With Group Ivb Transition Metal Compound (ti, Zr, Hf) Patents (Class 526/158)
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Patent number: 6303716Abstract: Disclosed is a catalyst for synthesizing low-, medium- and high-density polyethylene, prepared by using commercial powdered magnesium as a raw material, forming a magnesium halide in the nascent state, then reacting said magnesium halide with a titanium compound and an alkyl aluminum compound in the presence of an electron donor compound to form a complex, supporting said complex onto silica carrier and drying the resulting mixture by heating to form a solid main catalyst component, and finally mixing said main catalyst component with an organometallic compound as cocatalyst. The catalyst according to the present invention is characterized by a simple preparing procedure, smooth and stable reaction, uniform heat liberation and less agglomerates when used for gas phase polymerizing ethylene, high polymerization activity, high sensitivity to the modification by hydrogen and high copolymerization power, and the products thus obtained have good product morphology.Type: GrantFiled: July 13, 1999Date of Patent: October 16, 2001Assignees: China Retrochemical Corp., Shanghai Research Institute of Chemical Industry Sinopec UnilaInventors: Mingwei Xiao, Zixiao Chai, Xiaofeng Ye
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Patent number: 6300434Abstract: Propylene-ethylene copolymers obtainable by three-step polymerization from the gas phase in an agitated fixed bed by means of a Ziegler-Natta catalyst system which, in addition to a titanium-containing solid component, also contains, as cocatalyst, an aluminum compound, where, in a first polymerization step, propylene is polymerized at from 60 to 90° C. and at from 20 to 40 bar and at a mean residence time of the reaction mixture of from 0.5 to 5 hours, then, in a second polymerization step, a mixture of propylene and ethylene is polymerized onto the polymer obtained from the first polymerization step at from 40 to 110° C. and from 5 to 30 bar, this pressure being at least 7 bar below the pressure in the first polymerization step, and at a mean residence time of the reaction mixture of from 0.2 to 4 hours, and then, in a third polymerization step, ethylene or a mixture of ethylene and propylene is polymerized onto the polymer obtained from the second polymerization step at from 40 to 110° C.Type: GrantFiled: September 6, 1995Date of Patent: October 9, 2001Assignee: Basell Polyolefin GmbHInventors: Harald Schwager, Juergen Kerth
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Patent number: 6300450Abstract: The present invention provides a process for the production of a conjugated diene polymer having a controlled microstructure at a high polymerization activity in the presence of a metallocene type complex of compound of transition metal of the group V of the Periodic Table. A novel catalyst is provided comprising (A) a metallocene type complex of a transition metal of the group V of the Periodic Table, (B) an ionic compound of a non-coordinating anion and a cation, (C) an organic metal compound of the groups I to III and (D) water, wherein the molar ratio of (C)/(D) is from 0.66 to 5.Type: GrantFiled: November 19, 1998Date of Patent: October 9, 2001Assignee: UBE Industries, Ltd.Inventors: Nobuhiro Tsujimoto, Koji Maeda, Masato Murakami, Michinori Suzuki, Yasumasa Iwamoto, Sakae Yuasa, Satoshi Bandai, Yoshihira Hosoyama, Nobuharu Hisano
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Patent number: 6294626Abstract: A single-site olefin polymerization catalyst is described. The catalyst comprises an activator and an organometallic compound that includes a Group 3 to 10 transition or lanthanide metal, M, and a modified boraaryl ligand. We surprisingly found that the catalyst is more active in olefin polymerization compared to other catalysts containing non-modified boraaryl ligands. Most surprisingly, the supported catalyst gives polyolefins with a multimodal molecular weight distribution having separate components of distinct molecular weight.Type: GrantFiled: November 15, 1999Date of Patent: September 25, 2001Assignee: Equistar Chemicals, LPInventors: Shaotian Wang, Jean A. Merrick-Mack
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Patent number: 6294494Abstract: A novel loop/slurry olefin polymerization process is provided which produces ultra-high molecular weight ethylene homopolymer.Type: GrantFiled: December 18, 1998Date of Patent: September 25, 2001Assignee: Phillips Petroleum CompanyInventors: Max P. McDaniel, Elizabeth A. Benham
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Patent number: 6291609Abstract: The invention is directed to olefin polymerization processes using bridged hafnocene catalyst complexes comprising highly substituted noncoordinating anions that are surprisingly stable under high temperature olefin polymerization processes such that olefin copolymers having significant amount of incorporated comonomer can be prepared with high molecular weights. More specifically, the invention is a polymerization process for ethylene copolymers having a melt index of about 0.87 to about 0.930 comprising contacting, under homogeneous polymerization conditions at a reaction temperature at or above 140° C. to 225° C.Type: GrantFiled: March 3, 1999Date of Patent: September 18, 2001Assignee: ExxonMobil Chemical Patents Inc.Inventors: Donna J. Crowther, Bernard J. Folie, John F. Walzer, Jr., Rinaldo S. Schiffino
