USRE39156E1 - Process for the preparation of polyolefins - Google Patents
Process for the preparation of polyolefins Download PDFInfo
- Publication number
- USRE39156E1 USRE39156E1 US09/488,037 US48803700A USRE39156E US RE39156 E1 USRE39156 E1 US RE39156E1 US 48803700 A US48803700 A US 48803700A US RE39156 E USRE39156 E US RE39156E
- Authority
- US
- United States
- Prior art keywords
- group
- methyl
- zrcl
- indenyl
- different
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 0 [1*]C([2*])(C)C.[3*]c1c([5*])c2c([6*])c([4*])c([4*])c([4*])c2c1C[7*]Cc1c([3*])c([5*])c2c([6*])c([4*])c([4*])c([4*])c12 Chemical compound [1*]C([2*])(C)C.[3*]c1c([5*])c2c([6*])c([4*])c([4*])c([4*])c2c1C[7*]Cc1c([3*])c([5*])c2c([6*])c([4*])c([4*])c([4*])c12 0.000 description 11
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
- C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
- C08F297/083—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins the monomers being ethylene or propylene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/63912—Component covered by group C08F4/62 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/63916—Component covered by group C08F4/62 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/6392—Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/63922—Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/63927—Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
Definitions
- Such admixtures improve polyolefin moldings with respect to their surface gloss, their impact strength and their transparency.
- the processing properties of such polyolefins are likewise improved by admixing the high-molecular-weight atactic polyolefin. Likewise, tackiness and fogging do not occur.
- Homogeneous miscibility of the atactic component is so important because only with a homogeneous material can a usable molding with a good surface and long service life be produced and only in the case of homogeneous distribution do the qualities of the atactic component come out in full.
- the invention thus relates to the preparation of polyolefins which
- Polyolefins which conform to the description under 2) can either be prepared directly in the polymerization or are prepared by melt-mixing in an extruder or compounder.
- the invention thus relates to a process for the preparation of an olefin polymer by polymerization or copolymerization of an olefin of the formula R a —CH ⁇ CH—R b , in which R a and R b are identical or different and are a hydrogen atom or a hydrocarbon radical having 1 to 14 carbon atoms, or R a and R b , together with the atoms connecting them, can form a ring, at a temperature of from ⁇ 60° to 200° C., at a pressure of from 0.5 to 100 bar, in solution, in suspension or in the gas phase, in the presence of a catalyst formed from a metallocene as transition-metal compound and a cocatalyst, wherein the metallocene is a compound of the formula I which is used in the pure meso-form for the preparation of polyolefins of type 1 and used in a meso:rac ratio of greater than 1:99, preferably greater than 2:98, for the preparation
- Halogen means fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine.
- the catalyst to be used for the process according to the invention comprises a cocatalyst and a metallocene of the formula I.
- M 1 is a metal from group IVb, Vb or VIb of the Periodic Table, for example titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, preferably zirconium, hafnium or titanium.
- R 1 and R 2 are identical or different and are a hydrogen atom, a C 1 -C 10 -, preferably C 1 -C 3 -alkyl group, a C 1 -C 10 -, preferably C 1 -C 3 -alkoxy group, a C 6 -C 10 -, preferably C 6 -C 8 -aryl group, a C 6 -C 10 -, preferably C 6 -C 8 -aryloxy group, a C 2 -C 10 -, preferably C 2 -C 4 -alkenyl group, a C 7 -C 40 -, preferably C 7 -C 10 -arylalkyl group, a C 7 -C 40 -, preferably a C 7 -C 12 -alkylaryl group, a C 8 -C 40 -, preferably a C 8 -C 12 -arylalkenyl group, or a halogen atom, preferably chlorine.
- R 4 and R 5 are identical or different and are a hydrogen atom, a halogen atom, preferably a fluorine, chlorine or bromine atom, a C 1 -C 10 -, preferably C 1 -C 4 -alkyl group, which may be halogenated, a C 6 -C 10 -, preferably a C 6 -C 9 -aryl group, which may be halogenated, an —NR 10 2 , —SR 10 , —OSiR 10 3 , —SiR 10 3 or —PR 10 2 radical, in which R 10 is a halogen atom, preferably a chlorine atom, or a C 1 -C 10 -, preferably a C 1 -C 3 -alkyl group, or a C 6 -C 10 -, preferably C 6 -C 8 -aryl group.
- R 4 and R 5 are particularly preferably hydrogen, C 1 -C 4 -alkyl or C 6 -C 9
- R 3 and R 6 are identical or different and are defined for R 4 , with the proviso that R 3 and R 6 must not be hydrogen.
- R 3 and R 6 are preferably (C 1 -C 4 )-alkyl or C 6 -C 9 -aryl, both of which may be halogenated, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, trifluoromethyl, phenyl, tolyl or mesityl, in particular methyl, isopropyl or phenyl.
- radicals R 3 to R 6 may alternatively, together with the atoms connecting them, form an aromatic or aliphatic ring system. Adjacent radicals, in particular R 4 and R 6 , together preferably form a ring.
- R 11 , R 12 and R 13 are identical and are a hydrogen atom, a halogen atom, a C 1 -C 10 -, preferably C 1 -C 4 -alkyl group, in particular a methyl group, a C 1 -C 10 -fluoroalkyl group, preferably a CF 3 group, a C 6 -C 10 -, preferably C 6 -C 8 -aryl group, a C 6 -C 10 -fluoroaryl group, preferably a pentafluorophenyl group, a C 1 -C 10 -, preferably a C 1 -C 4 -alkoxy group, in particular a methoxy group,
- M 2 is silicon, germanium or tin, preferably silicon or germanium.
- R 7 is preferably ⁇ CR 11 R 12 , ⁇ SiR 11 R 12 , ⁇ GeR 11 R 12 , —O—, —S—, ⁇ SO, ⁇ PR 11 or ⁇ P(O)R 11 .
- R 8 and R 9 are identical or different and are as defined for R 11 .
- n and n are identical or different and are zero, 1 or 2, preferably zero or 1, where m plus n is zero, 1 or 2, preferably zero or 1.
- Particularly preferred metallocenes are thus the compounds of the formulae A and B where
- M 1 is Zr or Hf;
- R 1 and R 2 are methyl or chlorine;
- R 3 and R 6 are methyl, isopropyl, phenyl, ethyl or trifluoromethyl;
- R 4 and R 5 are hydrogen or as defined for R 3 and R 6 , or R 4 can form an aliphatic or aromatic ring with R 6 ; the same also applies to adjacent radicals R 4 ; and
- R 8 , R 9 , R 11 and R 12 are as defined above, in particular the compounds I listed in the working examples.
- indenyl radicals of the compounds I are substituted, in particular, in the 2,4-position, in the 2,4,6-position, in the 2,4,5-position or in the 2,4,5,6-position, and the radicals in the 3- and 7-positions are preferably hydrogen.
- the metallocenes described above can be prepared by the following reaction scheme, which is known from the literature:
- the compounds are formed from the synthesis as rac/meso mixtures.
- the meso or rac form can be increased in concentration by fractional crystallization, for example in a hydrocarbon. This procedure is known and is part of the prior art.
- the cocatalyst used according to the invention is preferably an aluminoxane of the formula (II) for the linear type and/or of the formula (III) for the cyclic type, where, in the formulae (II) and (III), the radicals R 14 may be identical or different and are a C 1 -C 6 -alkyl group, a C 6 -C 18 -aryl group, benzyl or hydrogen, and p is an integer from 2 to 50, preferably from 10 to 35.
