flat, and seamless. However, the invention is particularly advantageous when employed in circular knitting, i.e., knitting in the round, in which a circular needle is employed. The present invention may also be applicable to any type of woven fabric.
[0206| The dyed fabrics of the present invention preferably comprise one or more elastic fibers wherein the elastic fibers comprise the reaction product of at least one ethylene olefin block polymer and at least one crosslinking agent wherein the ethylene olefin block polymer is an ethy lenes-olefin interpolymer, wherein the ethylene/α- olefin interpolymer has one or more of the following characteristics prior to crosslinking:
( 1) an average block index greater than zero and up to about 1.0 and a molecular weight distribution. MwMn, greater than about 1.3, or
(2) at least one molecular fraction which elutes between 4O0C and 13O0C when fractionated using TREF. characterized in that the fraction has a block index of at least 0.5 and up to about 1 ; or
(3) an Mw Mn from about 1.7 to about 3.5. at least one melting point. Im. in degrees Celsius, and a density, d. in grams cubic centimeter, wherein the numerical v alues of Tm and ά correspond to the relationship:
I n - -2002.9 - 4538.5<J > 2422 2(d)\ or (4) an Mw 'Mn from about 1.7 to about 3.5. and is characterized b> a heat of fusion, ΔH in J/g. and a delta quantity, AT, in degrees Celsius defined as the temperature difference between the taUest DSC peak and the tallest CRYSTAF peak, wherein the numerical values of ΔT and ΔH ha\e the following relationships:
M > -0J299(ΔH) ■>- 62.81 for ΔH greater than /ero and up to 130 J<g,
ΔT > 48°C for ΔH greater than 130 J/g ,
wherein the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 3O0C; or
(5) an elastic recovery, Re, in percent at 300 percent strain and 1 cycle measured with a compression-molded film of the eth>lene/α-oϊefin interpolymer, and has a density, d, in grams/cubic centimeter, wherein the numerical values of Re and d satisfy the following relationship when ethylene/α-olefm interpohmer is substantially free of a cross-linked phase:
Re >148M 629(d): or
(6) a molecular fraction which elutes between 400C and 1300C when fractionated using TREF, characterized in that the fraction has a molar comonomer content of at least 5 percent higher than that of a comparable random ethylene interpolymer fraction eiuting between the same temperatures, wherein said comparable random ethylene interpolymer has the same comonomer(s) and has a melt index, density, and molar comonomer content (based on the whole polymer) within 10 percent of that of the ethylene, α-olefin interpolymer; or
(7) a storage modulus at 25 0C. G"(25 0C). and a storage modulus at 100 0C, G*(100 0C). w herein the ratio of G"(25 "C) to G-(IOO °C) is in the range of about 1 : 1 to about 9:1.
f0207] The amount of pohmer in the dyed fabric
Figure imgf000068_0001
depending upon the pohmcf. ihc application
Figure imgf000068_0002
fabrics tjpicαlh c cm prise at least aoout 1 . pre.erabh at least about 2. preferably at least about 5. preferabh a! Iea&ϊ about 7 weight percent ethylene u-oiefin interpoiymcr. I be fabr es typical!) comprise less than about 50. preferably less than about 40, preferabh less than about 30, preferably less than about 20. more preferably less than about 10 weight percent ethylenes-olefin interpotymer. The ethylene/a-olefm interpolymer may be in the form of a fiber and may be blended with another suitable polymer, e.g. polyolefins such as random ethylene copolymers. HDPE, LLDPE. LDPE. ULDPE. polypropylene homopolymers. copolymers, plastomers and elastomers, lastol, a polyamide. etc.
|0208| The ethyiene/α-olefin interpol>mer of the fabric may have any density but is usually at least about 0.85 and preferably at least about 0.865 g^cm3 (ASTM D 792). Correspondingly, the density is usually less than about 0.93, preferably less than about 0.92 g/cm3 (ASTM D 792). The ethylene/α-olefin interpolymer of the fabric is characterized by an uncrosslinked melt index of from about 0.1 to about 10 g/10 minutes. If crosslinking is desired, then the percent of cross-linked polymer is often at least 10 percent, preferably at least about 20, more preferably at least about 25 weight percent to about at most 90, preferably at most about 75, as measured by the weight percent of gels formed.
[0209] The fabrics often comprise another material selected from the group consisting of rayon, nylon, viscose, polyester such as microfiber polyester, polyamide. polypropylene, cellulose, cotton, flax, ramie, hemp, wool, silk, linen, bamboo, tencel, mohair, other natural libers, other svthetic fibers, and mixtures thereof. Often the other material comprises the majority of the fabric. In such case it is preferred that the other material comprise from at least about 50, preferably at least about 60. preferably at least about 70, preferably at least about 80, sometimes as much as 90-95. percent by weight of the fabric.