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Patent number: 6288192Abstract: An olefin polymer selected from the group consisting of a 1-butene homopolymer, a copolymers of 1-butene with propylene and a copolymer of 1-butene with an alkenyl hydrocarbon having 5 or more carbon atoms, wherein said olefin polymer is an amorphous polymer having a polystyrene-reduced number average molecular weight of 200,000 and substantially not having a melting point, an olefin polymerization catalyst obtained by contacting a specific transition metal compound(A), an organoaluminumoxy compound (B) soluble in an aromatic solvent and water (C), and a process for producing said olefin polymer with said catalyst.Type: GrantFiled: January 12, 1999Date of Patent: September 11, 2001Assignee: Sumitomo Chemical Company, Ltd.Inventors: Masayuki Fujita, Tatsuya Miyatake
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Patent number: 6231804Abstract: A high molecular weight polyethylene prepared by preliminary polymerization is added at the time of main polymerization of an olefin, for example, propylene, to prepare an olefin (co)polymer composition comprising the above high molecular weight polyethylene finely dispersed as fine particles in the polyolefin, such as polypropylene, and a cross-linked structure is formed in the olefin (co)polymer composition. This process can provide a modified olefin (co)polymer composition improved in the strength in a molten state in terms of melt tension or the like and in crystallization temperature and excellent in moldability such as high-speed producibility, and a molded modified olefin (co)polymer composition excellent in properties such as heat resistance and rigidity.Type: GrantFiled: October 1, 1999Date of Patent: May 15, 2001Assignee: Chisso CorporationInventors: Akira Yamauchi, Shingo Kikukawa, Jun Saito, Hitoshi Sato
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Patent number: 6200922Abstract: The catalyst systems comprise as active constituents a) a titanium-containing solid component comprising a compound of titanium, a compound of magnesium, a halogen, an inorganic oxide as support and a carboxylic ester as electron donor compound, and also, as cocatalyst, b) an aluminum compound and c) optionally a further electron donor compound, wherein the inorganic oxide used has a pH of from 1 to 6, an average particle diameter of from 5 to 200 &mgr;m, an average primary particle diameter of from 1 to 20 &mgr;M and voids or channels having an average diameter of from 0.1 to 20 &mgr;m and a macroscopic share of the volume of the overall particle within the range from 5 to 30%.Type: GrantFiled: June 5, 1997Date of Patent: March 13, 2001Assignee: BASF AktiengesellschaftInventors: Stephan Hüffer, Wolfgang Bidell, Patrik Müller, Ulrich Moll, Roland Hingmann, Günther Schweier
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Patent number: 6174973Abstract: Process for the preparation of crystalline vinylaromatic polymers with a high degree of syndiotaxy which comprises polymerizing vinylaromatic monomers in the presence of a catalytic system essentially consisting of: a) a complex of titanium having the general formula: CpTiX1X2X3 (I) wherein Cp represents a cyclopentadienyl ligand whereas X1, X2, X3, the same or different, are selected from a halogen such as chlorine, or from alkyl groups, alkoxides, carboxylates, di(alkyl)amides; b) a polyalkylaluminoxane wherein the alkyl group contains from 1 to 8 carbon atoms; c) aluminum trifluoride.Type: GrantFiled: October 12, 1999Date of Patent: January 16, 2001Assignee: Enichem S.p.A.Inventors: Riccardo Po', Luigi Abbondanza
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Patent number: 6174969Abstract: C2-C8-Alk-1-enes are polymerized by means of a Ziegler-Natta catalyst system in a reactor cascade comprising at least two reactors, a homo- or copolymer of C2-C8-alk-1-enes being prepared in a reactor RA, upstream of which one or more further reactors may be connected, the reaction mixture being discharged from RA and transferred to a subsequent reactor RB and the polymerization in RB and in the reactors which may be connected to RB being carried out in the presence of a liquid or dissolved regulator for regulating the catalyst activity, by a process in which the regulator is added to the reaction mixture after discharge from RA and before entry into RB, and an apparatus for polymerizing C2-C8-alk-1-enes by means of the novel process is described.Type: GrantFiled: July 2, 1998Date of Patent: January 16, 2001Assignee: BASF AktiengesellschaftInventors: Meinolf Kersting, Gerald Lutz, Franz Langhauser
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Patent number: 6121182Abstract: A catalyst component for polyolefin production catalysts comprising a metallocene compound represented by general formula (1) (symbols have the meanings as described in the specification), polyolefin production catalyst containing the component, and method for producing polyolefin with the catalyst are provided. Use of a catalyst containing the novel metallocene compound as a catalyst component of the invention in polymerization of .alpha.-olefin, particularly propylene, enables one to prepare high rigid, high melting point isotactic polypropylene useful as an industrial material for automobiles and the like, more specifically isotactic polypropylene having highly controlled stereoregulartity and regioregularity, particularly the one having a high regioregularity that has been difficult to achieve with conventional metallocene catalysts.Type: GrantFiled: December 11, 1997Date of Patent: September 19, 2000Assignee: Japan Polyolafins Co., Ltd.Inventors: Yoshikuni Okumura, Tsutomu Sakuragi, Michio Ono, Shintaro Inazawa