- the radicals R 14 are preferably identical and are preferably methyl, isobutyl, phenyl or benzyl, particularly preferably methyl.
- radicals R 14 are preferably methyl and hydrogen or alternatively methyl and isobutyl, where hydrogen and isobutyl are preferably present to the extent of 0.01-40% (number of radicals R 14 ).
- the aluminoxane can be prepared in various ways by known processes.
- One of the methods is, for example, to react an aluminum hydrocarbon compound and/or a hydridoaluminum hydrocarbon compound with water (in gas, solid, liquid or bonded form—for example as water of crystallization) in an inert solvent (such as, for example, toluene).
- an inert solvent such as, for example, toluene.
- an aluminoxane containing different alkyl groups R 14 two different trialkylaluminum compounds (AlR 3 +AlR′ 3 ) corresponding to the desired composition are reacted with water (cf. S. Pasynkiewicz, Polyhedron 9 (1990) 429 and EP-A 302 424).
- all the aluminoxane solutions have in common a varying content of unreacted aluminum starting compound, in free form or as an adduct.
- the preactivation of the transition-metal compound is carried out in solution.
- the metallocene is preferably dissolved in a solution of the aluminoxane in an inert hydrocarbon.
- Suitable inert hydrocarbons are aliphatic and aromatic hydrocarbons. Toluene is preferably used.
- the concentration of the aluminoxane in the solution is in the range from about 1% by weight to the saturation limit, preferably from 5 to 30% by weight, in each case based on the solution as a whole.
- the metallocene can be employed in the same concentration, but is preferably employed in an amount of from 10 ⁇ 4 to 1 mol per mol of aluminoxane.
- the preactivation time is from 5 minutes to 60 hours, preferably from 5 to 60 minutes.
- the reaction is carried out at a temperature of from ⁇ 78° C. to 100° C., preferably from 0° to 70° C.
- the metallocene can also be prepolymerized or applied to a support. Prepolymerization is preferably carried out using the (or one of the) olefin(s) employed in the polymerization.
- suitable supports are silica gels, aluminum oxides, solid aluminoxane or other inorganic support materials.
- Another suitable support material is a polyolefin powder in finely divided form.
- compounds of the formulae R x NH 4-x BR′ 4 , R x PH 4-x BR′ 4 , R 3 CBR′ 4 or BR′ 3 can be used as suitable cocatalysts instead of or in addition to an aluminoxane.
- x is a number from 1 to 4, preferably 3, the radicals R are identical or different, preferably identical, and are C 1 -C 10 -alkyl, or C 6 -C 18 -aryl or 2 radicals R, together with the atom connecting them, form a ring, and the radicals R′ are identical or different, preferably identical, and are C 6 -C 18 -aryl, which may be substituted by alkyl, haloalkyl or fluorine.
- R is ethyl, propyl, butyl or phenyl
- R′ is phenyl, pentafluorophenyl, 3,5-bistrifluoromethylphenyl, mesityl, xylyl or tolyl (cf. EP-A 277 003, EP-A 277 004 and EP-A 426 638).
- the actual (active polymerization catalyst comprises the product of the reaction of the metallocene and one of said compounds.
- this reaction product is preferably prepared first outside the polymerization reactor in a separate step using a suitable solvent.
- suitable cocatalysts are according to the invention any compounds which, due to their Lewis acidity, are able to convert the neutral metallocene into a cation and stabilize the latter (“labile coordination”).
- the cocatalyst or the anion formed therefrom should not undergo any further reactions with the metallocene cation formed (cf. EP-A 427 697).
- an alkylaluminum compound for example AlMe 3 or AlEt 3
- This purification can be carried out either in the polymerization system itself, or the olefin is brought into contact with the Al compound before addition to the polymerization system and is subsequently separated off again.
- the polymerization or copolymerization is carried out in known manner in solution, in suspension or in the gas phase, continuously or batchwise, in one or more steps, at a temperature of from ⁇ 60° to 200° C., preferably from 30° to 80° C., particularly preferably at from 50° to 80° C.
- the polymerization or copolymerization is carried out using olefins of the formula R a —CH ⁇ CH—R b .
- R a and R b are identical or different and are a hydrogen atom or an alkyl radical having 1 to 14 carbon atoms. However, R a and R b , together with the carbon atoms connecting them, may alternatively form a ring.
- olefins examples include ethylene, propylene, 1-butane, 1-hexene, 4-methyl-1-pentene, 1-octene, norbornene and norbonadiene.
- propylene and ethylene are polymerized.
- the overall pressure in the polymerization system is 0.5 to 100 bar.
- the polymerization is preferably carried out in the industrially particularly relevant pressure range of from 5 to 64 bar.
- the metallocene is used in a concentration, based on the transition metal, of from 10 ⁇ 3 to 10 ⁇ 8 mol, preferably from 10 ⁇ 4 to 10 ⁇ 7 mol, of transition metal per dm 3 of solvent or per dm 3 of reactor volume.
- the aluminoxane is used in a concentration of from 10 ⁇ 5 to 10 ⁇ 1 mol, preferably from 10 ⁇ 4 to 10 ⁇ 2 mol, per dm 3 of solvent or per dm 3 of reactor volume.
- the other cocatalysts mentioned are used in approximately equimolar amounts with respect to the metallocene. In principle, however, higher concentrations are also possible.
- an inert solvent which is customary for the Ziegler low-pressure process is used.
- the process is carried out in an aliphatic or cycloaliphatic hydrocarbon; examples of such hydrocarbons which may be mentioned are propane, butane, pentane, hexane, heptane, isooctane, cyclohexane and methylcyclohexane.
- Benzine or hydrogenated diesel oil fraction It is also possible to use a benzine or hydrogenated diesel oil fraction. Toluene can also be used.
- the polymerization is preferably carried out in the liquid monomer.
- the monomers are metered in as gases or liquids.
- the polymerization can have any desired duration, since the catalyst system to be used according to the invention only exhibits a slight drop in polymerization activity as a function of time.
- the process according to the invention is distinguished by the fact that the meso-metallocenes described give atactic polymers of high molecular weight in the industrially particularly relevant temperature range between 50° and 80° C. rac/meso mixtures of the metallocenes according to the invention give homogeneous polymers with particular good processing properties. Moldings produced therefrom are distinguished by good surfaces and high transparency. In addition, high surface hardnesses and good moduli of elasticity in flexing are characteristics of these moldings.
- the high-molecular-weight atactic component is not tacky, and the moldings are furthermore distinguished by very good fogging behavior.
- VI viscosity index in cm 3 /g determined
- M w weight average molecular weight by gel in g/mol permeation
- M w /M n polydispersity chromato- graphy
- m.p. melting point determined by DSC (20° C./min heating/ cooling rate)
- MFI/(230/5) melt flow index, measured in accordance with DIN 53735; in dg/min.
- a dry 24 dm 3 reactor was flushed with propylene and filled with 12 dm 3 of liquid propylene.
- 7.5 mg of the meso-metallocene shown in Table 1 were dissolved in 13.5 cm 3 of a toluene solution of methylaluminoxane (30 mmol of Al) and preactivated by standing for 15 minutes. The solution was then introduced into the reactor and heated to 70° C. or 50° C. (Table 1, 10° C./min).
