Ester Patents (Class 502/127)
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Patent number: 5082907Abstract: A complex alkoxide compound precursor of an olefin polymerization catalyst component is produced by contacting a magnesium alkoxide, a titanium alkoxide and a borate ester in alkanol solution. Alkanol is removed from the resulting complex alkoxide compound alcoholate and the resulting product is contacted with tetravalent titanium halide, halohydrocarbon and an electron donor. The resulting solid olefin polymerization procatalyst is contacted with organoaluminum cocatalyst and a selectivity control agent. The resulting olefin polymerization catalyst affords polyolefin product in good productivity and with good stereospecificity.Type: GrantFiled: October 18, 1990Date of Patent: January 21, 1992Assignee: Shell Oil CompanyInventor: Robert C. Job
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Patent number: 5081088Abstract: Ziegler-Natta-type catalyst systems contain as active constituentsa) atitanium-containing solid component which contains titanium, magnesium, halogen and a norbornadienedicarboxylate of the formula I ##STR1## as electron donor, where R.sup.1 and R.sup.2 are each C.sub.1 -C.sub.8 -alkyl or 5- to 7-membered cycloalkyl which in turn can carry C.sub.1 -C.sub.10 -alkyl groups,b) an aluminum component andc) another electron donor component,and are particularly suitable for preparing polypropylene and copolymers of propylene with minor amounts of other .alpha.-olefins with 2 to 8 carbon atoms.Type: GrantFiled: September 20, 1990Date of Patent: January 14, 1992Assignee: BASF AktiengesellschaftInventors: Peter Koelle, Juergen Kerth
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Patent number: 5081090Abstract: A solid hydrocarbon-insoluble, alpha-olefin polymerization catalyst component with superior activity, stereospecificity and morphology characteristics comprising the product formed by A) forming a solution of a magnesium-containing species from a magnesium alkyl (or hydrocarbyl) carbonate or a magnesium carboxylate; B) precipitating solid particles from such solution by treatment with a transition metal halide; C) reprecipitating such solid particles from a mixture containing a cyclic ether; D) treating the reprecipitated particles with a transition metal compound and an electron donor; and E) drying the resulting solid particles such that the residual volatile hydrocarbon content is between 0.1 and 0.9 weight percent.Type: GrantFiled: July 23, 1990Date of Patent: January 14, 1992Assignee: Amoco CorporationInventors: Gregory G. Arzoumanidis, Habet M. Khelghatian, Linda Ornellas
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Patent number: 5081087Abstract: A process for preparing an olefin polymerization catalyst which comprises halogenating a magnesium-di-(3-halo- or 3- C.sub.1 to C.sub.8 alkoxy-phenoxide) with a halide of tetravalent titanium in the presence of a halohydrocarbon, recovering the solid reaction product from the reaction mixture and combining the solid reaction product with an organo aluminium compound and an electron donor.Type: GrantFiled: October 17, 1990Date of Patent: January 14, 1992Assignee: Shell Research LimitedInventors: Alan Villena, Ronald P. Van Gaalen, John C. Chadwick, Theodorus K. Jurriens
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Patent number: 5077357Abstract: An improved olefin polymerization process employs an olefin polymerization catalyst produced from a polymerization procatalyst made from a magnesium alkoxide, a titanium tetraalkoxide, a tetravalent titanium halide, a phenolic compound and an alkanol. The procatalyst precursor is contacted with a tetravalent titanium halide and an electron donor to form the procatalyst which is subsequently converted to the olefin polymerization catalyst by contact with a cocatalyst and a selectivity control agent.Type: GrantFiled: October 22, 1990Date of Patent: December 31, 1991Assignee: Shell Oil CompanyInventor: Robert C. Job
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Patent number: 5077250Abstract: An olefin polymerization catalyst comprising:(A) a solid catalyst component containing a trivalent titanium, which is represented by the composition formulaMg.sub.m Ti(OR).sub.n X.sub.p [ED].sub.q(wherein R is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, ED is a electron donative compound, and m, n, p and q are each a number satisfying 1.ltoreq.m.ltoreq.51, 0<n.ltoreq.5, 5.ltoreq.p.ltoreq.106 and 0.2.ltoreq.q.ltoreq.2) obtained by reducing a titanium compound represented by the general formula Ti(OR.sup.1).sub.a X.sub.4-a (wherein R.sup.1 is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom and a is a number satisfying 0<a.ltoreq.Type: GrantFiled: April 24, 1990Date of Patent: December 31, 1991Assignee: Sumitomo Chemical Company, LimitedInventors: Yoshihiro Miyoshi, Hiroyuki Shiraishi, Takeshi Ebara, Toshio Sasaki, Kiyoshi Kawai