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Patent number: 6117957Abstract: A process for polymerization of olefins having increased molecular weight and melting point uses a catalyst formed by combining a chiral, stereorigid metallocene compound with an organoaluminum compound. The metallocene compound has a silicon hydrocarbyl radical as an interannular bridge between two cyclopentadienyl or substituted cyclopentadienyl rings which are coordinated with a metal which is bonded to a hydrocarbon radical or a halogen. The cyclopentadienyl rings are described by the formula (C.sub.5 R'.sub.m) wherein R' is hydrogen or hydrocarbyl radical having from 1-20 carbon atoms, each R' being the same or different. The metal is a group 4b, 5b or 6b metal as designated in the Periodic Table of Elements.Type: GrantFiled: March 5, 1997Date of Patent: September 12, 2000Assignee: Fina Technology, Inc.Inventor: John A. Ewen
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Patent number: 6111046Abstract: Amorphous polymers of propylene modified with ethylene units are prepared in high yields, by carrying out the polymerization reaction in the presence of a catalyst based on a metallocene compound that has two bridged fluorenyl ligands. These copolymers have glass transition temperatures (T.sub.g) well below 0.degree. C., making it possible for the products manufactured from them to be used at low temperatures.Type: GrantFiled: March 1, 1996Date of Patent: August 29, 2000Assignee: Montell Technology Company BVInventors: Luigi Resconi, Fabrizio Piemontesi
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Patent number: 6107231Abstract: In catalyst systems of the Ziegler-Natta type comprising as active constituentsa) a titanium-containing solid component which is obtained by reacting a compound of titanium with a compound of magnesium, a halogen, an inorganic oxide as support, a C.sub.1 -C.sub.8 -alkanol and a carboxylic ester as electron donor compound,and also as cocatalyst,b) an aluminum compound andc) if desired, a further electron donor compound,the reaction of the individual components for preparing the titanium-containing solid component a) is carried out in the presence of an aromatic hydrocarbon as solvent.Type: GrantFiled: September 12, 1997Date of Patent: August 22, 2000Assignee: BASF AktiengesellschaftInventors: Stephan Huffer, Ulrich Moll, Peter Kolle, Roland Hingmann
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Patent number: 6037433Abstract: A novel loop/slurry olefin polymerization process is provided which produces ultra high molecular weight ethylene homopolymer.Type: GrantFiled: November 13, 1998Date of Patent: March 14, 2000Assignee: Phillips Petroleum CompanyInventors: Joel L. Martin, Steven J. Secora, Elizabeth A. Benham, Max P. McDaniel, Eric Hsieh, Timothy W. Johnson
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Patent number: 5863995Abstract: The present invention relates to an ethylene polymerization process carried out with the aid of a catalyst system of the Ziegler-Natta type consisting essentially of titanium, halogen and magnesium. The process is performed such that the ethylene polymerization takes place in the presence of a polychlorinated saturated hydrocarbon compound. The halogenated hydrocarbon compound is used in a quantity such that the molar ratio of the halogenated hydrocarbon compound to titanium of the catalyst is in the range from 0.01 to 1.8. Preferably the halogenated hydrocarbon compound is chloroform or trichloro-1,1-ethane.Type: GrantFiled: November 10, 1997Date of Patent: January 26, 1999Assignee: BP Chemicals LimitedInventor: Erick Daire
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Patent number: 5696213Abstract: This invention is a solution process for the preparation of ethylene-.alpha.-olefin/diolefin copolymers comprising contacting ethylene, one or more .alpha.-olefin monomer, and optionally one or more diene monomer, with a catalyst system containing a catalyst activator and a Group 4 metallocene compound, comprising a) conducting the polymerization reaction at a temperature of about 60.degree. to 150.degree. C.; b) selecting as the Group 4 metallocene compound one or more members of the group consisting of cyclic monocyclopentadienyl Group 4 metal and covalently bridged (bis)indenyl hafnium metallocene compounds; and c) maintaining the .alpha.-olefin concentration at a molar ratio to that of ethylene of between about 0.3 to 7.0 and a diolefin to ethylene molar ratio of between about 0.01 and 0.4. In a preferred embodiment the process comprises: 1) mixing with a reaction solvent the one or more .alpha.Type: GrantFiled: April 21, 1995Date of Patent: December 9, 1997Assignee: Exxon Chemical Patents Inc.Inventors: Rinaldo Soria Schiffino, Javier Mario Zamora
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Patent number: 5571885Abstract: Immobilized Lewis Acid catalyst comprising polymer having at least one Lewis Acid immobilized within the structure therein, said polymer having monomer units represented by the structural formula:--[A].sub.a --[B].sub.b --[C].sub.c --whereina represents about 1 to about 99 mole %b represents about 0 to about 50 mole %c represents about 1 to about 99 mole %a+b+c is preferably about 100%; ##STR1## C is selected from the group consisting of: ##STR2## (III) combinations thereof, wherein D is OH, halide, OR.sup.4, NH.sub.2, NHR.sup.3, OM', or OM";E is the residue of the reaction of at least one Lewis Acid with the D substituent of monomer unit B;R.sup.1 represents proton, C.sub.1 -C.sub.24 alkyl group, or C.sub.3 -C.sub.24 cycloalkyl;R.sup.2 represents C.sub.1 -C.sub.24 alkylene group, C.sub.3 -C.sub.24 cycloalkylene, C.sub.6 -C.sub.18 arylene, or C.sub.7 -C.sub.30 alkylarylene;R.sup.3 represents C.sub.1 -C.sub.24 alkyl, C.sub.3 -C.sub.24 cycloalkyl, C.sub.1 -C.sub.24 aryl, or C.sub.7 -C.sub.30 alkylaryl;R.sup.Type: GrantFiled: March 3, 1995Date of Patent: November 5, 1996Assignee: Exxon Chemical Patents Inc.Inventors: Tze-Chiang Chung, Frank J.-Y. Chen, Jon E. Stanat, Alok Kumar