- the polymerization duration was 1 hour.
- the polymerization was terminated by addition of 20 dm 3 (s.t.p.) of CO 2 gas.
- the metallocene activities and the viscosity indices of the atactic polymers obtained are collated in Table 1.
- the triad distributions mm/mrar were typically about 25:50:25, and the isotactic index (mm+ 1/2 mr) was less than 60%.
- the products were therefore undoubtedly typical atactic polypropylenes. This is also confirmed by the solubility in boiling heptane or in diethyl ether.
- the DSC spectrum showed no defined melting point. T g transitions were observed in the range from 0° C. to ⁇ 20° C.
- the polymers obtained were extracted with boiling ether or dissolved in a hydrocarbon having a boiling range of 140°-170° C. and subjected to fractional crystallization; the high-molecular-weight atactic component was separated off and could thus be analyzed separately from the isotactic residue.
- the results are collated in Table 2. Products are non-tacky, and moldings produced therefrom do not exhibit fogging and have an excellent surface and transparency.
- Example 5 was repeated, but the pure meso-form of the metallocene was replaced by rac:meso ratios of 98:2, 95:5, 90:10, 85:15 and 75:25.
- the results are collated in Table 3.
- a non-tacky powder is obtained, and moldings produced therefrom have a good surface, are non-tacky and do not exhibit fogging.
- the molding hardness is good, as is the transparency.
- Example 24 was repeated using 12 dm 3 (s.t.p.) of hydrogen in the polymerization system.
- the polymerization duration was 30 minutes.
- the metallocene activity was 586 kg of PP/g of metallocene ⁇ h.
- the ether-soluble proportion was 1.1% by weight, with a VI of 107 cm 3 /g, and the ether-insoluble proportion was 98.9% by weight, with a VI of 151 cm 3 /g.
- Example 25 was repeated, but 70 g of ethylene were metered in continuously during the polymerization.
- the polymerization duration was 45 minutes.
- the metallocene activity was 468 kg of PP/g of metallocene ⁇ h, the ethylene content of the copolymer was 3.3% by weight, and, according to 13 C-NMR spectroscopy, the ethylene was incorporated substantially in an isolated manner (random compolymer).
- a dry 150 dm 3 reactor was flushed with nitrogen and filled at 20° C. with 80 dm 3 of a benzine cut having the boiling range from 100° to 120° C. from which the aromatic components had been removed.
- the reactor contents were heated to 60° C., and the hydrogen content in the reactor gas space was adjusted to 0.1% by metering in hydrogen and was kept constant during the entire polymerization time by further metering (checking on-line by gas chromatography).
- the block copolymer contained 12.2% by weight of ethylene. Fractionation gave a content of 31.5% by weight of ethylene/propylene rubber and 3.7% by weight of atactic polypropylene, with a VI of 117 cm 3 /g in the polymer as a whole.
- the isolated atactic component had an elastomeric consistency and was completely transparent.
- the polymer powder obtained from the polymerization is non-tacky, and moldings produced therefrom have a good surface, are very transparent and do not exhibit fogging.
- the process was as in Example 32, but the metallocene used was rac/meso-Me 2 Si(2-methyl-4-phenyl-1-indenyl) 2 ZrCl 2 in supported form, with a rac:meso ratio of 1:1.
- the supported metallocene was prepared in the following way:
- Polymerization were carried out in a manner comparable to the above examples using 1:1 rac:meso mixtures of metallocenes not according to the invention at polymerization temperatures of 70° C. and 30° C.
- the resultant polymers were likewise subjected to ether separation in order to characterize the polymer components.
- the results are collated in Table 6 and show that in no case could a polymer according to the invention having a high-molecular-weight atactic polymer component (ether-soluble component) be prepared.
- Products are generally tacky, and the moldings produced therefrom are soft, have a speckled surface and exhibit considerable fogging.
- Comparative Examples 1 to 10 were repeated using the pure meso-forms of the metallocenes used therein. Atactic polypropylene was obtained, but in no case was a viscosity index VI of >70 cm 3 /g obtained. These metallocenes which are not according to the invention can thus not be used to prepare high-molecular-weight atactic polypropylene.
- the products are liquid or at least soft and highly tacky.
Abstract
in which M1 is Zr or Hf, R1 and R2 are identical or different and are methyl or chlorine, R3 and R6 are identical or different and are methyl, isopropyl, phenyl, ethyl or trifluoromethyl, R4 and R5 are hydrogen or as defined for R3 and R6, or R4 forms an aliphatic or aromatic ring with R6, or adjacent radicals R4 form a ring of this type, and R7 is a
radical, and m plus n is zero or 1.
Description
-
- 1) are atactic, i.e. have an isotactic index of ≦60%, and are high-molecular, i.e. have a viscosity index of >80 cm3/g and a molecular weight Mw of >100,000 g/mol with a polydispersity Mw/Mn of 4.0, or
- 2) comprise at least two types of polyolefin chains, namely
- a) a maximum of 99% by weight, preferably a maximum of 98% by weight, of the polymer chains in the polyolefin as a whole comprise α-olefin units linked in a highly isotactic manner, with an isotactic index of >90% and a polydispersity of ≦4.0, and
- b) at least 1% by weight, preferably at least 2% by weight, of the polymer chains in the polyolefin as a whole comprise atactic polyolefins of the type described under 1).
in which
- M1 is a metal from group IVb, Vb or VIb of the Periodic Table,
- R1 and R2 are identical or different and are a hydrogen atom, a C1-C10-alkyl group, a C1-C10-alkoxy group, a C6-C10-aryl group, a C6-C10-aryloxy group, a C2-C10-alkenyl group, a C7-C40-arylalkyl group, a C7-C40-alkylaryl group, a C8-C40-arylalkenyl group, or a halogen atom,
- the radicals R4 and R5 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group, which may be halogenated, a C6-C10-aryl group, which may be halogenated, and an —NR10 2, —SR10, —OSiR10 3, —SiR10 3 or —PR10 2 radical in which R10 is a halogen atom, a C1-C10-alkyl group or a C6-C10-aryl group,
- R3 and R6 are identical or different and are as defined as for R4, with the proviso that R3 and R6 are not hydrogen,
or two or more of the radicals R3 to R6, together with the atoms connecting them, form a ring system,
═BR11, ═AlR11, —Ge—, —Sn—, —O—, —S—, ═SO, ═SO2, ═NR11, ═CO, ═PR11 or ═P(O)R11,
where - R11, R12 and R13 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group, a C1-C10-fluoroalkyl group, a C6-C10-aryl group, a C6-C10-fluoroalkyl group, a C1-C10-alkoxy group, a C2-C10-alkenyl group, a C7-C40-arylalkyl group, a C8-C40-arylalkenyl group or a C7-C40-alkylaryl group, or R11 and R12 or R11 and R13, in each case together with the atoms connecting them, form a ring,
- M2 is silicon, germanium or tin,
- R8 and R9 are identical or different and are as defined for R11, and
- m and n are identical or different and are zero, 1 or 2, where m plus n is zero, 1 or 2.
for the linear type and/or of the formula (III)
for the cyclic type, where, in the formulae (II) and (III), the radicals R14 may be identical or different and are a C1-C6-alkyl group, a C6-C18-aryl group, benzyl or hydrogen, and p is an integer from 2 to 50, preferably from 10 to 35.