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Patent number: 5075396Abstract: A process for producing a polymer or copolymer of an olefin which comprises polymerizing or copolymerizing at least one olefin with or without a diolefin in the presence of a catalyst composed of (A) a magnesium-containing solid titanium catalyst component containing magnesium, titanium, a halogen and an electron donor as essential ingredients and (B) an organoaluminum compound catalyst component; characterized in that(1) said catalyst further comprises (C) an organic silicon compound catalyst component having an Si--O--C or Si--N--C bond, and(2) said electron donor in the catalyst component (A) is a cyclic mono- or poly-ester such as diethyl furane-3,4-dicarboxylate, di-n-butyl 3,4-dihydro-2H-pyrane-5,6-dicarboxylate, di-isobutyl pyrrole-2,3-dicarboxylic, di-n-butyl thiophene-2,3-dicarboxylate, n-octyl pyrrolidine-2,3-dicarboxylate, and so on.Type: GrantFiled: March 31, 1989Date of Patent: December 24, 1991Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Norio Kashiwa, Akinori Toyota, Mamoru Kioka
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Patent number: 5070057Abstract: An improved support vanadium catalyst, especially an improved Beran et al. catalyst system and ethylene polymerization process in which the improvement derives from fixing the promoter to a component of the catalyst composition such that it is a molecularly structural component of the catalyst and thus is not separately fed to the polymerization reaction, but instead is part of the catalyst composition fed to the reaction.Type: GrantFiled: April 2, 1990Date of Patent: December 3, 1991Assignee: Union Carbide Chemicals and Plastics Technology CorporationInventors: Kevin J. Cann, Frederick J. Karol, Arthur E. Marcinkowsky
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Patent number: 5070056Abstract: Catalyst compositions enabling the production of polyalkenes with improved bulk density are prepared by combining the following catalyst components in the following order of addition: first introducing an electron donor component, then adding a reaction product of a di-alkylaluminium halide and a solid component comprising a magnesium di-halide, an electron donor and a halide of tetravalent titanium and lastly adding a tri-alkylaluminium compound.Type: GrantFiled: October 29, 1990Date of Patent: December 3, 1991Assignee: Shell Internationale Research Maatschappij, B.V.Inventors: Ian G. Carson, Petrus A. Bentvelsen
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Patent number: 5068213Abstract: Catalyst components for the polymerization of olefins comprising a titanium halide or alkoxyhalide and an electron-donor compound selected from ethers having two or more ether groups and containing at least one heteroatom selected from the group consisting of N, S, P, Si, non-ether O and halogen atoms or at least one double bond, or both at least one heteroatom and at least one double bond, supported on a magnesium halide in active form.Catalysts obtained from said catalyst components and an Al-alkyl compound, as well as catalysts obtained by the reaction of an Al-alkyl compound and an ether having the above defined characteristics with a solid catalyst component comprising a titanium halide or alkoxyhalide and an electron-donor compound having particular characteristics of extractability with Al-triethyl, supported on activated magnesium halide.Type: GrantFiled: March 26, 1991Date of Patent: November 26, 1991Assignee: Hinmont IncorporatedInventors: Enrico Albizzati, Giampiero Morini, Umberto Giannini, Luisa Barino, Raimondo Scordamaglia, BarbePier C., Luciano Noristi
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Patent number: 5066737Abstract: A complex, magnesium-containing, titanium-containing solid olefin polymerization procatalyst precursor is produced by reaction of magnesium alkoxide, titanium tetraalkoxide and a phenolic compound followed by removal of alkanol. Conversion of this solid to an olefin polymerization procatalyst and the procatalyst to an olefin polymerization catalyst results in a catalyst which is used to polymerize lower .alpha.-olefin monomers. The polymer product is obtained in good yield and has good properties including a relatively high bulk density and a relatively narrow particle size distribution.Type: GrantFiled: October 22, 1990Date of Patent: November 19, 1991Assignee: Shell Oil CompanyInventor: Robert C. Job
