WO2008089220A2 - Colorfast fabrics and garments of olefin block compositions - Google Patents
Colorfast fabrics and garments of olefin block compositions Download PDFInfo
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- 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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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/79—Polyolefins
- D06P3/794—Polyolefins using dispersed dyes
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- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/20—Woven 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
- D03D15/283—Woven 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
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- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/50—Woven 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
- D03D15/56—Woven 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
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/20—Physical treatments affecting dyeing, e.g. ultrasonic or electric
- D06P5/2066—Thermic treatments of textile materials
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2201/00—Cellulose-based fibres, e.g. vegetable fibres
- D10B2201/01—Natural vegetable fibres
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2201/00—Cellulose-based fibres, e.g. vegetable fibres
- D10B2201/01—Natural vegetable fibres
- D10B2201/02—Cotton
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2201/00—Cellulose-based fibres, e.g. vegetable fibres
- D10B2201/01—Natural vegetable fibres
- D10B2201/04—Linen
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2201/00—Cellulose-based fibres, e.g. vegetable fibres
- D10B2201/01—Natural vegetable fibres
- D10B2201/08—Ramie
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2201/00—Cellulose-based fibres, e.g. vegetable fibres
- D10B2201/01—Natural vegetable fibres
- D10B2201/10—Bamboo
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2211/00—Protein-based fibres, e.g. animal fibres
- D10B2211/01—Natural animal fibres, e.g. keratin fibres
- D10B2211/02—Wool
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2211/00—Protein-based fibres, e.g. animal fibres
- D10B2211/01—Natural animal fibres, e.g. keratin fibres
- D10B2211/04—Silk
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D10B2321/02—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins
- D10B2321/021—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins polyethylene
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/04—Fibres 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]
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/06—Load-responsive characteristics
- D10B2401/061—Load-responsive characteristics elastic
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/06—Load-responsive characteristics
- D10B2401/063—Load-responsive characteristics high strength
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/14—Dyeability
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2501/00—Wearing 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
Description
Claims
Priority Applications (7)
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EP08705940A EP2102396B1 (en) | 2007-01-16 | 2008-01-16 | Colorfast fabrics and garments of olefin block compositions |
AU2008206336A AU2008206336A1 (en) | 2007-01-16 | 2008-01-16 | Colorfast fabrics and garments of olefin block compositions |
CA002674597A CA2674597A1 (en) | 2007-01-16 | 2008-01-16 | Colorfast fabrics and garments of olefin block compositions |