[0210| The ethylene/α-olefin interpolymer. the other material or both may be in the form of a fiber. Preferred sizes include a denier from at least about 1. preferably at least about 20. preferably at least about 50. to at most about 180. preferably at most about 150, preferably at most about 100. preferably at most about 80 denier. [0211] Particularly preferred circular knit fabrics comprise eth\lene,α-olefm interpolymer in the form of a fiber in an amount of from about 5 to about 20 percent (by weight) of the fabric. Particular!} preferred warp knit fabrics comprise cthUene si-oleiln Inierpolymer in trie form of a fiber in an amount of from about 10 to about 30 percent (by weight) of the fabric in the form of a fiber. Often such warp knit and circular knit fabrics also comprise polyester or micro fiber polyester. J0212] The fabric, particularly knit fabrics, often
Figure imgf000070_0001
less than about 5, preferably less than 4, preferably less than 3. preferably less than 2. preferably less than 1, preferably less than 0.5, preferably less than 0.25. percent shrinkage after wash according to AATCC 135 in either the horizontal direction, the vertical direction, or both. More specifically, the fabric (after heat setting) often has a dimensional stability of from about 7% to about +7%. preferably -5% to about -5%, preferably from about -3% to about -<-3%, preferably -2% to about --2%, more preferably -1% to about -1% in the lengthwise direction, the vvidthwise direction, or both according to ΛATCC135 IVAi. In addition, the fabrics often have less shrinkage after wash according to AATCC 135 IVAi than a comparable fabric of elastic fibers with a higher amount of crosslinking.
[0213] Knit fabrics can be made to stretch in two dimensions if desired by controlling the type and amount of ethyl enc/α-ole fin interpolymer and other materials. Knit fabrics may sometimes be characterized by a stretch of at least about 30 percent measured according to ASTM D2594. Similarly, the fabric can be made such that the growth in the lengthwise and widthwise directions is less than about 7. preferably less than about 5. preferably less than about 4, preferably less than about 3, preferably less than about 2, preferably less than about 1. to as little as 0.5 percent according to ASTM D 2594. Using the same test (ASTM D 2594) the lengthwise growth at 60 seconds can be less than about 15. preferably less than about 12, preferably less than about 10, preferably less than about 8%. Correspondingly, using the same test (ASTM D 2594) the vvidthwise growth at 60 seconds can be less than about 20. preferably less than about 18, preferably less than about 16. preferably less than about 13%. In regard to the 60 minute test of ASTM D 2594. the widthwise growth can be less than about 10. preferably less than about 9, preferably less than about 8. preferably less than about 6% while the lengthwise growth at 60 minutes can be less than about 8. preferably less than about 7, preferably less than about 6, preferably less than about 5%. fhe lower growth described above allows the fabrics of the imention to be heat set at temperatures from less than about 180. preferably less than about 170. preferably less than about 160. preferably !cbs than about Ϊ 5^' C while still controlling
-t>8- size. In contrast to knit fabrics, woven fabrics may be characterized by a stretch of at least about 10 percent measured according to ASTM D3107.
[0214] Advantageously, knit fabrics of the present invention can be made without a substantia! number of breaks and using a knitting machine comprising an eyelet feeder system, a pulley system, or a combination thereof. Thus, the circular knitted stretch fabrics having improved moldability while having acceptable dimensional stability (lengthwise and widthwise), acceptable growth and shrinkage, the ability to be heat set at low temperatures while controlling size, low moisture regain can be made without significant breaks, with high throughput, and without derailing in a wide variety of circular knitting machines. Dyeing
(0215] The dyed fabrics of the present invention may be made by virtually any dyeing process. For example, many useful techniques are described in Fundamentals of Dyeing and Printing, by Garry Mock, North Carolina State University 2002, ISBN 9780000033871. One advantage of the fabrics of the present invention is that they may often be contacted with the dye at a temperature of at least about 1300C to produce a dyed fabric wherein the fabric exhibits a growth to stretch ratio of less than 0.5, preferably less than 0.4, preferably less than 0.35, preferably less than 0.3, preferably less than 0.25, preferably less than 0.2, preferably less than 0.15. preferably less than 0.1. preferably less than 0.05. Advantageously, the resulting dyed fabrics of the present invention are often characterized by a color change of greater than or equal to about 3.0, preferably greater than or equal to about 3.5, more preferably greater than or equal to about 4.0 according to AATCC evaluation after a first wash by AATCC61-2003-2 A. Another advantage is that the fabrics of the present invention may sometimes exhibit a color change of greater than or equal to about 2.5. preferably greater than or equal to about 3.0. more preferably greater than or equal to about 3.5 according to AATCC evaluation after a second wash by AA TCC61-2003-2 A. in essence this means that the dyed fabrics of the present invention may exhibit less fading when subjected to laundering than conventional dyed fabrics.