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Patent number: 5543484Abstract: Copolymers comprising poly(.alpha.-olefin) having at least few p-alkylstyrene (para-alkylstyrene) groups or/and p-alkylstyrene derivatives within the structure therein, said polymer having monomer units represented by the structural formula: ##STR1## in which R, R' and R" are, independently, either hydrogen, alkyl, or primary or secondary alkyls. Preferably, R is hydrogen and C.sub.1 to C.sub.10 linear and branched alkyl, and most preferably R is hydrogen, C.sub.1 and C.sub.2. R' and R" are hydrogen, C.sub.1 to C.sub.5 alkyl, or C.sub.1 to C.sub.5 primary or secondary alkyl, and most preferably R' and R" are hydrogen. F comprises a hydrogen or a functional group, such as --COOH, --OH, --NH.sub.2, --Cl, --Br, --M, --COOM (M=metals, e.g. Li, Na, K and Ca) etc., or a mixture of functional group and hydrogen. In the copolymer composition, the .alpha.-olefin mole % (m) is between about 5 and 99.9. Preferably, m is between 85 and 99.9, and most preferably m is between 95 and 99.9.Type: GrantFiled: November 18, 1994Date of Patent: August 6, 1996Assignee: The Penn State Research FoundationInventors: T. C. Chung, H. L. Lu
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Patent number: 5374597Abstract: Catalysts useful in olefin polymerization are a mixture of (a) (i) one or more compounds Zn(X.sup.1).sub.2 and one or more compounds Al(R.sup.1).sub.3, or (ii) Zn(X.sup.1).sub.2.2Al(R.sup.1).sub.3, wherein X.sup.1 is halide and R.sup.1 is C.sub.1-12 hydrocarbyl; and (b) one or more of V(X.sup.2).sub.c (OR.sup.2).sub.b-c, VO(X.sup.3).sub.d (OR.sup.3).sub.3-d, or VO(X.sup.4).sub.2, wherein X.sup.2, X.sup.3 and X.sup.4 are halogen, R.sup.2 and R.sup.3 are C.sub.1-18 hydrocarbyl, b is 3-4, c is 0-b, and d is 0-3; and can contain (c) one or more of M(R.sup.5).sub.e (X.sup.5).sub.3-e, Al.sub.2 (R.sup.5).sub.3 (X.sup.5).sub.3 or Mg(R.sup.6).sub.f Y.sub.2-f, wherein X.sup.1 and X.sup.2 are halide, R.sup.1, R.sup.5, R.sup.6 and R.sup.9 are C.sub.1- 12 hydrocarbyl, M is Al or B, e is 0-3, Y is halide, O--(C.sub.1-12 hydrocarbyl) or N(SiR.sup.9.sub.3).sub.2, and f is 0-2.Type: GrantFiled: February 12, 1993Date of Patent: December 20, 1994Assignee: Quantum Chemical CorporationInventors: Chi-I Kuo, Michael W. Lynch
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Patent number: 5317036Abstract: Gas phase polymerization processes are disclosed which utilize unsupported soluble transition metal coordination catalysts. The catalysts are introduced into the reactor as a solution.Type: GrantFiled: October 16, 1992Date of Patent: May 31, 1994Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Robert C. Brady, III, Frederick J. Karol, Timothy R. Lynn, Robert J. Jorgensen, Sun-Chueh Kao, Eric P. Wasserman
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Patent number: 5066736Abstract: A process for the continuous polymerization of one or more alpha-olefins with a transition metal catalyst, in a reactor having a fluidized and/or mechanically stirred bed, in which a very small amount of an activity retarder, generally less than 0.1 ppm, is introduced continuously into the reactor at a flow rate which is varied with time so as to keep substantially constant either the polymerization rate or the content of transition metal in the polymer produced. Suitable activity retarders include polymerization inhibitors such as, for example, oxygen, alcohols, carbon monoxide and carbon dioxide and electron donor compounds such as amides and ethers.Type: GrantFiled: September 5, 1989Date of Patent: November 19, 1991Assignee: BP Chemicals LimitedInventors: Andre Dumain, Jean Engel, Laszlo Havas
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Patent number: 4892914Abstract: Ziegler-Natta catalysts for polymerizing .alpha.-olefins are prepared by the addition of tetrakis(dialkylamide or diarylamide) derivatives of titanium, and a metal-containing reducing agent such as ethyl aluminum dichloride to a suitable support material such as magnesium chloride. Olefins are polymerized in the presence of these supported catalysts and an aluminum containing cocatalyst or activator such as triethylaluminum.Type: GrantFiled: January 11, 1989Date of Patent: January 9, 1990Assignee: The Dow Chemical CompanyInventor: John G. Hefner
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Patent number: 4880436Abstract: A method of viscosifying an organic liquid which comprises adding a sufficient quantity of a hydrolyzed Ziegler Natta-ester containing copolymer haivng a molecular weight of about 100,00 to about 10,000,000 to said organic liquid to increase the viscosity of said organic liquid, said copolymer having the formula: ##STR1## wherein R.sub.1 is an alkyl group having about 4 to about 6 carbon atoms, R.sub.2 is an alkylene group having 3 to 16 carbon atoms, x is about 95.0 to about 99.95 mole % and y is about 0.05 to about 5.0 mole %.Type: GrantFiled: November 20, 1987Date of Patent: November 14, 1989Assignee: Exxon Research and Engineering CompanyInventors: Kissho Kitano, Ilan Duvdevani, Donald N. Schulz
