CA1304854C - 1-olefin stereoblock polymer, and a process for its preparation - Google Patents

1-olefin stereoblock polymer, and a process for its preparation

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Publication number
CA1304854C
CA1304854C CA000553026A CA553026A CA1304854C CA 1304854 C CA1304854 C CA 1304854C CA 000553026 A CA000553026 A CA 000553026A CA 553026 A CA553026 A CA 553026A CA 1304854 C CA1304854 C CA 1304854C
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Canada
Prior art keywords
alumoxane
olefin
catalyst
polymer
formula
Prior art date
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Expired - Fee Related
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CA000553026A
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French (fr)
Inventor
Walter Kaminsky
Maria Buschermohle
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Hoechst AG
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Hoechst AG
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04Monomers containing three or four carbon atoms
    • C08F110/06Propene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; 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
    • C08F4/60Metals; 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
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/639Component covered by group C08F4/62 containing a transition metal-carbon bond
    • C08F4/63912Component covered by group C08F4/62 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; 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
    • C08F4/60Metals; 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
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/639Component covered by group C08F4/62 containing a transition metal-carbon bond
    • C08F4/6392Component 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
    • C08F4/63922Component 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
    • C08F4/63927Component 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
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943Polymerization with metallocene catalysts

Abstract

Abstract of the disclosure:

Stereoblock polymers of 1-olefins having a broad uni-, bi-, tri- or multimodal molecular weight distribution are obtained when a catalyst which comprises a chiral metal-locene containing bridges and an alumoxane is used for the polymerization of the 1-olefins. The polymers are part-icularly highly suitable for the production of transparent films.

Description

4~S~
..
i HOECHST AKTIENGESELLSCHAFT HOE 86/F 291 Dr.DA/mu Description 1-olefin stereoblock polymer, and a process for its preparation The invention relates to a stereoblock polymer having long isotactic sequences, and to a process for its preparation~

It is known that exclusively atact;c polymer is obtained when a catalyst based on bis-cyclopentadienyl compounds of zirconium and aluminoxane is used in the polymerization of propylene (cf. EP-A 69,951).

In addition, highly isotactic polypropylene can be prep-ared using soluble, stereor;gid, chiral zirconium compounds (cf. EP-A 185,918).

This polypropylene has a very narrow molecular weight distribution cf MW/Mn = 2.
A process is furthermore known for the preparation of polypropylene which has a blocklike structure and in which the isotactic sequences are 2 to 17 monomer un;ts long ~cf. US Patent 4,522,982). The catalyst employed ;s a metallocene o~ a metal of group 4b, 5b or 6b of the periodic table, for example titanium, vanadium or hafnium, in par ticular titanium. This metallocene is a mono-, di- or tricyclopentadienyl or substituted cyclopentadienyl metal compound. The cocatalyst used is an aluminoxane. The polypropylenes obta;ned having a blocklike structure like-wise have a very narro~ molecular weight distribution tMW/Mn = 2).

Finally, it is known that simultaneous polymerization using two or more metallocene catalyst systems gives polyethylene having a bimodal molecular weight distribution (MW/Mn up to 7.8) tcf. EP-A 128,045). However, so-called reactor ~ ~48~
, -- blends are obtained in this process and no homogeneous polymer produced by means of a catalyst system.

In addition, the purely ach;ral catalysts published in the publication mentioned give atactic polypropylene in the polymerization of propylene.

The object was therefore to find a uniform catalyst sys-tem ~hich produces a stereoblock polymer having a broad molecular weight distribution. Such a polymer promises higher homogeneity, which is the basis for better mech-anical properties te.g. ~reedom from specks in the case of fiLms, increased toughness).

It has now been found that the object can be achieved when the catalyst used is a metallocene which conta;ns br;dges between the pentahapto-bound cyclopentadienyl rings, and an alumoxane.

20! Th~ invent;on thus relates to the stereoblock polymer described in the claims and to the process for ;ts prep-aration.

The stereoblock polymer according to the invent;on is a polymer of a 1-olefin of the formula R-CH-CH2 in which ; R denotes an alkyl radical having 1 to 28 carbon atoms, preferably 1 to 10 carbon atoms, in particular one carbon atom, for example propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, or 1-octene. In particular, the polymer is a propylene polymer. Its molecular chains comprise alter-nating isotactic sequences with an opposed configuration and a length o~ three or more monomer units. In addition, the polymer has a broad molecular weight distribution which is Utli-, bi-, tri- or multimodal, preferably bi-, tri- or multimodal, in particular bi- or trimodal.