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Patent number: 5066738Abstract: The present invention provides a catalyst system that exhibits unprecedented catalyst efficiencies and control of desired properties in the polymer product. The catalyst system includes a new generation titanium catalyst in combination with an electron donor described by the formula: ##STR1## wherein R.sub.1 is bulky, basic alkyl or cycloalkyl group containing at least one secondary or tertiary carbon atom; R.sub.2 and R.sub.3 are alkyl or aryl groups; and R.sub.4 is an alkyl group with a primary carbon atom attached to the silicon atom. The system has a catalyst efficiency of at least about 30 kg/g-cat.2h as the Al/Si mole ratio varies from 20-200 in the system. The system easily achieves efficiencies over 60 kg/g-cat.2h. The system also exhibits good control over the xylene solubles, melt flow and molecular weight distribution of the polymer product.Type: GrantFiled: April 20, 1990Date of Patent: November 19, 1991Assignee: Fina Technology, Inc.Inventor: John A. Ewen
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Patent number: 5064799Abstract: Disclosed are catalyst components for the polymerization of olefins comprising the product of the reaction of a tetravalent titanium halide or alkoxy titanium halide and an electron-donor compound with a solid obtained by the reaction of a metal oxide containing surface hydroxyls, preferably together with chemically uncombined water, with an organometallic magnesium compound used in a quantity which does not cause reduction of the titanium in the subsequent reaction with the tetravalent titanium compound.Type: GrantFiled: January 4, 1991Date of Patent: November 12, 1991Assignee: Himont IncorporatedInventors: Antonio Monte, Luciano Noristi
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Patent number: 5061667Abstract: A catalytic component for olefin polymerization, produced by a process which comprises causing (A) magnesium metal, (B) a halogenated hydrocarbon represented by the general formula, RX [wherein R stands for an alkyl group, an aryl group, or a cycloalkyl group each having 1 to 20 carbon atoms and X for a halogen atom], and (C) a compound represented by the general formula, X.sub.n.sup.1 M(OR.sup.1).sub.m-n [wherein X.sup.1 stands for a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms, M for a boron, carbon, aluminum, silicon, or phorphorus atom, R.sup.1 stands for a hydrocarbon group having 1 to 20 carbon atoms, m for the valency of M, and m>n.gtoreq.Type: GrantFiled: August 29, 1990Date of Patent: October 29, 1991Assignee: Tog Nenryo Kogyo KK (Tonen Corporation)Inventors: Masahide Murata, Seizaburo Kanazawa, Hiroyuki Furuhashi, Kouji Maruyama, Masafumi Imai, Hiroshi Ueno
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Patent number: 5061666Abstract: A process for preparing a solid catalyst component which comprises halogenating a magnesium compound in the formula MgRR.sup.1.nCO.sub.2 l in which R and R.sup.1 are the same or different alkoxy or phenoxy groups and n is a number of from 0 to 2 with a halide of tetravalent titanium in the presence of dialkylester of a dihydric aromatic carboxylic acid and an inert hydrocarbon diluent by reacting at a temperature of from 120.degree. to 136.degree. C. and recovering the solid reaction product from the reaction mixture.Type: GrantFiled: April 24, 1990Date of Patent: October 29, 1991Assignee: Shell Research LimitedInventors: John C. Chadwick, Bart J. Ruisch
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Patent number: 5049533Abstract: Disclosed is a catalyst composition for use in the polymerization of olefins, which is comprised of (a) a catalyst component containing magnesium, titanium, a halogen, and an ingredient derived from a keto-ester compound, and (b) an organic aluminum compound. The catalyst activity and capability of providing a highly stereoregular polymer are enhanced by preparing the catalyst component (a) by a process wherein, during or after the formation of a solid catalyst component containing magnesium, titanium, and a halogen, the solid catalyst component is treated with a keto-ester of the formula: ##STR1## wherein R.sup.1, R.sup.2 and Z represent a hydrocarbon group.Type: GrantFiled: July 11, 1990Date of Patent: September 17, 1991Assignee: Showa Denko K.K.Inventors: Tetuo Nakajo, Hisayoshi Yanagihara, Masaki Fushimi, Shigenobu Miyake, Hideki Sakurai
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Patent number: 5041403Abstract: Disclosed is a catalyst composition for use in the polymerization of olefins, which is comprised of (a) a catalyst component containing magnesium, titanium, a halogen, and an ingredient derived from an ester compound, and (b) an organic aluminum compound. The catalyst activity and capability of providing a highly stereroregular polymer are enhanced by preparing the catalyst component (a) by a process wherein, during or after the formation of a solid catalyst component containing magnesium, titanium, and a halogen, the solid catalyst component is treated with an ester of the formula:(R.sup.1 O).sub.i (R.sup.2 O).sub.j (R.sup.3 O).sub.k --Z--COOR.sup.4 (I)whereinR.sup.1, R.sup.2, R.sup.3 and R.sup.4 are an aliphatic, alicyclic, aromatic, polycyclic or heterocyclic compound group,Z is an aliphatic or alicyclic hydrocarbon group in which hydrogen may be substituted with an aromatic or polycyclic group,and i, j and k are integers of 0 to 3 with the proviso that the sum of i, j and k is at least 1.Type: GrantFiled: February 16, 1990Date of Patent: August 20, 1991Assignee: Showa Denko K.K.Inventors: Tetuo Nakajo, Masaki Fushimi, Shigenobu Miyake, Hideki Sakurai