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Patent number: 4751276Abstract: The present invention relates to a process for the preparation of functional alpha-olefin homo- and copolymers by polymerization through a borane monomer intermediate.Borane monomers, derived from mono-hydroboration of appropriate dienes with dialkyl borane, have been found to be stable to Ziegler-Natta catalysts. In turn, the borane homo- and copolymers are easily converted to a variety of other functionalities; e.g., alcohols, aldehydes, amines, etc.Type: GrantFiled: July 27, 1987Date of Patent: June 14, 1988Assignee: Exxon Research and Engineering CompanyInventor: Tze-Chiang Chung
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Patent number: 4740570Abstract: Metal halide particles useful, among other things, as olefin polymerization catalyst precursors and catalyst supports, are prepared by vaporizing the metal halide and then condensing it in the presence of a diluent.Type: GrantFiled: November 13, 1986Date of Patent: April 26, 1988Assignee: E. I. Du Pont de Nemours and CompanyInventors: Ulrich Klabunde, Rolf Mulhaupt
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Patent number: 4715865Abstract: A method of viscosifying an organic liquid which comprises adding a sufficient quantity of a hydrolyzed Ziegler Natta-ester containing copolymer having a molecular weight of about 100,000 to about 10,000,000 to said organic liquid to increase the viscosity of said organic liquid, said copolymer having the formula: ##STR1## wherein R.sub.1 is an alkyl group having about 4 to about 6 carbon atoms, R.sub.2 is an alkylene group having about 3 to about 17 carbon atoms, x is about 95.0 to about 99.95 mole % and y is about 0.05 to about 5.0 mole %.Type: GrantFiled: December 9, 1985Date of Patent: December 29, 1987Assignee: Exxon Research and Engineering CompanyInventors: Kissho Kitano, Ilan Duvdevani, Donald N. Schulz
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Patent number: 4690991Abstract: The present invention concerns a procedure for copolymerization of ethylene and alpha olefins with at least eight carbon atoms in the presence of a catalyst of Ziegler-Natta type to become a polymer, in which the quantity of alpha olefin containing at least eight carbon atoms can be regulated between 0.01 and 15% by weight. Polymerization is carried out at a temperature not exceeding 120.degree. C. in a fluid in which the polymer is insoluble. The monomer mixture contains, for increasing the reactivity of the long-chained alpha olefin, 0.01 to 2.0 mol/dm.sup.3 of short-chained alpha olefin with not more than five carbon atoms. The alpha olefin containing not more than five carbon atoms is preferably 1-butylene or propylene.Type: GrantFiled: February 4, 1985Date of Patent: September 1, 1987Assignee: Neste OyInventor: Jukka Seppala
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Patent number: 4680351Abstract: A highly active catalyst suitable for the polymerization of olefins and its use are disclosed, said catalyst being prepared by(1) co-comminuting an aluminum halide; at least one electron donor; a Group IVB-VIB transition metal compound; and a support base selected from the group consisting of the Group IIA and IIIA salts and the salts of the multivalent metals of the first transition series with the exception of copper to produce a coground solid;(2) extracting said coground solid with an organic liquid; and(3) separating the solid from the liquid under such conditions that at least 5 weight percent of the aluminum in the coground solid is removed.Type: GrantFiled: October 10, 1986Date of Patent: July 14, 1987Assignee: Phillips Petroleum CompanyInventors: Nemesio D. Miro, Floyd E. Farha, Charles E. Capshew
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Patent number: 4605714Abstract: A catalyst component for olefin polymerization is a mixture of a transition metal composition with finely divided talc or a metal salt of an aromatic carboxylic acid. The talc or metal salt can be mixed with the transition metal composition during the production thereof or in a subsequent stage. Preferably an intimate mixture of the transition metal composition and the talc or metal salt is obtained, for example by grinding or by spray-drying. The catalyst component may be used to prepare an olefin polymer having improved properties.Type: GrantFiled: September 12, 1985Date of Patent: August 12, 1986Assignee: Imperial Chemical Industries, PLCInventor: Maurice G. Baker
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Patent number: 4460757Abstract: A process for producing highly crystalline .alpha.-olefin polymers of good particle form with high yield is provided, which comprises polymerizing .alpha.-olefin in the presence of a preactivated catalyst obtained by reacting a reaction product (I) of organoaluminum compound (A.sub.1) with electron donor (B.sub.1), with TiCl.sub.4 to obtain a solid product (II); further reacting (II) with electron donor (B.sub.2) and electron acceptor to obtain a solid product (III); during or/and after the reaction step for obtaining (II) or/and during or/and after the reaction step for obtaining (III), subjecting (II) or (III), to polymerization treatment with .alpha.-olefin; and combining the resulting final solid product with organo-aluminum compound (A.sub.2) and a reaction product (G) of organo-aluminum compound (A.sub.3) with electron donor (B.sub.3) to obtain a preactivated catalyst; and preferably, in this combination, further subjecting a part or the total of the catalyst to polymerization treatment with .alpha.Type: GrantFiled: July 29, 1982Date of Patent: July 17, 1984Assignee: Chisso CorporationInventors: Akihiro Sato, Masami Tachibana, Toshihiro Uwai, Kenji Matsuda, Yoshiharu Higuchi