The figure shows a typical gel-permeation chromatogram (GPC) of a stereobLock polymer according to the invention having a MW/Mn value of 14.9.

~L3~4~5~

The catalyst to be used for the process according to the invention comprises a metallocene compound of the formula I and an alumoxane. In the formula l R~ R4 )~r R 4 R5 R / ~CR1~?2) ( I ) 6> ~ R 3 Me is a metal of group lVb, Vb or VIb of the periodic table, for example titanium, zirconium, hafnium, vanadium~
chromium, molybdenum or tungstenr preferably titan;um.

R and R are identical or different and denote C1- to 15 C10-alkyl, C6- to C10-aryl, C2- to C10-alkenyL or C7-to C40-arylalkyl, preferably ethyl or methyl, in particular methyl.

R and R are identical or different and denote a hydrogen atom or a methyl group, preferably a hydrogen atom.
R5 and R6 are likewise identical or different and denote a halogen atom, such as chlorine, bromine or iodine, C1-to ~10-alky~, C6- to C10-aryl~ C2- to C10-alkenyl~
C7- to C40-arylalkyl or Cg- to C40-arylalkenyl, prefer-ably methyl or chlorine, in particular chlorine.m is 2, 3 or 4, preferably 2.

The metallocene compound which is part;cularly preferabLy enployed is tetramethylethylene-bis(cyclopentadienyl)-titanium dichloride. This type of compound can be prepared,for e~ample~ by reductive coupling of 6,6-dimethylfulvene with sodium amalgam, sodium anthracenide or magnesium metal/CCl4 as reducing agent with subsequent reaction of the anionic tetramethyldicyclopentadienylethane compound with TiCl3 or ZrCl4.

The second component of the catalyst according to the invention is an alumoxane of the formula II

~304as;4 A120R74- [- Al (R7 ) - - ] - s~ ( I I ) for the l;near type and/or of the formula III
S

-[-Al(R7)-~-]~n~2 (III) for the cyclic type. In these formulae, R7 denotes methyl, ethyl or isobutyl, preferably methyl~ and n denotes an integer from 4 to 20, preferably 10 to 16.

The alumoxane can be prepared in various ways.

One possibility is to carefully add water to a dilute solution of a trialkylaluminum, by introducing the solution of the trialkyLaluminum and the water, in each case in small portions, into an initially ;ntroduced, relat;vely large amount of an inert solvent, and in each case waiting between additions for the end of gas evolution.
ZO
In a further process, finely powdered copper sulfate penta-hydrate is slurried in toluene, and, in a glass flask under an inert gas, sufficient trialkylaluminum is added at about -20C so that about one mole of CuS04.5H20 is avail-able per 4 AL atoms. After slo~ hydrolysis with alkaneelimination, the reaction mixture is left at room temperature for 24 to 48 hours, cooling possibly being necessary to prevent the temperature increasing to above 30C. The copper sulfate is subsequently filtered off from the alum-oxane, dissolved in toluene, and the toluene is removedby distillation in vacuo. It is presumed that the low-molecular-weight alumoxanes condense in this process to form higher oligomers with elimination of trialkyl aluminum.

Finally~ alumoxanes are obtained when trialkylaluminum, dissolved in an inert aliphatic or aromatic solvent~ is reacted at a temperature of -20 to 100C ~ith aluminum salts, preferably alum;num sulfate, conta;ning water of crystall;zat;on.

'` ' ;' , ~ , : ,, . .

~3~ 354 - In this reaction, the volume ratio between the solvents and the alkyl aluminum used is 1:1 to 50:1 - preferably 5:1 - and the reaction time, which can be checked by means of the alkane elimination, is 1 to 200 hours -preferably 10 to 40 hours.

Df the aluminum salts contain;ng water of crystallization, those are preferably used which have a high content of water of crystallization. Aluminum sulfate hydrate, above all the compounds Al2S0$)3.18H20 and Al2(S04)3.16H20 hav;ng the particularly high content of ~ater of crystal-l;zat;on of 16 or 18 moles of H20/mole of Alz(504)3 respectively, is part;cularly preferred.