[02161 The dyed fabrics of the present invention are also characterized
Figure imgf000071_0001
an advantageous color strength atter dy eing, i.e.. the fabrics arc darker ϊ-ur example, the d\ed fabrics mav often be characterized bv a color -itremith after ύx mu of greater than
-ffy- or equal to about 600, preferably of greater than or equal to about 650, preferably of greater than or equal to about 700. preferably of greater than or equal to about 750. as measured with a spectrum photometer. Advantageous!}, the color is substantially retained e\en after a first and second wash. For example, the dyed fabrics may be characterized by a color strength after a first wash by AATCC61-2003-2Λ that is at least about 90, preferably at least about 95, more preferabh at least about 97 percent of the color strength after dying wherein each color strength is measured with a spectrum photometer. The dyed fabrics may sometimes also be characterized by a color strength after a second wash by AΛTCC61-2003-2Λ that is at least about 90. preferably at least about 92.5. more preferably at least about 94 percent of the color strength after dying wherein each color strength is measured with a spectrum photometer.
[0217] While not wishing to be bound by any theory it is belie\ed that the reason the dyed fabrics of the present invention dye darker is due to the fibers of the olefin block polymer. That is the olefin block polymer fibers dye to a lesser extent allowing the other material to get darker. Also, a higher dyeing temperature can be employed with less fiber breakage when olefin block polymers are used as the fibers. In a similar manner it is believed that the reason the dyed fabrics fade less upon laundering is that the olefin block polymer fibers are not dyed to as great of an extent as fibers made with other polymers, ϊn this manner, the olefin block polymers cannot fade or bleed as much.
EXAMPLES
Example 22 - Fibers of elastic ethylene/α-olefin interpolymer
[0218J The elastic ethyleneΛϊ-olefϊn interpolymer (olefin block polymer) of Example 20 was used to make monofilament fibers of 40 denier having an approximately round cross-section. Before the fiber v\as made the following additives were added to the polymer: 7000 pprn PDMSO(poly dimethyl siloxane). 3000 ppm CYAXOX I 790 (1.3.5-tris-(4-t-but> i-3-h>droxy-2.6-dimcth\lbenzyl)-I .3,5-triazine- 2.4.6-0 H.3H.5H)-trione, and 3000 ppm CHIMASORB 944 Pol>-f[6-( l.1.3.3- tetrameth} ihuty 1 }amino]-s-tria/ine-2.4-dh f ! [2e2.6.6-tetrameth% 1-4- pψeridy l
Figure imgf000072_0001
weight TiO;. I he fibers were produced using a die profile vvith circular 0.8 mm
^0- diameter, a spin temperature of 2993C, a winder speed of 650m/ minute, a spin finish of 2%. a cold draw of 6%. and a spool weight of 150g. The fibers were then crosslinked using a total of 176.4 kGy irradiation as the crosslmking agent. Example 23 - Hard yarns of fibers jO219| A hard yarn was made that comprised the elastic fibers of Example 22 and 150 denier. 288 fiiament polyester. The filament of micro fiber is fine as 0.52 denier per filament. TWO comparative examples were also made. One comparative example hard yarn employed 40 denier fibers of a random ethylene-octene copolymer made with a line speed of 450 m/min and the same 150 denier. 288 filament polyester fibers. The random ethylene-octene copolymer had an average melt index of 3.0 g/1 Omin, a density of 0.875 g/cm3 and was crosslinked with a dosage of of 166.4 kGy irradiation as the crosslinking agent. The second comparative example hard yarn was made with multi-filament fibers of Lycra rM 162 C polymer and the same 150 denier, 288 filament polyester fibers. Example 24 - Dyeing
[0220] An experiment was designed to evaluate the elastic fiber color staining and the color darkness of microfiber polyester based fabrics. The experiment evaluated the disperse dyestuff staining on the fibers comprised of olefin block polymers, the fibers comprised of Lycra™ 162C. and the fibers comprised of random ethylene- octene copolymer. 1 gram of each of the three different tjpes of fibers and 9 grams of micro-fiber polyester fabric (witness fabric) that made the hard >arn was loaded in a lab rapid dyeing machine that is shown in Figure 8. '1 he d\eing and reduction wash process as shown in Figure 9 was then conducted on each of the three different types of fibers. Clariant dyestuff Foron Black S-WF was used to d>e the fibers and fabrics into black. The Lycra based fibers were dyed at 125 CC since this elastic fiber may undergo severe damage at higher temperatures. The other two types of fibers were dyed at 135 °C. The specimens of after dyeing, after 1 si reduction wash and after 2nd reduction wash were collected for evaluation.