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Patent number: 4451688Abstract: Olefins are polymerized in the presence of a catalyst which comprises the combination of:[I] a solid substance obtained by the reaction of at least the following two components:(i) a magnesium compound represented by the general formula R.sup.1.sub.m (OR.sup.2).sub.n MgX.sub.2-m-n wherein R.sup.1 and R.sup.2 are each a hydrocarbon radical having 1 to 24 carbon atoms, X is a halogen atom, m is 0.ltoreq.m.ltoreq.2 and n is 0.ltoreq.n.ltoreq.2, provided 0.ltoreq.m+n.ltoreq.2, and(ii) a titanium compound and/or a vanadium compound;[II] a silicon compound represented by general formula R.sup.1 mSi(OR.sup.2).sub.n X.sub.4-m-n wherein R.sup.1 and R.sup.2 are each hydrocarbon radical having 1 to 24 carbon atoms, X is a halogen atom, m is 0.ltoreq.m<4 and n is 0<n.ltoreq.4, provided 0 m+n 4;[III] an organometallic compound, where said catalyst comprises a product obtained by pre-reacting said silicon compound (II) and said organometallic compound (III).Type: GrantFiled: September 1, 1982Date of Patent: May 29, 1984Assignee: Nippon Oil Company, LimitedInventors: Nobuyuki Kuroda, Toru Nakamura, Yutaka Shikatani, Kazuo Matsuura, Mituji Miyoshi
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Patent number: 4379074Abstract: This application relates to a process for the homopolymerization (or copolymerization) of unsaturated compounds, particularly ethylene and higher alpha olefines, to give homopolymers (or copolymers) having a wide molecular weight distribution.The polymerization yields are very high, even at relatively low pressures (10 bars), i.e. such as not to require scrubbing in order to remove the catalytic residue from the polymer.These results are obtained by using, in union with an organometallic aluminium compound, a catalyst in the form of a new titanium trihalide-based chemical composition satisfying the following formula:TiX.sub.3.mM'Y.sub.n.qM"Y'.sub.p.cAlY".sub.3-s R.sub.Type: GrantFiled: December 5, 1980Date of Patent: April 5, 1983Assignees: Anic S.p.A., Snamprogetti, S.p.A.Inventors: Agostino Balducci, Margherita Corbellini, Mirko Osellame
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Patent number: 4368305Abstract: A process for producing polyolefins and particularly polyethylene which are high in molecular weight or which are wide in molecular weight distribution and thus suitable for extrusion or blow molding purposes, the process comprising polymerizing olefins such as ethylene by the use of a catalytic system which is comprised of a solid catalytic component obtained by mixing or interacting oxygen-containing organometal compounds or halides of (a) vanadium and (b) hafnium or a solid catalytic component obtained by mixing or interacting oxygen-containing organometal compounds or halides of (A) vanadium, (B) hafnium and (C) titanium, and (D) an organoaluminum compound, and of an organoaluminum compound.Type: GrantFiled: August 1, 1980Date of Patent: January 11, 1983Assignee: Mitsubishi Chemical Industries, Ltd.Inventors: Toru Tanaka, Eiji Tanaka
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Patent number: 4368304Abstract: A process for producing .alpha.-olefin polymers is provided, which comprises: reacting an organoaluminum compound with an electron donor in a specified ratio in a solvent at a specified temperature to obtain a solid product (I); reacting solid product (I) with TiCl.sub.4 at a specified temperature in a specified ratio of Al/Ti and then removing a liquid portion from the resulting material followed by washing to obtain a solid product (II) having no free TiCl.sub.4 ; reacting solid product (II) with an electron donor and an electron acceptor in a specified ratio at a specified temperature to obtain a solid product (III); and polymerizing .alpha.-olefin(s) in the presence of a catalyst comprising a combination of solid product (III) with an organoaluminum compound. This process provides a catalyst having a high storing and thermal stability and a polymer having a uniform particle size.Type: GrantFiled: February 4, 1981Date of Patent: January 11, 1983Assignee: Chisso CorporationInventors: Akihiro Sato, Toshihiro Uwai, Tohru Hanari, Kazutsune Kikuta, Masazumi Miyajima
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Patent number: 4357452Abstract: Propylene is polymerized in the presence of a catalytic system of the type which comprises a solid titanium trichloride-based complex serving as a catalyst, said complex having an atomic ratio of aluminum to titanium in the range of below 0.15:1 and containing a complexing agent, and an organic aluminum compound of the general formula, AlR.sup.1.sub.n Cl.sub.3-n wherein R.sup.1 represents an n-propyl group or an n-hexyl group and n is a value of 1.95-2.10. The catalytic system may further comprise an electron-donor compound as a third catalytic component.Type: GrantFiled: July 16, 1980Date of Patent: November 2, 1982Assignee: Mitsubishi Chemical Industries LimitedInventors: Genjiro Kakogawa, Masayoshi Hasuo, Yoshinori Suga, Hisashi Kitada, Yumito Uehara