The catalyst to be used according to the invention is employed for the polymerization of 1-olefins of the formula R-CH=CH2 as ment;oned above.

The polymerizat;on is carried out in a known fashion in solution, in suspension or in the gas phase, continuously or batchwise, in one or several stages, at a temperature of -60 to 100C, preferably -20 to ~10C. The pressure is O.S to 60 bar. Polymerization in the pressure range 5 to 60 bar, ~hich is particularly interesting industrially, is preferred.

In this process, the metallocene compound is used in a concentration, relative to titanium or zirconium, of 10 3 to 10 6~ preferably 10 4 to 10 5 mole of Ti or Zr respec-tively per liter of solvent or per liter of the reactorvolumeu The alumoxane is used in a concentration of 10 4 to 10 1 mole, preferably 10 3 to 10 2 mole, per liter of solvent or per liter of the reactor volumeO However, higher concentrations are also possible in principle.
The polymerization is carried out in an inert solvent which is customary for the Ziegler low-pressure process, for ~L3al4~54 example, in an aliphatic or cycloaliphatic hydrocarbon;
butane~ pentane, hexane, heptane, ;sooctane, cyclohexane and methylcyclohexane may be mentioned as examples of such hydrocarbons. It ;s furthermore poss;ble to use a petrol-eum or hydrogenated d;esel o;l fraction which has been care-fully freed from oxygen, sulfur compounds and moisture.
Toluene can also be used. Finally, the monomers to be poly-merized can also be employed as solvents or suspending agents. The molecular weight of the polymer can be regula-ted in a known fashion; hydrogen is preferably used for thispurpose.

Example 1 A dry, argon-filled gas autoclave was filled at -~0C with 250 ml of dry toluene, 300 mg of methylalumoxane having a degree of oLigomerization of n = 16, and 45 9 of propylene.
2 x 10 5 mol of tetramethylethylene-bis(cyclopentadienyl)-titanium chloride was added to this solution.
After a polymerization time of 42 hours, 9.6 9 of rubber-l;ke polypropylene was obta;ned. The activity was 11~4 kg of PP/mol of Ti.h, and the viscosimetrically determined molecular we;ght average was Meta = 190,000.
The isotact;c sequence length was 5.2; MWtMn = 14.9.

Example 2 ~he polymeri~at;on was carried out as in Example 1, but at a temperature of -40C. The polymerization time was 47 hours, yield 9 9 of PP.
Activity 9.6 kg/mmol of Ti.h, MW/Mn = 15.0, isotactic sequence length 4.3~ Meta = 170,000.
Example 3 The polymerization was carried out as in Example 2, but 13(~ 5~

at a temperature of -20C. The polymerizat;on time was 66 hours, yield 8.6 g of PP.
Activity 6.5 kg/mmol of T;.h, MW/Mn = 12.9, ;sotact;c sequence length; 4.2. Meta = 160,000.

.:.. ;.;: ... ~, ..... . ..

Claims (3)

1. A process for the preparation of a 1-olefin stereoblock polymer through polymerization of a 1-olefin of the formula R-CH=CH2 in which R is an alkyl group having 1 to 28 carbon atoms, at a temperature of -60° to 100°C., at a pressure of 0.5 to 60 bar, in solution in suspension or in the gas phase, in the presence of a catalyst which comprises metallocene compound and an alumoxane, the metallocene compound being tetramethylethylene-bis(cyclopentadienyl)-titanium dichloride, and the alumoxane being a compound of the formula II
Al2OR47-[-A?(R7-O-]n- (II) for the linear type and/or of the formula III
-[-Al(R7)-O-]-n+2 (III) for the cyclic type, or combinations thereof, and where, in the formulae II and III, R7 denotes methyl, ethyl, or isobutyl, and n is an integer from 4 to 20.
2. A process as claimed in claim 1, wherein the 1-olefin is propylene.
3. A process as claimed in claim 1, wherein the catalyst consists essentially of said metallocene and said alumoxane.
CA000553026A 1986-11-29 1987-11-27 1-olefin stereoblock polymer, and a process for its preparation Expired - Fee Related CA1304854C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP3640924.3 1986-11-29
DE19863640924 DE3640924A1 (en) 1986-11-29 1986-11-29 1-OLEFIN STEREOBLOCK POLYMER AND METHOD FOR THE PRODUCTION THEREOF