[Θ221 | The three different ty pes of fibers after dyeing and reduction wash were evaluated visually . The polyester micro fiber fabric was also tested to get color strength, color change and coior staining as an indication for color fastness. I lu. JKeJ fibers were e\ dluated \ isαally under D65 standard ύ&y light to dcilne the color >taining on fiber. Color strength ( K S) was measured with u speciruni photometer (Datacolor modei-600PIXS). High K S value represented darker color Color change was measured according to AATCC 61-2003-2A that reports the color difference between original specimen and the specimen after wash. The quotation ranges from 1~5
Figure imgf000074_0001
grey scale according to AA FCC evaluation procedure. A lower grade indicates a bigger color change and therefore less colorfastness. The specimens after dyeing, after ls! reduction wash and after 2nd reduction wash were washed by AATCC 61 -2003-2 A and the color change before and after was measured. [0222] Color staining is also based on the tesl of AATCC 61-20G3-2A. A multi- fiber test fabric that consists of acetate, cotton, polyamide, acrylic and wool fiber, is attached to the specimen to wash. The test grades 1~5 and a lower grade means heavier color staining. Textile industry practice is to use the grade result of poly amide as an indication of color staining.
[0223] Lab dips of the three different types of elastic fibers after dyeing, after 1st reduction wash and after 2nd reduction wash were done. The results indicated good colorfastness and darker color for the fabrics comprising the olefin block polymer. Table 12 shows the elastic fiber color staining after dyeing, after 1 st reduction wash and after 2nd reduction wash. More dvestuff uptake makes darker color on elastic fiber itself. High dvestuff uptake is positive to obtain dark colors but can be detrimental if it bleeds out during washing (home laundry). The Ly era™ fiber shows darkest color after dyeing, after 1st reduction wash and after 2 reduction wash. The random cthvlene-oclene copolymer and olefin block polymer fiber shows lighter color staining. The specimens are very similar after dyeing, after 1 st reduction wash and after 2 reduction wash. The olefin block polymer fiber shows less dvestuff uptake that helps better colorfastness in micro fiber polyester fabric colorfastness. Table 12 Color staining
Figure imgf000074_0002
Kt ReJUi-t'on i fCdnins
TJ [0224] 7 able 13 shows the color strength (K/S) \aiue of micro fiber polyester fabric. The higher value of K/ S represented darker color. Witness micropoK ester fabrics with random ethy lene-octene copolymer and olefin block polymer fibers showed darker black compared with Lycra. While not wishing to be bound to any theory it is believed that this result is due to the higher dyeing temperature employed. There were no significant differences among the samples after dyeing, after F1 reduction wash and after 2nd reduction wash. However, the microfiber polyester of olefin block polymer can reach a darker color. Table 13 Color strength(K/S) value of fabrics
Figure imgf000075_0002
[0225] Table 14 shows the color change \alue of micro fiber polyester after dveing, after 1st reduction wash and after 2"ά reduction wash. The higher v alue means lighter color change. All specimens show good color change results. Table 14 Result of color change of micro polyester
Figure imgf000075_0001
{0226) I able 15 show ^5 the αilor staining to poh jmiae fabric {testing fabric s I he higher \ aiue means less color htainhm. 1 he fabrics after reduction vuish show better color staining. There is no obvious difference between the results shown after Vx and
2sd reduction wash. The dyed, witness fabrics of random ethy iene-octene copolymer and olefin block polymer are darker than the dyed Lycra fabric and this has an effect on the color fastness as ghen in Table 12 . None of the results invoke fabric heat setting.
Table 15 Color staining to polyamide fabric
Figure imgf000076_0001
[0227] Three single jersey knits are use in this test. They are micro fiber polyester hard jam knitted with 40 denier Lycra, 40 denier random ethylcne-octene copolymer and 40 denier olefin block polymer fiber. The knitting speed, elastic draft and the fabric weight of greige are given in Table 16.
Table 16 Fabric description of various elastic fiber contented fabric
Figure imgf000076_0002
[0228] Random ethy Iene-octene copolymer and olefin block polymer greige are scoured at 85CC for 20 minutes, dried at 135CC for 45 minutes, tensionless dryed at 130C for 60 minutes, set at 1653C for 120 seconds (15 yards per minute) at 20% overfeed, and finished. The dyeing and reduction conditions are gh en in Figure 9 for random eih> Iene-octene eopoh mer and olefin block poly mer containing fabric I he s yera greige ^ d>ec aϊ 125 J and heat >et dl 185 C ' e * ' -'kι, u h „ i- ,,s. >'v_ Table 17 Fabric weight of various elastic fiber contented fabric
Figure imgf000077_0001
[0229| Table 18 shows the test result of AATCC 61 -2003-2Λ. random ethy lene- octene copolymer and olefin block polymer both have excellent performance in color change compared with Lycra 162 before or after heat setting. The reason is random ethylene-octene copolymer and olefin block polymer fiber were dyed at 135 'C - the disperse dyestutϊhas better reaction in this temperature. In the dye lot of micro-fiber polyester/ Ly era, there is un-reacted disperse dyestuff because of low dyeing temperature that stained on fabric and bleeds out that makes specimen color fading during testing. Random ethylene-octene copolymer and OBC both has good color fastness to polyamide compared with Lycra. Lycra shows poor color fastness after heat setting. The reason is the disperse dyes migrated during 185 C high temperature heat setting.