DE602008006667T DE602008006667D1 (en) | 2007-01-16 | 2008-01-16 | COLOR-RESISTANT FIBERS AND CLOTHES OF OLEFINE BLOCK COMPOSITIONS |
BRPI0806226-9A BRPI0806226A2 (en) | 2007-01-16 | 2008-01-16 | dyed fabric and process to produce a dyed fabric |
JP2009546488A JP2010516909A (en) | 2007-01-16 | 2008-01-16 | Dye fastness fabrics and clothing of olefin block compositions |
AT08705940T ATE508217T1 (en) | 2007-01-16 | 2008-01-16 | COLOR-RESISTANT FIBERS AND GARMENTS MADE OF OLEFIN BLOCK COMPOSITIONS |
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Cited By (2)
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CN110029422A (en) * | 2019-04-12 | 2019-07-19 | 愉悦家纺有限公司 | A kind of tencel/diacetate fibre blended yarn weaved fabric and its method for weaving |
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Families Citing this family (4)
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US7622179B2 (en) * | 2004-03-17 | 2009-11-24 | Dow Global Technologies Inc. | Three dimensional random looped structures made from interpolymers of ethylene/α-olefins and uses thereof |
CN102009534B (en) * | 2010-09-07 | 2012-07-25 | 淄博兰雁集团有限责任公司 | Fabric printing and dyeing device with electron accelerator mechanism |
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Citations (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3039895A (en) | 1960-03-29 | 1962-06-19 | Du Pont | Textile |
US3296063A (en) | 1963-11-12 | 1967-01-03 | Du Pont | Synthetic elastomeric lubricated filament |
US4322027A (en) | 1980-10-02 | 1982-03-30 | Crown Zellerbach Corporation | Filament draw nozzle |
US4340563A (en) | 1980-05-05 | 1982-07-20 | Kimberly-Clark Corporation | Method for forming nonwoven webs |
US4413110A (en) | 1981-04-30 | 1983-11-01 | Allied Corporation | High tenacity, high modulus polyethylene and polypropylene fibers and intermediates therefore |
US4663220A (en) | 1985-07-30 | 1987-05-05 | Kimberly-Clark Corporation | Polyolefin-containing extrudable compositions and methods for their formation into elastomeric products including microfibers |
US4668566A (en) | 1985-10-07 | 1987-05-26 | Kimberly-Clark Corporation | Multilayer nonwoven fabric made with poly-propylene and polyethylene |
US4762890A (en) | 1986-09-05 | 1988-08-09 | The Dow Chemical Company | Method of grafting maleic anhydride to polymers |
US4798081A (en) | 1985-11-27 | 1989-01-17 | The Dow Chemical Company | High temperature continuous viscometry coupled with analytic temperature rising elution fractionation for evaluating crystalline and semi-crystalline polymers |
US4927888A (en) | 1986-09-05 | 1990-05-22 | The Dow Chemical Company | Maleic anhydride graft copolymers having low yellowness index and films containing the same |
US4950541A (en) | 1984-08-15 | 1990-08-21 | The Dow Chemical Company | Maleic anhydride grafts of olefin polymers |
US4999120A (en) | 1990-02-26 | 1991-03-12 | E. I. Du Pont De Nemours And Company | Aqueous emulsion finish for spandex fiber treatment comprising a polydimethyl siloxane and an ethoxylated long-chained alkanol |
US5336552A (en) | 1992-08-26 | 1994-08-09 | Kimberly-Clark Corporation | Nonwoven fabric made with multicomponent polymeric strands including a blend of polyolefin and ethylene alkyl acrylate copolymer |
US5382400A (en) | 1992-08-21 | 1995-01-17 | Kimberly-Clark Corporation | Nonwoven multicomponent polymeric fabric and method for making same |
US6140442A (en) | 1991-10-15 | 2000-10-31 | The Dow Chemical Company | Elastic fibers, fabrics and articles fabricated therefrom |