VI = | viscosity index in cm3/g | ||
determined | |||
Mw = | weight average molecular weight | by gel | |
in g/mol | permeation | ||
Mw/Mn = | polydispersity | chromato- | |
graphy | |||
m.p. = | melting point determined by | ||
DSC (20° C./min heating/ | |||
cooling rate) | |||
II = | isotactic index (II = mm + | ||
½ mr) determined by 13C-NMR | |||
spectroscopy | |||
niso = | isotactic block length | ||
(niso = 1 + 2 mm/mr) | |||
nsyn = | syndiotactic block length | ||
(nsyn = 1 + 2 n/mr) | |||
MFI/(230/5) = | melt flow index, measured | ||
in accordance with DIN 53735; | |||
in dg/min. | |||
TABLE 1 | ||||
Activity | ||||
Polymerization | [kg of PP/g of | VI | ||
Meso-metallocene | temperature [° C.] | metallocene × h] | [cm3/g] | Ex. |
Me2Si(2,4-dimethyl-1-indenyl)2ZrCl2 | 50 | 35.7 | 125 | 1 |
Me2Si(2-methyl-4-isopropyl-1-indenyl)2ZrCl2 | 70 | 60.4 | 93 | 2 |
Me2Si(2-ethyl-4-methyl-1-indenyl)2ZrCl2 | 70 | 70.3 | 101 | 3 |
Ph(Me)Si(2-methyl-4-isopropyl-1-indenyl)2ZrCl2 | 50 | 20.6 | 120 | 4 |
Me2Si(2-methyl-4,5-benzoindenyl)2ZrCl2 | 70 | 200.0 | 120 | 5 |
Me2Si(2-methyl-4,5-benzoindenyl)2ZrCl2 | 50 | 60.4 | 150 | 6 |
Me2Si(2,4,6-trimethyl-1-indenyl)2ZrCl2 | 50 | 30.1 | 163 | 7 |
Me2Si(2-methyl-4,6-diisopropyl-1-indenyl)2ZrCl2 | 50 | 24.5 | 89 | 8 |
Me2Si(2-methyl-α-acenaphthindenyl)2ZrCl2 | 50 | 49.3 | 224 | 9 |
Me2Si(2-methyl-α-acenaphthindenyl)2ZrCl2 | 70 | 189.4 | 140 | 10 |
Me2Si(2-methyl-4-phenylindenyl)2ZrCl2 | 70 | 64.5 | 131 | 11 |
Me2Si(2-methyl-4-phenyl-1-indenyl)2ZrCl2 | 50 | 32.5 | 169 | 12 |
Ethylene(2,4,6-trimethyl-1-indenyl)2ZrCl2 | 70 | 145.5 | 124 | 13 |
Ethylene(2-methyl-4,5-benzoindenyl)2ZrCl2 | 50 | 94.9 | 109 | 14 |
Methylethylene(2-methyl-α-acenaphthindenyl)2ZrCl2 | 50 | 64.3 | 204 | 15 |
Ph(Me)Si(2-methyl-α-acenaphthindenyl)2ZrCl2 | 50 | 69.8 | 198 | 16 |
TABLE 2 | |||
Activity | Ether-soluble | Ether-insoluble | |
Rac:meso = 1:1 | [kg of PP/g of | atactic component | isotactic component |
Ex. | metallocene mixture | metallocene × h] | % by weight | VI [cm3/g] | % by weight | VI [cm3/g] |
17 | Me2Si(2,4-dimethyl-1- | 69.5 | 25.4 | 117 | 74.6 | 216 |
indenyl)2ZrCl2 | ||||||
18 | Ph(Me)Si(2-methyl-4- | 102.3 | 12.0 | 124 | 88.0 | 280 |
isopropyl-1-indenyl)2ZrCl2 | ||||||
19 | Me2Si(2,4,6-trimethyl-1- | 114.0 | 18.5 | 152 | 71.5 | 245 |
indenyl)2ZrCl2 | ||||||
20 | Me2Si(2-methyl-α- | 61.4 | 44.9 | 209 | 53.1 | 438 |
acenaphthindenyl)2ZrCl2 | ||||||
21 | Me2Si(Si(2-methyl-4-phenyl- | 334.5 | 5.5 | 177 | 94.5 | 887 |
1-indenyl)2ZrCl2 (5 mg) | ||||||
22 | Methylthylene(2-methyl-α- | 85.2 | 36.9 | 199 | 63.1 | 365 |
acenaphthindenyl)2ZrCl2 | ||||||
23 | Ph(Me)Si(2-methyl-α-acena- | 79.1 | 31.2 | 205 | 68.8 | 465 |
phthindenyl)2ZrCl2 | ||||||
TABLE 3 | |||||
Activity | Ether-soluble | Ether-insoluble | |||
[kg PP/g | atactic | isotactic | |||
Rac: | metallo- | component | component |
Ex. | meso | cene × h] | % by wt. | VI [cm3/g] | % by wt. | VI [cm3/g] |
24 | 98:2 | 436 | 0.95 | 134 | 99.05 | 285 |
25 | 95:5 | 410 | 2.7 | 119 | 97.3 | 276 |
26 | 90:10 | 415 | 4.3 | 122 | 95.7 | 296 |
27 | 85:15 | 370 | 7.3 | 125 | 92.7 | 300 |
28 | 75:25 | 347 | 15.2 | 130 | 84.8 | 280 |
TABLE 4 | ||||
Activity | ||||
Polymerization | [kg of PP/g of | VI | Mw | |
temperature [° C.] | metallocene × h] | [cm3/g] | Mw/Mn | [g/mol] |
70 | 58.3 | 205 | 2.0 | 249 500 |
50 | 31.7 | 335 | 2.1 | 425 500 |
TABLE 5 | ||||
Activity | ||||
Polymerization | [kg of PP/g of | VI | Mw | |
temperature [° C.] | metallocene × h] | [cm3/g] | Mw/Mn | [g/mol] |
70 | 112.5 | 559 | 3.5 | 738 000 |
50 | 51.0 | 1084 | 3.6 | 1.35 · 106 |
-
- The supported cocatalyst was prepared as described in EP 92 107 331.8 in the following way in an explosion-proofed stainless-steel reactor fitted with a 60 bar pump system, inert-gas supply, temperature control by jacket cooling and a second cooling circuit via a heat exchanger in the pump system. The pump system drew the contents out of the reactor via a connector in the reactor base into a mixer and back into the reactor through a riser pipe via a heat exchanger. The mixer was installed in such a way that a narrowed tube cross-section, where an increased flow rate occurred, was formed in the feed line, and a thin feed line through which—in cycles—in each case a defined amount of water under 40 bar of argon could be fed in ran into its turbulence zone axially and against the flow direction. The reaction was monitored via a sampler in the pump circuit.