Table 18 Test result of color change and color fastness of fabrics
Figure imgf000077_0002
heat setting
[0230] Three finished fabrics after heat setting were tested by spectrum photometer (Datacolor model-όGOPLLS ). fable 19 hhows the color strength (K, S) ϊrut indicates darkness. F he micro- liber polye&ier knits containing random ethylene- octene copolymer and oioiϊn block poly mer habe darker color compared with the knit- containiπn ϊ \cra thai used same d\dni* fomiuiatioπ
-15- Table 19 Fabric width of greige and finished goods
Figure imgf000078_0001
Example 25 - Varying Amounts of Fiber CrossHnking [0231] The elastic ethylene/α-olefin inlerpolymcr of Example 20 was used to make monofilament fibers of 40 denier having an approximately round cross-section. Before the fiber was made the following additives were added to the polymer: 7000 ppm PDMSO (polydimethyl siloxane). 3000 ppm CYANOX 1790 (1.3,5-tris-(4-t- butyl-3-hydroxv-2.6-dimethylbenzyl)-l,3,5-triazine-2.4,6-(l H,3H,5H)-trione. and 3000 ppm CHlMASORB 944 Poly-| [6-(l,l,3,3-telrameth>lbutyl)amino]-s-triazine- 2,4-diylJ[2,2,6,6-tetramethyl-4-piperidyl)imino|hexamethylene[(2,2,6.6-tetramethyl- 4-piperidyl)iminoj] and 0.5% by weight TiOi. The fibers were produced using a die profile with circular 0.8 mm diameter, a spin temperature of 2990C, a winder speed of 650m/minute. a spin finish of 2%. a cold draw of 6%, and a spool weight of 15Og. Fibers were then crosslinked using varying amounts of irradiation from an e-beam as the crosslinking agent.
[0232] The gel content versus the amount of irradiation is shown in Figure 1 1. The gel content was determined by weighing out an approximately 25 mg fiber sample to 4 significant figure accuracy. The sample is then combined with 7 ml xylene in a capped 2-dram vial. The vial is heated 90 minutes at 1250C to 135°C. with inversion mixing (i.e. turning vial upside down) every 15 minutes, to extract essentially all the non-crosslinked polymer. Once the vial has cooled to approximately 250C, the xylene is decanted from the gel. The gel is rinsed in the vial with a small portion of fresh xylenes. The rinsed gel is transferred to a tared aluminum weighing pan. The tared dish with gel is \ acuum dried at 125CC for 30 minutes to remo\e the xylene by evaporation. The pan with dried gel is weighed on an analytical balance. The gel content is calculated based on the extracted gel weight and original fiber weight. Figure 1 i shows that as the e-beam dosage increases, lhe amount of ercssϋπking (gel content^ increases. One skilled in me art will appreciate that the precise relationship between the amount ofcrosslinking and e-beam dosage may be affected by a given polymer's properties, e.g.. molecular weight or melt index.
.1",

Claims

We claim:
1. A dyed fabric comprising one or more elastic fibers wherein the elastic libers comprise the reaction product of at least one ethylene olefin block polymer and at least one crosslinking agent and wherein said fabric is characterized by a color change of greater than or equal to about 3.0 according to AATCC
Figure imgf000080_0001
after a first wash by AATCC61-2003-2A.
2. The dyed fabric of Claim 1 wherein said fabric is characterized by a color change of greater than or equal to about 3.5 according to AATCC e\aluation after a first wash by AΛTCC61 -2003-2 A.
3. The dyed fabric of Claim 1 wherein said fabric is characterized by a color change of greater than or equal to about 4.0 according to AATCC evaluation after a first wash by AATCC61-2003-2A.
4. The fabric of Claim 1 wherein the fabric is a woven fabric which is characterized by a stretch of at least about 10 percent measured according to ASTM D3107.