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Patent number: 4352915Abstract: In a slurry polymerization for producing an ethylene homopolymer or ethylene-.alpha.-olefin copolymer in multiple stages, in which the gas phase hydrogen concentration in each stage is different, using a catalyst system comprising a transition metal compound component and an organoaluminum compound component, the improvement which comprises conducting the polymerization by the use of a solid catalyst component comprising a titanium compound and/or vanadium compound supported on a specified magnesium compound, as the transition metal compound component, in a molar ratio of gas phase hydrogen to ethylene of 0.5 to 15 in the first stage thereby obtaining 30 to 95% by weight, of the total polymer, and in the second stage in a molar ratio of gas phase hydrogen to ethylene, not exceeding 0.2. By this process, it is possible to produce polyethylene having high melt flow and good homogeneity to give molded articles having fewer fish-eyes and less unevenness.Type: GrantFiled: May 23, 1980Date of Patent: October 5, 1982Assignee: Sumitomo Chemical Company, LimitedInventors: Kentaro Mashita, Katsumi Hanji
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Patent number: 4309522Abstract: A process for preparing an extensively amorphous butene-1-propene-ethene terpolymer having a high softening point comprises low pressure solution polymerizing butene-1, propene and ethene by contacting these monomers with a catalytically effective amount of a mixed catalyst of a thermally unstable crystalline TiCl.sub.3 .multidot.0.30 to 0.35 AlCl.sub.3 and a trialkyl aluminum or dialkyl aluminum hydride, each having alkyl groups of 2-4 carbon atoms, the atomic ratio of Al:Ti being 0.8-4.0.Type: GrantFiled: July 24, 1980Date of Patent: January 5, 1982Assignee: Chemische Werke Huels, AktiengesellschaftInventors: Johannes Dietrich, Walter Dittmann, Albert Frese, Wolfgang Kilian
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Patent number: 4309521Abstract: A process for producing .alpha.-olefin polymers is provided which comprises:reacting an organoaluminum compound (A.sub.1) with an electron donor (B.sub.1) to obtain a reaction product (I);reacting (I) with TiCl.sub.4 to obtain a solid product (II);reacting (II) with an electron donor (B.sub.2) and an electron acceptor to obtain a solid product (III);combining (III) with an organoaluminum compound (A.sub.2) and a reaction product (G) of an organoaluminum (A.sub.3) with an electron donor (B.sub.3) ((III), (A.sub.2) and (G) being referred to as catalyst components), and in this combination, subjecting a part or the whole of the catalyst components to polymerization treatment with an .alpha.-olefin at least in the presence of (III) and said (A.sub.2) to obtain a preliminarily activated catalyst;andpolymerizing an .alpha.-olefin in the presence of the catalyst.Type: GrantFiled: May 14, 1980Date of Patent: January 5, 1982Assignee: Chisso CorporationInventors: Akihiro Sato, Kazutsune Kikuta, Kenji Matsuda, Toshihiro Uwai, Tohru Hanari
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Patent number: 4285834Abstract: A catalyst mixture containing at least two independently supported catalysts, at least one of which is an inorganic halide supported titanium and/or vanadium Ziegler type catalyst and at least one other is an inorganic oxide supported, chromium catalyst.These catalyst mixtures are suitable for polymerizing one or more .alpha.-olefins.Type: GrantFiled: December 31, 1979Date of Patent: August 25, 1981Assignee: The Dow Chemical CompanyInventors: Kirby Lowery, Jr., Fred L. Vance, Jr.
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Patent number: 4258161Abstract: Propylene is polymerized in the presence of a catalytic system of the type which comprises a solid titanium trichloride-based complex serving as a catalyst, said complex having an atomic ratio of aluminum to titanium in the range of below 0.15:1 and containing a complexing agent, and an organic aluminium compound of the general formula, AlR.sub.n.sup.1 Cl.sub.3-n wherein R.sup.1 represents an n-propyl group or an n-hexyl group and n is a value of 1.95-2.10. The catalytic system may further comprise an electron-donor compound as a third catalytic component.Type: GrantFiled: January 22, 1979Date of Patent: March 24, 1981Assignee: Mitsubishi Chemical Industries Ltd.Inventors: Genjiro Kakogawa, Masayoshi Hasuo, Yoshinori Suga, Hisashi Kitada, Yumito Uehara
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Patent number: 4238355Abstract: Compositions exhibiting high catalytic activity in the polymerization of .alpha.-olefins, particularly higher olefins, are prepared by reacting tetravalent or trivalent titanium compounds such as a titanium tetraalkoxide, an anhydrous zinc compound such as diethyl zinc, an organomagnesium component such as a hydrocarbon soluble complex of dialkyl magnesium and an alkyl aluminum and a halide source such as a hydrogen halide or an alkyl aluminum halide and an aluminum compound if the halide source of organomagnesium component does not contain sufficient quantities of aluminum. Polymerization processes employing this catalyst composition do not require conventional catalyst removal steps in order to provide polymers having suitable color and other physical characteristics and these catalysts produce polymers having broader molecular weight distributions than do corresponding catalysts without the anhydrous zinc compound.Type: GrantFiled: September 10, 1979Date of Patent: December 9, 1980Assignee: The Dow Chemical CompanyInventors: Randall S. Shipley, Donald F. Birkelbach, Kirby Lowery, Jr.