US6225243B1 (en) | 1998-08-03 | 2001-05-01 | Bba Nonwovens Simpsonville, Inc. | Elastic nonwoven fabric prepared from bi-component filaments |
US20030024052A1 (en) | 2000-07-31 | 2003-02-06 | Ikunori Azuse | Lubricants for elastic fiber |
WO2003040195A1 (en) | 2001-11-06 | 2003-05-15 | Dow Global Technologies Inc. | Supported catalysts for manufacture of polymers |
US6652599B1 (en) | 1997-03-13 | 2003-11-25 | Takemoto Oil & Fat Co., Ltd. | Treatment agent for elastic polyurethane fibers and elastic polyurethane fibers treated therewith |
US6667351B2 (en) | 1998-05-18 | 2003-12-23 | Dow Global Technologies Inc. | Articles having elevated temperature elasticity made from irradiated and crosslinked ethylene polymers and method for making the same |
WO2004024740A1 (en) | 2002-09-12 | 2004-03-25 | Dow Global Technologies Inc. | Preparation of metal complexes |
US6803014B2 (en) | 2000-05-11 | 2004-10-12 | Dow Global Technologies Inc. | Method of making elastic articles having improved heat-resistance |
US20050142360A1 (en) | 1999-07-30 | 2005-06-30 | Ralf Klein | Spin finish |
WO2006102149A2 (en) | 2005-03-17 | 2006-09-28 | Dow Global Technologies Inc. | Fibers made from copolymers of ethylene/alpha-olefins |
Family Cites Families (78)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2973344A (en) * | 1957-12-11 | 1961-02-28 | Exxon Research Engineering Co | Modified polymers |
US2997432A (en) * | 1958-08-14 | 1961-08-22 | Phillips Petroleum Co | Dyeing of 1-olefin polymers |
US4146492A (en) * | 1976-04-02 | 1979-03-27 | Texaco Inc. | Lubricant compositions which exhibit low degree of haze and methods of preparing same |
US4299931A (en) * | 1980-03-10 | 1981-11-10 | Monsanto Company | Compatibilized polymer blends |
JPS5734145A (en) * | 1980-08-07 | 1982-02-24 | Mitsui Petrochem Ind Ltd | Ethylene-alpha-olefin copolymer composition |
JPS5975929A (en) * | 1982-10-25 | 1984-04-28 | Sekisui Chem Co Ltd | Production of polyolefin foam |
CA1264880A (en) * | 1984-07-06 | 1990-01-23 | John Brooke Gardiner | Viscosity index improver - dispersant additive useful in oil compositions |
US5391629A (en) * | 1987-01-30 | 1995-02-21 | Exxon Chemical Patents Inc. | Block copolymers from ionic catalysts |
US5266626A (en) * | 1989-02-22 | 1993-11-30 | Norsolor | Thermoplastic elastomer based on an ethylene/α-olefin copolymer and on polynorbornene |
JP2682130B2 (en) * | 1989-04-25 | 1997-11-26 | 三井石油化学工業株式会社 | Flexible long-fiber non-woven fabric |
US6025448A (en) * | 1989-08-31 | 2000-02-15 | The Dow Chemical Company | Gas phase polymerization of olefins |
US5068047A (en) * | 1989-10-12 | 1991-11-26 | Exxon Chemical Patents, Inc. | Visosity index improver |
US5783638A (en) * | 1991-10-15 | 1998-07-21 | The Dow Chemical Company | Elastic substantially linear ethylene polymers |
KR100253826B1 (en) * | 1991-12-30 | 2000-04-15 | 그레이스 스티븐 에스. | Ethylene interpolymer polymerizations |
TW272985B (en) * | 1992-09-11 | 1996-03-21 | Hoechst Ag | |
US5322728A (en) * | 1992-11-24 | 1994-06-21 | Exxon Chemical Patents, Inc. | Fibers of polyolefin polymers |
TW275076B (en) * | 1992-12-02 | 1996-05-01 | Hoechst Ag | |
WO1994018250A1 (en) * | 1993-02-05 | 1994-08-18 | Idemitsu Kosan Co., Ltd. | Polyethylene, thermoplastic resin composition containing the same, and process for producing polyethylene |
JP3031142B2 (en) * | 1993-11-01 | 2000-04-10 | 住友化学工業株式会社 | Polypropylene resin composition |
US6030917A (en) * | 1996-07-23 | 2000-02-29 | Symyx Technologies, Inc. | Combinatorial synthesis and analysis of organometallic compounds and catalysts |