5. The fabric of Claim 1 wherein the ethy icne olefin block polymer is an ethylene/α-olefin interpolymer characterized by one or more of the following characteristics prior to crosslinking:
(a) has a Mw /Mn from about 1.7 to about 3.5. at least one melting point. Tm, in degrees Celsius, and a density , d. in grams7cubic centimeter, wherein the numerical \alues of Tm and d correspond to the relationship:
Tn, > -2002.9 + 4538.5(d) - 2422.2(d)2, or
(b) has a MwMn from about 1.7 to about 3.5. and is characterized by a heat of fusion, ΔH in J/g, and a delta quantity. ΔT. in degrees Celsius defined as the temperature difference between the tallest DSC peak and the tallest CRYSTAF peak, wherein the numerical values of AT and \H have the following relationships:
A 1 > -0.1299{ AH ) - 62.81 for AH greater than zero and up to ϊ 30 J g.
AT > 480C for \H greater than 130 J'g . wherein the CRYS FAF peak is determined using at least 5 percent of the v,ι,mufatι *e polymer, and if Ie-*- than 5 percent of the polymer has- .m identifiable CRYS F M peak, ϊhen the C RYS I Vt temperature is 1OX . ι>r (c) is characterized by an elastic recovery. Re. in percent at 300 percent strain and 1 c>cle measured with a compression-molded film of the ethylenes-olefin interpoiymer. and has a density, d. in grams/cubic centimeter, wherein the numerical values of Re and d satisfy the following relationship when the cthylene/α-olefm interpoiymer is substantially free of a cross-linked phase:
Re >1481-1629(d); or
(d) has a molecular fraction which elutes between 4O0C and 1300C when fractionated using TREF. characterized in that the fraction has a molar comonomer content of at least 5 percent higher than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, wherein said comparable random ethylene interpoiymer has the same comonomer(s) and a melt index, density, and molar comonomer content (based on the whole polymer) within 10 percent of that of the ethylene/α-olefm interpolymer; or
Ce) is characteri/ed by a storage modulus at 25°C, G"(25°C), and a storage modulus at 100°C, G*(100°C), wherein the ratio of G'(25°C) to G"(100°C) is from about 1 : 1 to about 10:1 ; or
(f) at least one molecular fraction which elutes between 400C and 13O0C when fractionated using TREF, characteri/ed in that the fraction has a block index of at least 0.5 and up to about 1 and a molecular weight distribution, Mw, Mn, greater than about 1.3 or
(g) an average block index greater than zero and up to about 1.0 and a molecular w eight distribution, Mw Mn, greater than about 1.3.
6. The fabric of Claim 1 wherein the fabric is a knit fabric which is characterized by a stretch of at least about 30 percent measured according to AS r\t D2594.
7. 1 he fabric of Claim 1 wherein said elastic fibers comprise from about 2 to about 30 weight percent of the fabric.
8. T he fabric of Claim 1 w herein said fabric further comprises poly ester, nyort. cellulose, cotton, flax, ramie, hemp. wool. sSk. linen, bamboo, teπccL mohair, other natural fibers and mixtures thereof
9. The fabric of Claim S A herein said polyester h mere fiber polyester.
10. The fabric of Claim 8 wherein the polyester comprises at least about 50 percent by weight of the fabric.
11. The fabric of Claim 9 wherein the micro fiber polyester comprises at least about 50 percent bv weight of the fabric.
12. The fabric of Claim 5 wherein the eth> lene/α-olefin mterpohmer is blended with another polymer.
13. The fabric of Claim 5 wherein the ethyiene/α-olcfin interpolymer is characterized by a density of from about 0.865 to about 0.92 g/cm3 (ASTM D 792) and an uncrossiinked melt index of from about 0.1 to about 10 g, 10 minutes.
14. The fabric of Claim 1 wherein the fabric is a knit fabric and comprises a majority of the fibers that have a denier of from about 1 denier to about 180 denier.
15. The dyed fabric of Claim 1 wherein said fabric is characterized by a color change of greater than or equal to about 2.5 according to AATCC evaluation after a second wash by AATCC61 -2003-2 A.
16. The dyed fabric of Claim 1 wherein said fabric is characterized by a color change of greater than or equal to about 3.0 according to AAlCC evaluation after a second wash by AATCC61-2003-2A.
17. The dyed fabric of Claim 1 wherein said fabric is characterized by a color change of greater than or equal to about 3.5 according to AATCC evaluation after a second wash by AATCC61-2003-2A.
18. A d\ed fabric comprising one or more elastic libers wherein the elastic fibers comprise the reaction product of at least one ethylene olefin block polymer and at least one crosslinking agent and wherein said fabric is characterized by a color strength after dying of greater than or equal to about 600 as measured with a spectrum photometer.
19. The dyed fabric of Claim 18 wherein said fabric is characterized by a color strength after d\ing of greater than or equal to about 650 as measured with a spectrum photometer.
20. The
Figure imgf000082_0001
fabric of Claim 18 wherein said fabric is characterized bv a color strength after
Figure imgf000082_0002
ing of greater than or equal to about 700 as measured with a spectrum photometer.