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Patent number: 4237029Abstract: A catalyst system is made up of a catalyst and a cocatalyst. The catalyst component is made by intensely mixing a titanium trihalide component with triaryl phosphite and aluminum trihalide adjuvants. The cocatalyst is an organoaluminum compound. An example of such a system is a ball milled mixture of TiCl.sub.3..sup.1/ 3AlCl.sub.3, triphenyl phosphite, and aluminum trichloride as the catalyst and diethylaluminum chloride as the cocatalyst. Such catalyst systems give both high productivity and low solubles in the polymerization of propylene. The catalytic activity and/or stereospecificity of the catalyst can be enhanced by heat treatment at a moderate temperature subsequent to milling the mixture.Type: GrantFiled: January 29, 1979Date of Patent: December 2, 1980Assignee: Phillips Petroleum CompanyInventor: Lawrence M. Fodor
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Patent number: 4222893Abstract: A process is described herein for improving the crystalline olefin polymerization yield and soluble polymer production of a high surface area, large porosity, brown catalyst component comprising beta titanium trichloride and some of at least one organic electron pair donor compound, which component is prepared by organoaluminum compound reduction of titanium tetrachloride followed by incorporation of the reduced solid with said donor compound and thereafter treatment with an electron pair acceptor compound. The improved process employs in the reduction a dialkylaluminum compound and a second material, which second material is subsequently substantially extracted prior to use of said component for polymerization.Type: GrantFiled: April 3, 1978Date of Patent: September 16, 1980Assignee: Standard Oil Company (Indiana)Inventors: Nicholas M. Karayannis, Harold Grams
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Patent number: 4218551Abstract: A polybutene-1 mixture which forms heat sealable, transparent film having good initial tear resistance and resistance to tear propagation are produced by polymerizing liquid butene-1 at 60.degree.-120.degree. C. employing as catalyst a dihalidefree mixture of diethylaluminum monochloride and TiCl.sub.3.nAlCl.sub.3 wherein n is 0.2 to 0.6, and isolating the unfractionated mixture of polymers.Type: GrantFiled: April 6, 1978Date of Patent: August 19, 1980Assignee: Chemische Werke Huls AktiengesellschaftInventor: Albert Frese
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Patent number: 4217245Abstract: A novel catalyst system for the polymerization or copolymerization of olefines, more particularly to ethylene is disclosed. For preparing the novel catalyst system, a titanium compound (Ti IV) is previously attached to a solid supporting member, whereafter the so anchored Ti is reacted with vapors of a metal, in the presence of a halogenated compound or not. Very high polymer yields are obtained and examples are given.Type: GrantFiled: June 2, 1978Date of Patent: August 12, 1980Assignee: Snamprogetti, S.p.A.Inventors: Margherita Corbellini, Alessandro Gamba, Carlo Busetto
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Patent number: 4210735Abstract: Process for the polymerization of .alpha.-olefins in the presence of an activator selected from among the organic compounds of metals of groups Ia, IIa, IIb and IIIa of the Periodic Table and a solid catalytic element prepared by(a) reducing TiCl.sub.4 by means of a reducing metal selected from among the metals of groups Ia, IIa, IIb, IIIa of the Periodic Table so as to prepare a double chloride of titanium and the reducing metal(b) treating the double chloride thus prepared by means of a complexant(c) reacting the double chloride thus treated with TiCl.sub.4(d) separating the solid catalytic element thus prepared.Type: GrantFiled: October 12, 1972Date of Patent: July 1, 1980Assignee: Solvay & Cie.Inventors: Jean-Pierre Hermans, Paul Henrioulle
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Patent number: 4210738Abstract: Solid catalytic complexes are useful for stereospecific polymerization of .alpha.-olefins to solid crystalline polymers. The complexes are formed by reducing TiCl.sub.4 with an alkylaluminum, treating thus-obtained reduced solid with a complexing agent and contacting the resultant with TiCl.sub.4. They have a specific surface greater than 75 m.sup.2 /g.Type: GrantFiled: March 21, 1972Date of Patent: July 1, 1980Assignee: Solvay & Cie.Inventors: Jean P. Hermans, Paul Henrioulle
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Patent number: 4210729Abstract: Storage stability of Ziegler-type catalysts for .alpha.-olefin polymerization and having a specific surface greater than 75 m.sup.2 /g is improved by treating the catalysts with a preactivator which is an organic compound of a metal of one of Groups Ia, IIa, IIb and IIIa of the Periodic Table.CROSS-REFERENCE TO RELATED APPLICATIONThe invention described herein is directly related to that described in copending Application Ser. No. 236,407, filed Mar. 21st, 1972. The entire text of that application is incorporated herein by reference.BACKGROUND OF THE INVENTIONZiegler-type microporous catalytic complexes having a specific surface area greater than 75 m.sup.2 /g and useful for the polymerization of .alpha.-olefins are prepared by (a) reducing TiCl.sub.4 by means of an aluminum alkyl; (a') optionally isolating the reduced solid, based on TiCl.sub.Type: GrantFiled: August 27, 1973Date of Patent: July 1, 1980Assignee: Solvay & Cie.Inventors: Jean-Pierre Hermans, Paul Henrioulle