- 5 dm3 of decane were introduced under inert conditions into the above-described reactor with a capacity of 16 dm3. 0.3 dm3 (=3.1 mol) of trimethyl-aluminum were added at 25° C. 250 g of silica gel SD 3216-30 (Grace AG) which had previously been dried at 120° C. in an argon fluidized bed were then metered into the reactor via a solids funnel and homogeneously distributed with the aid of the stirrer and the pump system. The total amount of 45.9 g of water was added to the reactor in portions of 0.1 cm3 every 15 seconds over the course of 2 hours. The pressure, caused by the argon and the evolved gases, was kept constant at 10 bar by pressure-regulation valves. When all the water had been introduced, the pump system was switched off and the stirring was continued at 25° C. for a further 5 hours. The solvent was removed via a pressure filter, and the cocatalyst solid was washed with decane and then dried in vacuo. The isolated solid contains 19.5% by weight of aluminum. 15 g of this solid (108 mmol of Al) were suspended in 100 cm3 of toluene in a stirrable vessel and cooled to −30° C. At the same time, 200 mg (0.317 mmol) of rac/meso 1:1 Me2Si(2-methyl-4-phenyl-indenyl)2ZrCl2 were dissolved in 75 cm3 of toluene and added dropwise to the suspension over the course of 30 minutes. The mixture was slowly warmed to room temperature with stirring, during which time the suspension took on a red color. The mixture was subsequently stirred at 70° C. for 1 hour, cooled to room temperature and filtered, and the solid was washed 3 times with 100 cm3 of toluene in each case and once with 100 cm3 of hexane. The hexane-moist filter residue which remained was dried in vacuo, giving 14.1 g of free-flowing, pink supported catalyst. Analysis gave a content of 11.9 mg of zirconocene per gram of catalyst.
b) Polymerization - 0.7 g of the catalyst prepared under a) were suspended in 50 cm3 of a benzine fraction having the boiling range 100°-120° C. from which the aromatic components had been removed.
- In parallel, a dry 24 dm3 reactor was flushed first with nitrogen and subsequently with propylene and filled with 12 dm3 of liquid propylene and with 1.5 dm3 of hydrogen. 3 cm3 of triisobutylaluminum (12 mmol) were then diluted with 30 ml of hexane and introduced into the reactor, and the batch was stirred at 30° C. for 15 minutes. The catalyst suspension was subsequently introduced into the reactor, and the polymerization system was heated to the polymerization temperature of 70° C. (10° C./min) and kept at 70° C. for 1 hour by cooling. The polymerization was terminated by addition of 20 mol of isopropanol. The excess monomer was removed as a gas, and the polymer was dried in vacuo, giving 1.57 kg of polypropylene powder.
- Fractionation of the polymer by ether extraction gave an ether-soluble atactic content of 8.9% by weight (VI=149 cm3/g) and an insoluble isotactic content of 91.1% by weight, with a VI of 489 cm3/g. The powder prepared in this way was non-tacky, and moldings produced therefrom do not exhibit fogging in the heat-aging test, and the hardness and transparency of the moldings are very good.
TABLE 6 | ||
Polymer data |
Polymerization temperature 70° C. | Polymerization temperature 30° C. |
Metallocene | VI ether-soluble | VI ether-insoluble | VI ether-soluble | VI ether-insoluble |
rac:meso = 1:1 mixture | [cm3/g] | [cm3/g] | [cm3/g] | [cm3/g] |
Me2Si(indenyl)2ZrCl2 | 45 | 42 | 46 | 75 |
Me2Si(2-methyl-1-indenyl)2ZrCl2 | 50 | 180 | 56 | 340 |
Methylethylene(2-methyl-1- | 56 | 127 | 59 | 409 |
indenyl)2ZrCl2 | ||||
Ph(Me)Si(2-methyl-1- | 50 | 202 | 57 | 501 |
indenyl)2ZrCl2 | ||||
Me2Si(2-ethyl-1-indenyl)2ZrCl2 | 59 | 187 | 61 | 443 |
Me2Si(2,4,5-trimethyl-1-cyclo- | 45 | 50 | 47 | 236 |
pentadienyl)2ZrCl2 | ||||
Me2Si(2,4,5-trimethyl-1-cyclo- | 59 | 175 | 69 | 356 |
pentadienyl)2HfCl2 | ||||
Me2Si(indenyl)2HfCl2 | 61 | 237 | 63 | 398 |
Ethylene(2-methyl-1- | 47 | 85 | 50 | 135 |
indenyl)2ZrCl2 | ||||
Me2Si(2-methyl-4-t-butyl-1- | 28 | 31 | 35 | 105 |
cyclopentadienyl)2ZrCl2 | ||||
Claims (3)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/488,037 USRE39156E1 (en) | 1992-08-15 | 2000-01-19 | Process for the preparation of polyolefins |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4227049 | 1992-08-15 | ||
US08/107,187 US5672668A (en) | 1992-08-15 | 1993-08-16 | Process for the preparation of polyolefins |
US08/484,457 US5693836A (en) | 1992-08-15 | 1995-06-07 | Process for the preparation of polyolefins |
US09/488,037 USRE39156E1 (en) | 1992-08-15 | 2000-01-19 | Process for the preparation of polyolefins |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US08/484,457 Reissue US5693836A (en) | 1992-08-15 | 1995-06-07 | Process for the preparation of polyolefins |
Publications (1)
Publication Number | Publication Date |
---|---|
USRE39156E1 true USRE39156E1 (en) | 2006-07-04 |
Family
ID=27204094
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/488,037 Expired - Lifetime USRE39156E1 (en) | 1992-08-15 | 2000-01-19 | Process for the preparation of polyolefins |
Country Status (1)
Country | Link |
---|---|
US (1) | USRE39156E1 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070135623A1 (en) * | 2005-12-14 | 2007-06-14 | Voskoboynikov Alexander Z | Halogen substituted heteroatom-containing metallocene compounds for olefin polymerization |
US7812104B2 (en) | 2008-01-18 | 2010-10-12 | Exxonmobil Chemical Patents Inc. | Production of propylene-based polymers |
US8008412B2 (en) | 2002-09-20 | 2011-08-30 | Exxonmobil Chemical Patents Inc. | Polymer production at supersolution conditions |
US8058371B2 (en) | 2002-09-20 | 2011-11-15 | Exxonmobil Chemical Patents Inc. | Super-solution homogeneous propylene polymerization |
US8242237B2 (en) | 2006-12-20 | 2012-08-14 | Exxonmobil Chemical Patents Inc. | Phase separator and monomer recycle for supercritical polymerization process |
US8318875B2 (en) | 2008-01-18 | 2012-11-27 | Exxonmobil Chemical Patents Inc. | Super-solution homogeneous propylene polymerization and polypropylenes made therefrom |
Citations (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0129368A1 (en) | 1983-06-06 | 1984-12-27 | Exxon Research And Engineering Company | Process and catalyst for polyolefin density and molecular weight control |