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CA1304854C true CA1304854C (en) 1992-07-07

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US (1) US4849487A (en)
EP (1) EP0269986B1 (en)
JP (1) JP2540174B2 (en)
AU (1) AU599171B2 (en)
CA (1) CA1304854C (en)
DE (2) DE3640924A1 (en)
ES (1) ES2025618T3 (en)
ZA (1) ZA878922B (en)

Families Citing this family (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5391629A (en) * 1987-01-30 1995-02-21 Exxon Chemical Patents Inc. Block copolymers from ionic catalysts
DE3726067A1 (en) 1987-08-06 1989-02-16 Hoechst Ag METHOD FOR PRODUCING 1-OLEFIN POLYMERS
US4892851A (en) * 1988-07-15 1990-01-09 Fina Technology, Inc. Process and catalyst for producing syndiotactic polyolefins
US5225500A (en) * 1988-07-15 1993-07-06 Fina Technology, Inc. Process and catalyst for producing syndiotactic polyolefins
KR100197327B1 (en) * 1988-07-15 1999-06-15 치어즈 엠. 노우드 Syndiotactic polypropylene
DE3825814A1 (en) * 1988-07-29 1990-02-01 Hoechst Ag METHOD FOR PRODUCING L-OLEFIN POLYMERS
DE3826075A1 (en) * 1988-07-30 1990-02-01 Hoechst Ag 1-OLEFIN ISO BLOCK POLYMER AND METHOD FOR THE PRODUCTION THEREOF
DE3826074A1 (en) * 1988-07-30 1990-02-01 Hoechst Ag PROPYLENE ISO BLOCK POLYMER AND METHOD FOR THE PRODUCTION THEREOF
US5700896A (en) * 1988-07-30 1997-12-23 Hoechst Aktiengesellschaft Polymer having long isotactic sequences and randomly-distributed ethylene content obtained by polymerizing propylene in presence of specific catalysts
JP2835729B2 (en) * 1988-10-24 1998-12-14 チッソ株式会社 Method for producing olefin polymer
US5043515A (en) * 1989-08-08 1991-08-27 Shell Oil Company Ethylene oligomerization catalyst and process
DE3916553A1 (en) * 1989-05-20 1990-11-22 Hoechst Ag SYNDIO ISO BLOCK POLYMER AND METHOD FOR THE PRODUCTION THEREOF
DE3916555A1 (en) * 1989-05-20 1990-11-22 Hoechst Ag PROCESS FOR THE PRODUCTION OF ETHYLENE POLYMERS
US5420217A (en) * 1989-09-13 1995-05-30 Exxon Chemical Patents Inc. Process for producing amorphous poly-α-olefins with a monocyclopentadienyl transition metal catalyst system
US5036034A (en) * 1989-10-10 1991-07-30 Fina Technology, Inc. Catalyst for producing hemiisotactic polypropylene
US5387568A (en) * 1989-10-30 1995-02-07 Fina Technology, Inc. Preparation of metallocene catalysts for polymerization of olefins
US5104956A (en) * 1989-12-19 1992-04-14 Board Of Trustees Of The Leland Stanford Junior Univ. Stereoregular cyclopolymers and method
ES2110437T3 (en) * 1990-02-09 1998-02-16 Exxon Chemical Patents Inc COPOLYMERS OF BLOCKS FROM IONIC CATALYSTS.
GB2241244B (en) * 1990-02-22 1994-07-06 James C W Chien Thermoplastic elastomers
DE4005947A1 (en) * 1990-02-26 1991-08-29 Basf Ag SOLUBLE CATALYST SYSTEMS FOR POLYMERIZING C (DOWN ARROW) 2 (DOWN ARROW) - TO C (DOWN ARROW) 1 (DOWN ARROW) (DOWN ARROW) 0 (DOWN ARROW) -ALK-1-ENEN
DE4019053A1 (en) * 1990-06-15 1991-12-19 Basf Ag POLYMERISATES OF PROPYLENE WITH A WIDE MOLECULAR RATIO Q
US5218052A (en) * 1991-02-04 1993-06-08 Amoco Corporation Olefin polymerization and copolymerization process
DE59209964D1 (en) 1991-03-09 2002-10-10 Basell Polyolefine Gmbh Metallocene and catalyst
ES2082274T3 (en) * 1991-05-27 1996-03-16 Hoechst Ag PROCEDURE FOR THE PREPARATION OF SYNDIOTACTIC POLYOLEFINS WITH WIDE DISTRIBUTION OF MOLECULAR MASSES.
ES2155492T3 (en) * 1991-05-27 2001-05-16 Basell Polyolefine Gmbh PROCEDURE FOR OBTAINING POLYOLEFINS WITH A LARGE DISTRIBUTION OF MOLECULAR WEIGHTS.
US5744677A (en) * 1991-10-16 1998-04-28 Amoco Corporation Ethylene oligomerization
US6184326B1 (en) 1992-03-20 2001-02-06 Fina Technology, Inc. Syndiotactic polypropylene
DE4333128A1 (en) * 1993-09-29 1995-03-30 Hoechst Ag Process for the preparation of polyolefins
US6784269B2 (en) 1998-05-13 2004-08-31 Exxonmobil Chemical Patents Inc. Polypropylene compositions methods of making the same
US6306960B1 (en) 1998-05-13 2001-10-23 Exxonmobil Chemical Patents Inc. Articles formed from foamable polypropylene polymer
US6174930B1 (en) 1999-04-16 2001-01-16 Exxon Chemical Patents, Inc. Foamable polypropylene polymer
JP4075495B2 (en) * 2002-04-17 2008-04-16 三菱化学株式会社 Polyurethane modified polypropylene resin solution
US7541402B2 (en) 2002-10-15 2009-06-02 Exxonmobil Chemical Patents Inc. Blend functionalized polyolefin adhesive
EP1558655B1 (en) 2002-10-15 2012-08-29 ExxonMobil Chemical Patents Inc. Multiple catalyst system for olefin polymerization and polymers produced therefrom
US7223822B2 (en) 2002-10-15 2007-05-29 Exxonmobil Chemical Patents Inc. Multiple catalyst and reactor system for olefin polymerization and polymers produced therefrom
US7700707B2 (en) 2002-10-15 2010-04-20 Exxonmobil Chemical Patents Inc. Polyolefin adhesive compositions and articles made therefrom
US7550528B2 (en) 2002-10-15 2009-06-23 Exxonmobil Chemical Patents Inc. Functionalized olefin polymers