21. The d\ed fabric of Claim 18 wherein
Figure imgf000083_0001
a color strength after dying of greater than or equal to about 750 as measured with a spectrum photometer.
22. The dyed fabric of Claim 18 wherein said fabric is characterized by a coior strength after a first wash by ΛATCC61-20G3-2A that is at least about 90 percent of the color strength after dying wherein each color strength is measured with a spectrum photometer.
23. The dyed fabric of Claim 18 wherein said fabric is characterized by a color strength after a first wash by AATCC61-2003-2A that is at least about 95 percent of the color strength after dying wherein each color strength is measured with a spectrum photometer.
24. The dyed fabric of Claim 18 wherein said fabric is characterized by a color strength after a first wash by AATCC61-2003-2A that is at least about 97 percent of the color strength after dying wherein each color strength is measured with a spectrum photometer.
25. The dyed fabric of Claim 18 wherein said fabric is characteri/ed by a color strength after a second wash by AATCC61-2003-2A that is at least about 90 percent of the coior strength after dying wherein each color strength is measured with a spectrum photometer.
26. The dyed fabric of Claim 18 wherein said fabric is characterized by a color strength after a second wash
Figure imgf000083_0002
AAfCCόl-2003-2A that is at least about 92.5 percent of the color strength after dying wherein each color strength is measured with a spectrum photometer.
27. The dyed fabric of Claim 18 wherein said fabric is characterized by a color strength after a second wash by ΛA ICC61-20G3-2A that is at least about 94 percent of the color strength after dying wherein each color strength is measured with a spectrum photometer.
28. The fabric of Claim 18 w herein the fabric is a
Figure imgf000083_0003
fabric and is characterized by a stretch of at least about 10 percent measured according to AS TM D3107.
29. f'he fabric of Claim I 8 wherein the L*ne olefin block polymer is an ethj iene α-olefin inteφohmer characterized b> one ur more of the following characteristics prior to crosslinking: (a) has a Mw/Mn from about 1.7 to about 3.5, at least one melting point. Tm, in degrees Celsius, and a density, d, in grams/cubic centimeter, wherein the numerical \ alues of Fm and d correspond to the relationship:
Tm > -2002.9 - 4538.5(d) - 2422.2{d}\ or
(b) has a VIw 'Mn from about 1.7 to about 3.5. and is characterized b> a heat of fusion, ΔH in J, g. and a delta quantity , ΔT. in degrees Celsius defined as the temperature difference between the tallest DSC peak and the tallest CRYSTAF peak, wherein the numerical values of ΔT and ΔH ha\e the following relationships:
ΔT > -0.1299(ΔH) - 62.81 for ΔH greater than zero and up to 130 J/g,
ΔT > 48°C for ΔH greater than 130 J/g , wherein the CRYSTAF peak is determined using at ieast 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 300C: or
(c) is characterized by an elastic recovery, Re, in percent at 300 percent strain and 1 cycle measured with a compression-molded film of the ethylene/ α-olefin interpolymer, and has a density, d, in grams/cubic centimeter, wherein the numerical values of Re and d satisfy the following relationship when the ethylene/α-oiefm mterpolymer is substantially free of a cross-linked phase:
Re >1481-1629(d); or
(d) has a molecular fraction which elutes between 400C and 1300C when fractionated using TREF, characterized in that the fraction has a molar comonomer content of at least 5 percent higher than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, wherein said comparable random ethylene interpolymer has the same comonomer(s) and a melt index, density, and molar comonomer content (based on the whole polymer) within 10 percent of that of the ethylene α-olefin interpolymer: or
(e) is characterized by a storage modulus at 25CC. ϋ'(25°C), and a storage modulus at 1000C. ϋ'( Uκrθ, wherein the ratio of G\2SCC ; to
CJ" ( 10o°C) is from about 1 : 1 io uboui 10: L or (f) at least one molecular fraction which elutes between 40°C and 130"C when fractionated using TREF. characterized in that the fraction has a block index of at least 0,5 and up to about 1 and a molecular weight distribution, Mw /Mn. greater than about 1.3 or
(g) an average block index greater than zero and up to about 1.0 and a molecular weight distribution, Mw, Mn. greater than about 1.3.
30. The fabric of Claim 18 wherein said elastic fibers compose from about 2 to about 30 weight percent of the fabric.
31. The fabric of Claim 18 wherein said fabric further comprises polyester, nylon, or mixtures thereof.
32. The fabric of Claim 18 wherein said polyester is microfϊber poh ester.
33. The fabric of Claim 31 wherein the polyester comprises at least about 80 percent b> weight of the fabric.
34. The fabric of Claim 32 wherein the microfiber polyester comprises at least about 80 percent by weight of the fabric.
35. The fabric of Claim 28 wherein the ethy lene/α-olefin interpohmer is blended with another polymer.
36. The fabric of Claim 28 wherein the ethylene/u-oiefin interpolymer is characterized by a density of from about 0,865 to about 0.92 g/cm3 (ASTM D 792) and an uncrosslinked melt index of from about 0.1 to about 10 g/10 minutes.