EP0185918A2 (en) | 1984-11-27 | 1986-07-02 | Hoechst Aktiengesellschaft | Process for preparing polyolefins |
DE3726067A1 (en) | 1987-08-06 | 1989-02-16 | Hoechst Ag | METHOD FOR PRODUCING 1-OLEFIN POLYMERS |
EP0316155A2 (en) | 1987-11-09 | 1989-05-17 | Chisso Corporation | A transition-metal compound having a substituted, bridged bis-cyclopentadienyl ligand |
EP0320762A2 (en) | 1987-12-18 | 1989-06-21 | Hoechst Aktiengesellschaft | Process for the preparation of a chiral, stereorigid metallocen compound |
EP0336128A2 (en) | 1988-03-12 | 1989-10-11 | Hoechst Aktiengesellschaft | Process for preparing an alpha-olefin polymer |
EP0344887A2 (en) | 1988-03-21 | 1989-12-06 | Exxon Chemical Patents Inc. | Silicon bridged transition metal compounds |
US4892851A (en) | 1988-07-15 | 1990-01-09 | Fina Technology, Inc. | Process and catalyst for producing syndiotactic polyolefins |
DE3826075A1 (en) * | 1988-07-30 | 1990-02-01 | Hoechst Ag | 1-OLEFIN ISO BLOCK POLYMER AND METHOD FOR THE PRODUCTION THEREOF |
EP0355289A1 (en) | 1988-07-01 | 1990-02-28 | ATOCHEM NORTH AMERICA, INC. (a Pennsylvania corp.) | Accelerometer |
EP0366290A2 (en) | 1988-10-24 | 1990-05-02 | Chisso Corporation | Process for producing olefin polymers |
EP0407870A2 (en) | 1989-07-08 | 1991-01-16 | Hoechst Aktiengesellschaft | Process for preparing cycloolefin polymers |
EP0426643A1 (en) | 1989-10-30 | 1991-05-08 | Fina Research S.A. | Process for the preparation of metallocenes |
EP0433990A2 (en) | 1989-12-21 | 1991-06-26 | Hoechst Aktiengesellschaft | Process for preparing polypropylene molding compositions |
EP0442725A2 (en) | 1990-02-13 | 1991-08-21 | Mitsui Petrochemical Industries, Ltd. | Olefin polymerization solid catalysts and process for the polymerization of olefins |
EP0485821A1 (en) | 1990-11-12 | 1992-05-20 | Hoechst Aktiengesellschaft | Metallocenes with 2-substituted indenyl-derivates as ligands, process for their preparation and their use as catalysts |
EP0500005A1 (en) | 1991-02-18 | 1992-08-26 | Hoechst Aktiengesellschaft | Process for the preparation of substituted indenes |
US5145819A (en) * | 1990-11-12 | 1992-09-08 | Hoechst Aktiengesellschaft | 2-substituted disindenylmetallocenes, process for their preparation, and their use as catalysts in the polymerization of olefins |
EP0503422A1 (en) * | 1991-03-09 | 1992-09-16 | Hoechst Aktiengesellschaft | Process for the preparation of chemically homogenous cycloolefinic copolymers |
EP0529908A1 (en) | 1991-08-20 | 1993-03-03 | Mitsubishi Chemical Corporation | Catalyst useful for the polymerization of olefin |
EP0530647A1 (en) * | 1991-08-26 | 1993-03-10 | Hoechst Aktiengesellschaft | Metallocenes, catalysts containing these and process for the manufacture of olefinic polymers by using these catalysts |
US5243001A (en) | 1990-11-12 | 1993-09-07 | Hoechst Aktiengesellschaft | Process for the preparation of a high molecular weight olefin polymer |
US5296434A (en) | 1991-06-18 | 1994-03-22 | Basf Aktiengesellschaft | Soluble catalyst systems for the preparation of polyalk-1-enes having high molecular weights |
US5304614A (en) * | 1991-10-15 | 1994-04-19 | Hoechst Aktiengesellschaft | Process for the preparation of an olefin polymer using metallocenes having specifically substituted indenyl ligands |
US5324800A (en) | 1983-06-06 | 1994-06-28 | Exxon Chemical Patents Inc. | Process and catalyst for polyolefin density and molecular weight control |
US5328969A (en) * | 1991-11-30 | 1994-07-12 | Hoechst Aktiengellschaft | Process for the preparation of a high molecular weight olefin polymer |
US5672668A (en) | 1992-08-15 | 1997-09-30 | Hoechst Aktiengesellschaft | Process for the preparation of polyolefins |
-
2000
- 2000-01-19 US US09/488,037 patent/USRE39156E1/en not_active Expired - Lifetime
Patent Citations (38)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0129368A1 (en) | 1983-06-06 | 1984-12-27 | Exxon Research And Engineering Company | Process and catalyst for polyolefin density and molecular weight control |
US5324800A (en) | 1983-06-06 | 1994-06-28 | Exxon Chemical Patents Inc. | Process and catalyst for polyolefin density and molecular weight control |
EP0185918A2 (en) | 1984-11-27 | 1986-07-02 | Hoechst Aktiengesellschaft | Process for preparing polyolefins |
US4769510A (en) | 1984-11-27 | 1988-09-06 | Hoechst Aktiengesellschaft | Process for the preparation of polyolefins |
DE3726067A1 (en) | 1987-08-06 | 1989-02-16 | Hoechst Ag | METHOD FOR PRODUCING 1-OLEFIN POLYMERS |
US5661096A (en) | 1987-08-06 | 1997-08-26 | Hoechst Ag | Catalysts and cocatalysts for the preparation of polyolefins |
EP0316155A2 (en) | 1987-11-09 | 1989-05-17 | Chisso Corporation | A transition-metal compound having a substituted, bridged bis-cyclopentadienyl ligand |
US4931417A (en) | 1987-11-09 | 1990-06-05 | Chisso Corporation | Transition-metal compound having a bis-substituted-cyclopentadienyl ligand of bridged structure |
US5103030A (en) | 1987-12-18 | 1992-04-07 | Hoechst Aktiengesellschaft | Process for the preparation of a chiral stereorigid metallocene |
EP0320762A2 (en) | 1987-12-18 | 1989-06-21 | Hoechst Aktiengesellschaft | Process for the preparation of a chiral, stereorigid metallocen compound |
EP0336128A2 (en) | 1988-03-12 | 1989-10-11 | Hoechst Aktiengesellschaft | Process for preparing an alpha-olefin polymer |
EP0344887A2 (en) | 1988-03-21 | 1989-12-06 | Exxon Chemical Patents Inc. | Silicon bridged transition metal compounds |
EP0355289A1 (en) | 1988-07-01 | 1990-02-28 | ATOCHEM NORTH AMERICA, INC. (a Pennsylvania corp.) | Accelerometer |
US4892851A (en) | 1988-07-15 | 1990-01-09 | Fina Technology, Inc. | Process and catalyst for producing syndiotactic polyolefins |
EP0351392A2 (en) | 1988-07-15 | 1990-01-17 | Fina Technology, Inc. | Process and catalyst for producing syndiotactic polyolefins |
DE3826075A1 (en) * | 1988-07-30 | 1990-02-01 | Hoechst Ag | 1-OLEFIN ISO BLOCK POLYMER AND METHOD FOR THE PRODUCTION THEREOF |
EP0366290A2 (en) | 1988-10-24 | 1990-05-02 | Chisso Corporation | Process for producing olefin polymers |
US5087677A (en) | 1989-07-08 | 1992-02-11 | Hoechst Aktiengesellschaft | Process for the preparation of cycloolefin polymers |
EP0407870A2 (en) | 1989-07-08 | 1991-01-16 | Hoechst Aktiengesellschaft | Process for preparing cycloolefin polymers |