AR006240A1 (en) * | 1996-03-14 | 1999-08-11 | Fuller H B Licensing Financ | HOT MELTING ADHESIVE INCLUDING INTERPOLYMERS, NON-WOVEN ARTICLE THAT UNDERSTANDS IT, POLYMERIZATION PROCEDURE FOR PREPARATION AND BOX, CONTAINER, TRAY AND BOOK UNITED WITH SUCH ADHESIVE |
US5916953A (en) * | 1996-03-15 | 1999-06-29 | Bp Amoco Corporation | Stiff, strong, tough glass-filled olefin polymer |
RU2178422C2 (en) * | 1996-03-27 | 2002-01-20 | Дзе Дау Кемикал Компани | Olefin polymerization catalyst activator, catalytic system, and polymerization process |
JP2000507560A (en) * | 1996-03-27 | 2000-06-20 | ザ ダウ ケミカル カンパニー | Allyl-containing metal complex and olefin polymerization method |
JP3835852B2 (en) * | 1996-04-19 | 2006-10-18 | 日本化薬株式会社 | Disperse dye composition and method for dyeing hydrophobic fiber material using the same |
NZ333878A (en) * | 1996-08-08 | 2000-08-25 | Dow Chemical Co | 3-heteroatom substituted cyclopentadienyl-containing metal complexes and olefin polymerization process |
US6362252B1 (en) * | 1996-12-23 | 2002-03-26 | Vladimir Prutkin | Highly filled polymer composition with improved properties |
CN1113915C (en) * | 1997-02-07 | 2003-07-09 | 埃克森美孚化学专利公司 | Thermoplastic elastomer compositions from branched olefin copolymers |
US5783531A (en) * | 1997-03-28 | 1998-07-21 | Exxon Research And Engineering Company | Manufacturing method for the production of polyalphaolefin based synthetic greases (LAW500) |
CA2299717A1 (en) * | 1997-08-08 | 1999-02-18 | The Dow Chemical Company | Sheet materials suitable for use as a floor, wall or ceiling covering material, and processes and intermediates for making the same |
US6096668A (en) * | 1997-09-15 | 2000-08-01 | Kimberly-Clark Worldwide, Inc. | Elastic film laminates |
US6469103B1 (en) * | 1997-09-19 | 2002-10-22 | The Dow Chemical Company | Narrow MWD, compositionally optimized ethylene interpolymer composition, process for making the same and article made therefrom |
US6197404B1 (en) * | 1997-10-31 | 2001-03-06 | Kimberly-Clark Worldwide, Inc. | Creped nonwoven materials |
DE69909057T2 (en) * | 1998-02-20 | 2004-05-06 | Dow Global Technologies, Inc., Midland | Catalyst activators containing expanded anions |
US6815023B1 (en) * | 1998-07-07 | 2004-11-09 | Curwood, Inc. | Puncture resistant polymeric films, blends and process |
US6306658B1 (en) * | 1998-08-13 | 2001-10-23 | Symyx Technologies | Parallel reactor with internal sensing |
US6316663B1 (en) * | 1998-09-02 | 2001-11-13 | Symyx Technologies, Inc. | Catalyst ligands, catalytic metal complexes and processes using and methods of making the same |
US6680265B1 (en) * | 1999-02-22 | 2004-01-20 | Kimberly-Clark Worldwide, Inc. | Laminates of elastomeric and non-elastomeric polyolefin blend materials |
US6362309B1 (en) * | 1999-04-01 | 2002-03-26 | Symyx Technologies, Inc. | Polymerization catalyst ligands, catalytic metal complexes and compositions and processes using and method of making same |
US6451234B1 (en) * | 2000-02-26 | 2002-09-17 | Milliken & Company | Process for producing dyed textile materials having high levels of colorfastness |
US6537472B2 (en) * | 2000-02-29 | 2003-03-25 | Asahi Kasei Kabushiki Kaisha | Process for producing a cushioning article |
US6160029A (en) * | 2000-03-08 | 2000-12-12 | The Dow Chemical Company | Olefin polymer and α-olefin/vinyl or α-olefin/vinylidene interpolymer blend foams |
US6455638B2 (en) * | 2000-05-11 | 2002-09-24 | Dupont Dow Elastomers L.L.C. | Ethylene/α-olefin polymer blends comprising components with differing ethylene contents |