37. The fabric of Claim 18 wherein a majority of the fibers have a denier of from about 1 denier to about 180 denier.
38. In a process of producing a dyed fabric wherein said fabric comprises one or more elastic fibers comprised of the reaction product of at least one ethylene olefin block polymer and at least one crosslinking agent, wherein said process comprises contacting said fabric and said dye at a temperature above room temperature and then drying said fabric wherein the impro\ement comprises contacting said fabric and said dye at a temperature of at least about 130cC to produce a djed fabric wherein the fabric exhibits a growth to stretch ratio of less than 0.5.
39. The process of Claim 38 wherein said
Figure imgf000085_0001
fabric exhibits a growth to stretch ratio of less than 0.25.
-!O-
40. The process of Claim 38 w herein said dyed fabric is characterized b> a color change of greater than or equal to about 3.0 according to AATCC evaluation after a first wash by AATCC61-2003-2Λ.
41. The process of Claim 38 wherein said dyed fabric is characterized by a color strength after a first wash by AATCC61-2003-2Λ that is at least about 90 percent of the color strength after dy ing wherein each color strength is measured with a spectrum photometer.
42. The process of Claim 38 wherein said process is conducted in the substantial absence of penetration agents.
43. The process of Claim 38 wherein said dyed fabric is characterized by a color strength after dying of greater than or equal to about 600 as measured with a spectrum photometer.
44. The process of Claim 38 wherein said d>ed fabric is characterized by a color strength after a first wash by AATCC61-2003-2A that is at least about 90 percent of the color strength after dying wherein each color strength is measured with a spectrum photometer.
45. The process of Claim 38 w herein the ethy lene olefin block polymer is an ethylenes-olefin interpolymer characterized by one or more of the following characteristics prior to crosslinking:
(a) has a Mw 'Mn from about 1.7 to about 3.5. at least one melting point. 1 m. in degrees Celsius, and a density, d. in grams cubic centimeter, wherein the numerical values of Tm and d correspond to the relationship: rm > -2002.9 ^ 4538.5(d) - 2422.2(d)2, or
(b) has a Mw Mn from about 1.7 to about 3.5. and is characterized by a heat of fusion, Λ1I in J g, and a delta quantity. ΛT, in degrees Celsius defined as the temperature difference between the tallest DSC peak and the tallest CRYS FAF peak, wherein the numerical v alues of ΔT and AH have the following relationships:
M > -0.1299(AH) - 62.81 for ΔH greater than zero and up to 130 J g.
A 1 > 48T for ΔH greater than 130 J g . u herein ihe CRYS IAI peak is determined using ai least 5 percent of the cumulative polymer, and if Ic-- than 5 percent of the polymer
Figure imgf000086_0001
ar identifiable i RYS f Xl peak, then the CRY^ I \I temperature I* 3U1C. or (c) is characterized by an elastic reeo\ery. Re. in percent at 300 percent strain and 1 cycle measured with a compression-molded film of the ethylene α-olefin interpolymer . and has a density, d. in grams 'cubic centimeter, wherein the numerical \ aiues of Re and d satisfy the following relationship when the ethy lene, α-olcfin interpolymer is substantially free of a cross-linked phase:
Re >1481-1629(d); or
(d) has a molecular fraction which elutes between 4O0C and 13O0C when fractionated using TREF, characterized in that the fraction has a molar comonomer content of at least 5 percent higher than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, wherein said comparable random ethylene interpolymer has the same comonomer(s) and a melt index, density, and molar comonomer content (based on the whole polymer) within 10 percent of that of the ethylene/α-olefin interpolymer: or
(e) is characterized by a storage modulus at 25°C, G"(25°C). and a storage modulus at 1000C, G-(IOO0C), wherein the ratio of G'(25°C) to
G'( 1000C) is from about 1 : 1 to about 10: 1 : or
(f) at least one molecular fraction which elutes between 400C and 13O0C when fractionated using TREF, characterized in that the fraction has a block index of at least 0,5 and up to about 1 and a molecular weight distribution, Mw Mn, greater than about 1.3 or
(g) an average block index greater than zero and up to about 1.0 and a molecular weight distribution, Mw7Mn. greater than about 1.3.
46. The fabric of Claim 1 wherein the fabric is a wo\en fabric and comprises a majority of the fibers that have a denier of less than about 3000 denier.
47. The fabric of Claim 18 wherein the fabric is a knit fabric and is characterized by a stretch of at least about 30 percent measured according to ΛS f M D2594.
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