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3472829A (en) * 1968-06-10 1969-10-14 Exxon Research Engineering Co Process for broadening the molecular weight distribution in polymers
DE3127133A1 (en) * 1981-07-09 1983-01-27 Hoechst Ag, 6000 Frankfurt METHOD FOR PRODUCING POLYOLEFINS AND THEIR COPOLYMERISATS
JPS58219207A (en) * 1982-06-15 1983-12-20 Chisso Corp Polypropylene having high rigidity and melt viscoelasticity and preparation thereof
US4522982A (en) * 1983-06-06 1985-06-11 Exxon Research & Engineering Co. Isotactic-stereoblock polymers of alpha-olefins and process for producing the same
US4530914A (en) * 1983-06-06 1985-07-23 Exxon Research & Engineering Co. Process and catalyst for producing polyethylene having a broad molecular weight distribution
DE3443087A1 (en) * 1984-11-27 1986-05-28 Hoechst Ag, 6230 Frankfurt METHOD FOR PRODUCING POLYOLEFINES
US4931417A (en) * 1987-11-09 1990-06-05 Chisso Corporation Transition-metal compound having a bis-substituted-cyclopentadienyl ligand of bridged structure
IT1221653B (en) * 1987-11-27 1990-07-12 Ausimonti Spa PROPYLENE CRYSTALLINE COPOLYMERS

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US4849487A (en) 1989-07-18
EP0269986B1 (en) 1991-07-31
AU599171B2 (en) 1990-07-12
DE3771849D1 (en) 1991-09-05
EP0269986A2 (en) 1988-06-08
ES2025618T3 (en) 1992-04-01
AU8187387A (en) 1988-06-02
JP2540174B2 (en) 1996-10-02
EP0269986A3 (en) 1989-05-17
ZA878922B (en) 1988-07-27
JPS63142005A (en) 1988-06-14
DE3640924A1 (en) 1988-06-01

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