ATE295391T1 (en) * | 2000-05-26 | 2005-05-15 | Dow Global Technologies Inc | PELYETHYLENE-RICH BLENDS WITH POLYPROPYLENE AND THEIR USE |
WO2002077361A1 (en) * | 2001-03-22 | 2002-10-03 | Milliken & Company | Dyed microfiber textiles |
US20040092662A1 (en) * | 2001-03-29 | 2004-05-13 | Yasuhiro Goto | Propylene polymer composition, molded object, and polyolefin copolymer |
DE10127926A1 (en) * | 2001-06-08 | 2002-12-12 | Bayer Ag | 1,3-disubstituted indene complexes |
WO2003040201A1 (en) * | 2001-11-06 | 2003-05-15 | Dow Global Technologies Inc. | Isotactic propylene copolymers, their preparation and use |
WO2003040204A1 (en) * | 2001-11-09 | 2003-05-15 | Japan Polypropylene Corporation | Propylene block copolymer |
US7005395B2 (en) * | 2002-12-12 | 2006-02-28 | Invista North America S.A.R.L. | Stretchable composite sheets and processes for making |
US6992049B2 (en) * | 2002-01-31 | 2006-01-31 | Exxonmobil Research And Engineering Company | Lubricating oil compositions |
CA2483192A1 (en) * | 2002-04-24 | 2003-11-06 | Symyx Technologies, Inc. | Bridged bi-aromatic ligands, complexes, catalysts and processes for polymerizing and poymers therefrom |
WO2004031292A2 (en) * | 2002-10-02 | 2004-04-15 | Dow Global Technologies Inc. | POLYMER COMPOSITIONS COMPRISING A LOW VISCOSITY, HOMOGENEOUSLY BRANCHED ETHYLENE/α-OLEFIN EXTENDER |
US6869679B1 (en) * | 2002-10-08 | 2005-03-22 | Edward J. Negola | Dyed olefin yarn and textile fabrics using such yarns |
US6953764B2 (en) * | 2003-05-02 | 2005-10-11 | Dow Global Technologies Inc. | High activity olefin polymerization catalyst and process |
AR053693A1 (en) * | 2004-03-17 | 2007-05-16 | Dow Global Technologies Inc | COMPOSITIONS OF ETHYLENE / ALFA-OLEFINE INTERPOLIMERO MULTIBLOCK SUITABLE FOR FILMS |
US7524911B2 (en) * | 2004-03-17 | 2009-04-28 | Dow Global Technologies Inc. | Adhesive and marking compositions made from interpolymers of ethylene/α-olefins |
US7557147B2 (en) * | 2004-03-17 | 2009-07-07 | Dow Global Technologies Inc. | Soft foams made from interpolymers of ethylene/alpha-olefins |
US7622529B2 (en) * | 2004-03-17 | 2009-11-24 | Dow Global Technologies Inc. | Polymer blends from interpolymers of ethylene/alpha-olefin with improved compatibility |
US7714071B2 (en) * | 2004-03-17 | 2010-05-11 | Dow Global Technologies Inc. | Polymer blends from interpolymers of ethylene/α-olefins and flexible molded articles made therefrom |
US7803728B2 (en) * | 2004-03-17 | 2010-09-28 | Dow Global Technologies Inc. | Fibers made from copolymers of ethylene/α-olefins |
US7687442B2 (en) * | 2004-03-17 | 2010-03-30 | Dow Global Technologies Inc. | Low molecular weight ethylene/α-olefin interpolymer as base lubricant oils |
US7666918B2 (en) * | 2004-03-17 | 2010-02-23 | Dow Global Technologies, Inc. | Foams made from interpolymers of ethylene/α-olefins |
US7671131B2 (en) * | 2004-03-17 | 2010-03-02 | Dow Global Technologies Inc. | Interpolymers of ethylene/α-olefins blends and profiles and gaskets made therefrom |
US7582716B2 (en) * | 2004-03-17 | 2009-09-01 | Dow Global Technologies Inc. | Compositions of ethylene/α-olefin multi-block interpolymer for blown films with high hot tack |
US7355089B2 (en) * | 2004-03-17 | 2008-04-08 | Dow Global Technologies Inc. | Compositions of ethylene/α-olefin multi-block interpolymer for elastic films and laminates |
US7514517B2 (en) * | 2004-03-17 | 2009-04-07 | Dow Global Technologies Inc. | Anti-blocking compositions comprising interpolymers of ethylene/α-olefins |