EP0426643A1 (en) | 1989-10-30 | 1991-05-08 | Fina Research S.A. | Process for the preparation of metallocenes |
EP0433990A2 (en) | 1989-12-21 | 1991-06-26 | Hoechst Aktiengesellschaft | Process for preparing polypropylene molding compositions |
EP0442725A2 (en) | 1990-02-13 | 1991-08-21 | Mitsui Petrochemical Industries, Ltd. | Olefin polymerization solid catalysts and process for the polymerization of olefins |
US5243001A (en) | 1990-11-12 | 1993-09-07 | Hoechst Aktiengesellschaft | Process for the preparation of a high molecular weight olefin polymer |
EP0485821A1 (en) | 1990-11-12 | 1992-05-20 | Hoechst Aktiengesellschaft | Metallocenes with 2-substituted indenyl-derivates as ligands, process for their preparation and their use as catalysts |
US5145819A (en) * | 1990-11-12 | 1992-09-08 | Hoechst Aktiengesellschaft | 2-substituted disindenylmetallocenes, process for their preparation, and their use as catalysts in the polymerization of olefins |
US5276208A (en) | 1990-11-12 | 1994-01-04 | Hoechst Aktiengesellschaft | Metallocenes containing ligands of 2-substituted idenyl derivatives, process for their preparation, and their use as catalysts |
EP0500005A1 (en) | 1991-02-18 | 1992-08-26 | Hoechst Aktiengesellschaft | Process for the preparation of substituted indenes |
EP0503422A1 (en) * | 1991-03-09 | 1992-09-16 | Hoechst Aktiengesellschaft | Process for the preparation of chemically homogenous cycloolefinic copolymers |
US5296434A (en) | 1991-06-18 | 1994-03-22 | Basf Aktiengesellschaft | Soluble catalyst systems for the preparation of polyalk-1-enes having high molecular weights |
US5514760A (en) | 1991-06-18 | 1996-05-07 | Basf Aktiengesellschaft | Soluble catalyst systems for the preparation of polyalk-1-enes having high molecular weights |
EP0529908A1 (en) | 1991-08-20 | 1993-03-03 | Mitsubishi Chemical Corporation | Catalyst useful for the polymerization of olefin |
US5561093A (en) | 1991-08-20 | 1996-10-01 | Mitsubishi Chemical Corporation | Catalyst useful for the polymerization of olefins |
US5278264A (en) * | 1991-08-26 | 1994-01-11 | Hoechst Ag | Process for the preparation of an olefin polymer |
US5329033A (en) | 1991-08-26 | 1994-07-12 | Hoechst Aktiengesellschaft | Process for the preparation of an olefin polymer |
EP0530647A1 (en) * | 1991-08-26 | 1993-03-10 | Hoechst Aktiengesellschaft | Metallocenes, catalysts containing these and process for the manufacture of olefinic polymers by using these catalysts |
US5304614A (en) * | 1991-10-15 | 1994-04-19 | Hoechst Aktiengesellschaft | Process for the preparation of an olefin polymer using metallocenes having specifically substituted indenyl ligands |
US5328969A (en) * | 1991-11-30 | 1994-07-12 | Hoechst Aktiengellschaft | Process for the preparation of a high molecular weight olefin polymer |
US5672668A (en) | 1992-08-15 | 1997-09-30 | Hoechst Aktiengesellschaft | Process for the preparation of polyolefins |
Non-Patent Citations (19)
Title |
---|
Adcock et al., Austr. J. Chem., vol. 29, "Substituent Effects by <SUP>19 </SUP>F Nuclear Magnetic Resonance: Polar and pi-Electron Effects", pp. 2571-2581. |
ansa-Metallocene derivatives by Peter Burger et al., Journal of Organometallic Chemistry, Bd. 417, No. 1-2, Oct. 1, 1991, pp. 9-27, Lausanne. * |
Bulletin De La Societe Chimique De France, "Etude de monomeres halogenes et de leur polymerisation cationique", No. 11, pp. 3092-3095, (1973). |
Criegee et al., Chem. Ber., vol. 94, "Uber den Nickelkomplex C<SUB>18 </SUB>H<SUB>22 </SUB>Ni und en daraus gewonnenen Kohlenwasserstoff C<SUB>13 </SUB>H<SUB>18 </SUB>", pp. 3461-3468 (1964). |
Esperas, S., Acta Chemica Scandinavica, "The Crystal and Molecular Structure of Cyano(methylisocyanide)gold(I)", A 30, No. 7, pp. 527-530 (1976). |
Ewen, J.A., et al, J. Am. Chem. Soc., Crystal Structures and Sterospecific Propylene Polymerizations with Chiral Hafnium Metallocene Catalysts, vol. 109, 1987, pp. 6544-6545. |
Hart et al., NOTES, J. Am. Chem. Soc., vol. 72, "Acylation-Alkylation Studies", pp. 3286-3287 (1950). |
High Molecular Weight Polypropylene through Specifically Designed Zirconocene Catalysts by Walter Spaleck et al., Angewandie Chemie, Bd. 31, Nr. 10, Oct. 1992, pp. 1347-1350, Weinheim, Germany. * |
J. Org. Chem., "Friedel-Crafts Chemistry. A Mechanistic Study of the Reaction of 3-Chloro-4'-fluoro-2-methylpropiophenone with AlCl<SUB>3 </SUB>and AlCl<SUB>3 </SUB>-CH<SUB>3 </SUB>NO<SUB>2</SUB>", vol. 43, No. 16, pp. 3126-3131 (1978). |
J. Org. Chem., "Friedel-Crafts Reactions of Ethyl Cyclopropanecarboxylate", vol. 46, pp. 3758-3760 (1981). |
Katz, Thomas J., J. Am. Chem. Soc., "Asymmetric Synthesis of Helical Metallocenes", vol. 108, 1986, pp. 179-181. |
Marechal et al., Bull. Soc. Chim. Fr. 6, "Homopolymerisation cationlique des dimethyl-4,7,dimethyl-4,6 et dimethyl-5,6 indenes", No. 348, pp. 1981-2039, (1969). |
Mechanisms of Stereochemical Control in Propylene Polymerizations with Soluble Group 4B Metallocene/Methylalumoxane Catalyst by John A. Ewen, J. Am. Chem. Soc., Bd. 106, 1984, pp. 6355-6364 * |
Miyamota, T.K., et al., Chemistry Letters, The Chemical Society of Japan, "A Bulky Ligand and its Organometallic Compound: Synthesis of Heptamethylidene and a Ferrocene-Type Complex, Fe(n<SUP>5 </SUP>-C<SUB>9 </SUB>Me<SUB>7</SUB>)<SUB>2</SUB>", pp. 729-730 (1981). |
Piccoliovazzi, N. et al., ORGANOMETALLICS, "Electronic Effects in Homogeneous Indenylzirconium Ziegler-Natta Catalysts", vol. 9, pp. 3098-3105 (1990). |
Röll, V.W., et al., Angew. Chem., "Stereo-und Regioselektivitat von chiralen, alkylsubstituierten ansar-Zirconocen-Katalysatoren bei der Methylalumoxan-aktivierten Propen-Polymerization", vol. 102, No. 3, pp. 339-341 (1990). |
Soga, K. et al., MACROMOLECULES, "Perfect Conversion of Aspecific Sites into Isopecific Sites in Ziegler-Natta Catalysts", vol. 22, pp. 3824-3826 (1989). |
Spaleck et al., New J. Chem., "Stereorigid Metallocenes: Correlations Between Structure and Behaviour in Homopolymerizations of Propylene", vol. 14, pp. 499-503 (1990). |
Stevens, Metallocene and Other Site Catalysts, The Dow Chemical Co., PTO Presentation, Dec. 8, 1994. * |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8008412B2 (en) | 2002-09-20 | 2011-08-30 | Exxonmobil Chemical Patents Inc. | Polymer production at supersolution conditions |