US7741397B2 (en) * | 2004-03-17 | 2010-06-22 | Dow Global Technologies, Inc. | Filled polymer compositions made from interpolymers of ethylene/α-olefins and uses thereof |
US7662881B2 (en) * | 2004-03-17 | 2010-02-16 | Dow Global Technologies Inc. | Viscosity index improver for lubricant compositions |
US7579408B2 (en) * | 2004-03-17 | 2009-08-25 | Dow Global Technologies Inc. | Thermoplastic vulcanizate comprising interpolymers of ethylene/α-olefins |
US7622179B2 (en) * | 2004-03-17 | 2009-11-24 | Dow Global Technologies Inc. | Three dimensional random looped structures made from interpolymers of ethylene/α-olefins and uses thereof |
US7863379B2 (en) * | 2004-03-17 | 2011-01-04 | Dow Global Technologies Inc. | Impact modification of thermoplastics with ethylene/alpha-olefin interpolymers |
US7608668B2 (en) * | 2004-03-17 | 2009-10-27 | Dow Global Technologies Inc. | Ethylene/α-olefins block interpolymers |
US7795321B2 (en) * | 2004-03-17 | 2010-09-14 | Dow Global Technologies Inc. | Rheology modification of interpolymers of ethylene/α-olefins and articles made therefrom |
US7897689B2 (en) * | 2004-03-17 | 2011-03-01 | Dow Global Technologies Inc. | Functionalized ethylene/α-olefin interpolymer compositions |
US7504347B2 (en) * | 2004-03-17 | 2009-03-17 | Dow Global Technologies Inc. | Fibers made from copolymers of propylene/α-olefins |
US7671106B2 (en) * | 2004-03-17 | 2010-03-02 | Dow Global Technologies Inc. | Cap liners, closures and gaskets from multi-block polymers |
TW200902780A (en) * | 2006-11-30 | 2009-01-16 | Dow Global Technologies Inc | Olefin block compositions for heavy weight stretch fabrics |
-
2008
- 2008-01-16 AT AT08705940T patent/ATE508217T1/en not_active IP Right Cessation
- 2008-01-16 US US12/015,278 patent/US20080184498A1/en not_active Abandoned
- 2008-01-16 TW TW097101632A patent/TW200900545A/en unknown
- 2008-01-16 EP EP08705940A patent/EP2102396B1/en not_active Not-in-force
- 2008-01-16 WO PCT/US2008/051142 patent/WO2008089220A2/en active Application Filing
- 2008-01-16 BR BRPI0806226-9A patent/BRPI0806226A2/en not_active IP Right Cessation
- 2008-01-16 CN CNA2008800024386A patent/CN101595253A/en active Pending
- 2008-01-16 AU AU2008206336A patent/AU2008206336A1/en not_active Abandoned
- 2008-01-16 CA CA002674597A patent/CA2674597A1/en not_active Abandoned
- 2008-01-16 JP JP2009546488A patent/JP2010516909A/en active Pending
- 2008-01-16 DE DE602008006667T patent/DE602008006667D1/en active Active
Patent Citations (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3039895A (en) | 1960-03-29 | 1962-06-19 | Du Pont | Textile |
US3296063A (en) | 1963-11-12 | 1967-01-03 | Du Pont | Synthetic elastomeric lubricated filament |
US4340563A (en) | 1980-05-05 | 1982-07-20 | Kimberly-Clark Corporation | Method for forming nonwoven webs |
US4322027A (en) | 1980-10-02 | 1982-03-30 | Crown Zellerbach Corporation | Filament draw nozzle |
US4413110A (en) | 1981-04-30 | 1983-11-01 | Allied Corporation | High tenacity, high modulus polyethylene and polypropylene fibers and intermediates therefore |
US4950541A (en) | 1984-08-15 | 1990-08-21 | The Dow Chemical Company | Maleic anhydride grafts of olefin polymers |
US4663220A (en) | 1985-07-30 | 1987-05-05 | Kimberly-Clark Corporation | Polyolefin-containing extrudable compositions and methods for their formation into elastomeric products including microfibers |
US4668566A (en) | 1985-10-07 | 1987-05-26 | Kimberly-Clark Corporation | Multilayer nonwoven fabric made with poly-propylene and polyethylene |