US8058371B2 (en) | 2002-09-20 | 2011-11-15 | Exxonmobil Chemical Patents Inc. | Super-solution homogeneous propylene polymerization |
US20070135623A1 (en) * | 2005-12-14 | 2007-06-14 | Voskoboynikov Alexander Z | Halogen substituted heteroatom-containing metallocene compounds for olefin polymerization |
US7868197B2 (en) | 2005-12-14 | 2011-01-11 | Exxonmobil Chemical Patents Inc. | Halogen substituted heteroatom-containing metallocene compounds for olefin polymerization |
US8173828B2 (en) | 2005-12-14 | 2012-05-08 | Exxonmobil Chemical Patents Inc. | Halogen substituted heteroatom-containing metallocene compounds for olefin polymerization |
US8546595B2 (en) | 2005-12-14 | 2013-10-01 | Exxonmobil Chemical Patents Inc. | Halogen substituted heteroatom-containing metallocene compounds for olefin polymerization |
US8242237B2 (en) | 2006-12-20 | 2012-08-14 | Exxonmobil Chemical Patents Inc. | Phase separator and monomer recycle for supercritical polymerization process |
US7812104B2 (en) | 2008-01-18 | 2010-10-12 | Exxonmobil Chemical Patents Inc. | Production of propylene-based polymers |
US8318875B2 (en) | 2008-01-18 | 2012-11-27 | Exxonmobil Chemical Patents Inc. | Super-solution homogeneous propylene polymerization and polypropylenes made therefrom |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6359095B1 (en) | Process for the preparation of polyolefins | |
US5576260A (en) | Metallocene-based catalysts | |
JP3394997B2 (en) | Process for producing olefin polymers using metallocenes having specifically substituted indenyl ligands | |
US6197902B1 (en) | Syndio-isoblock polymer and process for its preparation | |
US5776851A (en) | Metallocenes, process for their preparation and their use as catalysts | |
US5741868A (en) | Olefin polymerization process by using a substituted indenyl containing metallocene catalyst | |
US5962719A (en) | Process for the preparation of a polyolefin wax | |
US5243001A (en) | Process for the preparation of a high molecular weight olefin polymer | |
US6096912A (en) | Soluble catalyst systems for the preparation of polyalk-1-enes having high molecular weights | |
US5239022A (en) | Process for the preparation of a syndiotactic polyolefin | |
US6407189B1 (en) | Polyolefin wax | |
US6150481A (en) | Process for the preparation of polyolefins | |
US6713426B1 (en) | Metallocene capable of being used for the process for the preparation of a syndiotactic polyolefin | |
US5350817A (en) | Process for the preparation of polyolefins having a broad molecular weight distribution | |
USRE37384E1 (en) | 2-substituted disindenylmetallocenes, process for their preparation, and their use as catalysts in the polymerization of olefins | |
JPH07258321A (en) | Preparation of high-molecular olefin polymer | |
US20030105237A1 (en) | Polyolefin molding composition having a broad melting range, process for its preparation, and its use | |
US5985784A (en) | Catalyst and process for the polymerization and copolymerization of olefins | |
US5457171A (en) | Catalyst systems for the polymerization of C2 -C10 -alkenes | |
USRE39156E1 (en) | Process for the preparation of polyolefins | |
US5670436A (en) | Metallocene compound |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: BASELL POLYPROPYLEN GMBH, GERMANY Free format text: CHANGE OF NAME;ASSIGNOR:TARGOR GMBH;REEL/FRAME:014125/0001 Effective date: 19990105 |
|
AS | Assignment |
Owner name: BASELL POLYOLEFINE GMBH, GERMANY Free format text: MERGER;ASSIGNOR:BASELL POLYPYLEN GMBH;REEL/FRAME:014129/0344 Effective date: 20020903 |
|
AS | Assignment |
Owner name: CITIBANK, N.A., AS COLLATERAL AGENT,NEW YORK Free format text: GRANT OF SECURITY INTEREST IN UNITED STATES PATENTS AND PATENT APPLICATIONS;ASSIGNORS:BASELL POLYOLEFINE GMBH;ARCO CHEMICAL TECHNOLOGY L.P.;ARCO CHEMICAL TECHNOLOGY, INC.;AND OTHERS;REEL/FRAME:020704/0562 Effective date: 20071220 Owner name: CITIBANK, N.A., AS COLLATERAL AGENT, NEW YORK Free format text: GRANT OF SECURITY INTEREST IN UNITED STATES PATENTS AND PATENT APPLICATIONS;ASSIGNORS:BASELL POLYOLEFINE GMBH;ARCO CHEMICAL TECHNOLOGY L.P.;ARCO CHEMICAL TECHNOLOGY, INC.;AND OTHERS;REEL/FRAME:020704/0562 Effective date: 20071220 |
|
AS | Assignment |
Owner name: CITIBANK, N.A., AS COLLATERAL AGENT,NEW YORK Free format text: SECURITY AGREEMENT;ASSIGNORS:BASELL POLYOLEFINE GMBH;ARCO CHEMICAL TECHNOLOGY L.P.;ARCO CHEMICAL TECHNOLOGY, INC.;AND OTHERS;REEL/FRAME:021354/0708 Effective date: 20071220 Owner name: CITIBANK, N.A., AS COLLATERAL AGENT, NEW YORK Free format text: SECURITY AGREEMENT;ASSIGNORS:BASELL POLYOLEFINE GMBH;ARCO CHEMICAL TECHNOLOGY L.P.;ARCO CHEMICAL TECHNOLOGY, INC.;AND OTHERS;REEL/FRAME:021354/0708 Effective date: 20071220 |
|
FPAY | Fee payment |
Year of fee payment: 12 |
|
AS | Assignment |
Owner name: EQUISTAR CHEMICALS, LP, TEXAS Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:CITIBANK, N.A., AS COLLATERAL AGENT;REEL/FRAME:024337/0856 Effective date: 20100430 Owner name: LYONDELL CHEMICAL TECHNOLOGY, L.P., DELAWARE Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:CITIBANK, N.A., AS COLLATERAL AGENT;REEL/FRAME:024337/0856 Effective date: 20100430 Owner name: EQUISTAR CHEMICALS, LP, TEXAS Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:CITIBANK, N.A., AS COLLATERAL AGENT;REEL/FRAME:024337/0705 Effective date: 20100430 Owner name: LYONDELL CHEMICAL TECHNOLOGY, L.P., DELAWARE Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:CITIBANK, N.A., AS COLLATERAL AGENT;REEL/FRAME:024337/0705 Effective date: 20100430 Owner name: EQUISTAR CHEMICALS, LP,TEXAS Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:CITIBANK, N.A., AS COLLATERAL AGENT;REEL/FRAME:024337/0856 Effective date: 20100430 Owner name: LYONDELL CHEMICAL TECHNOLOGY, L.P.,DELAWARE Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:CITIBANK, N.A., AS COLLATERAL AGENT;REEL/FRAME:024337/0856 Effective date: 20100430 Owner name: EQUISTAR CHEMICALS, LP,TEXAS Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:CITIBANK, N.A., AS COLLATERAL AGENT;REEL/FRAME:024337/0705 Effective date: 20100430 Owner name: LYONDELL CHEMICAL TECHNOLOGY, L.P.,DELAWARE Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:CITIBANK, N.A., AS COLLATERAL AGENT;REEL/FRAME:024337/0705 Effective date: 20100430 |