US4798081A (en) | 1985-11-27 | 1989-01-17 | The Dow Chemical Company | High temperature continuous viscometry coupled with analytic temperature rising elution fractionation for evaluating crystalline and semi-crystalline polymers |
US4927888A (en) | 1986-09-05 | 1990-05-22 | The Dow Chemical Company | Maleic anhydride graft copolymers having low yellowness index and films containing the same |
US4762890A (en) | 1986-09-05 | 1988-08-09 | The Dow Chemical Company | Method of grafting maleic anhydride to polymers |
US4999120A (en) | 1990-02-26 | 1991-03-12 | E. I. Du Pont De Nemours And Company | Aqueous emulsion finish for spandex fiber treatment comprising a polydimethyl siloxane and an ethoxylated long-chained alkanol |
US6140442A (en) | 1991-10-15 | 2000-10-31 | The Dow Chemical Company | Elastic fibers, fabrics and articles fabricated therefrom |
US5382400A (en) | 1992-08-21 | 1995-01-17 | Kimberly-Clark Corporation | Nonwoven multicomponent polymeric fabric and method for making same |
US5336552A (en) | 1992-08-26 | 1994-08-09 | Kimberly-Clark Corporation | Nonwoven fabric made with multicomponent polymeric strands including a blend of polyolefin and ethylene alkyl acrylate copolymer |
US6652599B1 (en) | 1997-03-13 | 2003-11-25 | Takemoto Oil & Fat Co., Ltd. | Treatment agent for elastic polyurethane fibers and elastic polyurethane fibers treated therewith |
US6667351B2 (en) | 1998-05-18 | 2003-12-23 | Dow Global Technologies Inc. | Articles having elevated temperature elasticity made from irradiated and crosslinked ethylene polymers and method for making the same |
US6225243B1 (en) | 1998-08-03 | 2001-05-01 | Bba Nonwovens Simpsonville, Inc. | Elastic nonwoven fabric prepared from bi-component filaments |
US20050142360A1 (en) | 1999-07-30 | 2005-06-30 | Ralf Klein | Spin finish |
US6803014B2 (en) | 2000-05-11 | 2004-10-12 | Dow Global Technologies Inc. | Method of making elastic articles having improved heat-resistance |
US20030024052A1 (en) | 2000-07-31 | 2003-02-06 | Ikunori Azuse | Lubricants for elastic fiber |
WO2003040195A1 (en) | 2001-11-06 | 2003-05-15 | Dow Global Technologies Inc. | Supported catalysts for manufacture of polymers |
US20030204017A1 (en) | 2001-11-06 | 2003-10-30 | Stevens James C. | Isotactic propylene copolymers, their preparation and use |
WO2004024740A1 (en) | 2002-09-12 | 2004-03-25 | Dow Global Technologies Inc. | Preparation of metal complexes |
WO2006102149A2 (en) | 2005-03-17 | 2006-09-28 | Dow Global Technologies Inc. | Fibers made from copolymers of ethylene/alpha-olefins |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20210368891A1 (en) * | 2013-07-16 | 2021-12-02 | Bimla Picot | Clothing Configurations With Multiple Reclosable Access Regions |
US11812797B2 (en) * | 2013-07-16 | 2023-11-14 | Bimla Picot | Clothing configurations with multiple reclosable access regions |
CN110029422A (en) * | 2019-04-12 | 2019-07-19 | 愉悦家纺有限公司 | A kind of tencel/diacetate fibre blended yarn weaved fabric and its method for weaving |
Also Published As
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ATE508217T1 (en) | 2011-05-15 |
DE602008006667D1 (en) | 2011-06-16 |
EP2102396B1 (en) | 2011-05-04 |
US20080184498A1 (en) | 2008-08-07 |
CN101595253A (en) | 2009-12-02 |
WO2008089220A9 (en) | 2009-02-05 |
WO2008089220A3 (en) | 2008-10-23 |
EP2102396A2 (en) | 2009-09-23 |
AU2008206336A1 (en) | 2008-07-24 |
JP2010516909A (en) | 2010-05-20 |
CA2674597A1 (en) | 2008-07-24 |
BRPI0806226A2 (en) | 2011-09-06 |
TW200900545A (en) | 2009-01-01 |
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