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Patent number: 5034366Abstract: A vanadium-based catalyst is treated with a polysiloxane oil as a means of enhancing catalyst activity and polymer productivity.Type: GrantFiled: December 29, 1989Date of Patent: July 23, 1991Assignee: Union Carbide Chemicals and Plastics Technology CorporationInventors: Frederick J. Karol, Sun-Chueh Kao
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Patent number: 5032562Abstract: There is disclosed a supported olefin polymerization catalyst composition comprising a precursor and a catalyst activator. The precursor comprises a magnesium compound, e.g., dibutylmagnesium, a cyclopentadienyl group-containing zirconium compound, and a titanium and/or a vanadium compound, e.g., TiCl.sub.4, and an organic compound, e.g., an alcohol. The catalyst activator is a mixture of a conventional Ziegler/Natta co-catalyst and a zirconium sites activator, e.g., methylaluminumoxane. The catalyst is used in the presence of small amounts of hydrogen to produce polymers having multimodal molecular weight distribution in a single reactor.Type: GrantFiled: December 27, 1989Date of Patent: July 16, 1991Assignee: Mobil Oil CorporationInventors: Frederick Y. Lo, Thomas E. Nowlin, Pradeep P. Shirodkar
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Patent number: 5030605Abstract: A vanadium-based catalyst is treated with certain alkylaluminum alkoxide compounds as a means of narrowing and effectively regulating the molecular weight distribution of the polymers produced with the catalyst.Type: GrantFiled: December 29, 1989Date of Patent: July 9, 1991Assignee: Union Carbide Chemicals and Plastics Technology CorporationInventors: Sun-Chueh Kao, Frederick J. Karol
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Patent number: 5028574Abstract: A catalyst and method is provided for the production of ultra-high molecular weight polymers characterized as having an inherent viscosity of above 12.0 by contacting ethylenically unsaturated monomers with a dual electron donor catalyst under polymerization conditions.Type: GrantFiled: March 14, 1990Date of Patent: July 2, 1991Assignee: Conoco Inc.Inventors: Donald E. Gessell, Donald P. Hosman
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Patent number: 5028671Abstract: A catalyst formed from(A) a solid titanium catalyst component containing magnesium, titanium, halogen and a polycarboxylic acid ester as essential ingredients and being obtained by contacting a magnesium compound, a titanium compound and a polycarboxylic acid ester,(B) an organoaluminum compound, and(C) an organosilicon compound represented by the following formula (1)SiR.sup.1 R.sup.2 (OR.sup.3).sub.2 (1)wherein R.sup.1 is selected from the class consisting of linear alkyl groups having at least 3 carbon atoms and arylalkyl groups in which the alkyl moiety has a secondary or tertiary alpha-carbon atom, R.sup.2 is selected from the class consisting of alkyl groups and arylalkyl groups in which the alkyl moiety has a secondary or tertiary alpha-carbon atom, and R.sup.3 is a hydrocarbon group, with the proviso that when R.sup.1 is a linear alkyl group having at least 3 carbon atoms and R.sup.2 is an alkyl group, the alkyl group for R.sup.Type: GrantFiled: November 1, 1989Date of Patent: July 2, 1991Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Mamoru Kioka, Norio Kashiwa
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Patent number: 5026889Abstract: A catalyst system comprising(A) a halogen compound of trivalent titanium,(B) an organo-aluminum compound of the formula,R.sub.3-(m+n) AlY.sub.m X.sub.nwhereinY is a group having at least one of oxygen, nitrogen, sulfur and phosphorus atoms linked to the aluminum atom, R is a hydrogen atom, an alkyl having 1 to 18 carbon atoms, an alkenyl having 2 to 18 carbon atoms, a cycloalkyl having 3 to 18 carbon atoms, an aryl having 6 to 18 carbon atoms, or an aralkyl having 7 to 18 carbon atoms,X is a halogen atom, and m and n are numbers satisfying the equations, 0<m<1, 0.ltoreq.n<2, 0<m+n.ltoreq.2, and(C) an electron-donor, and a method for producing an olefin polymer which comprises polymerizing olefins using said catalyst system. According to this method, highly crystalline olefin polymers having a broad melecular weight distribution can be produced.Type: GrantFiled: December 21, 1988Date of Patent: June 25, 1991Assignee: Sumitomo Chemical Company, LimitedInventors: Akinobu Shiga, Yoshiharu Fukui, Toshio Sasaki, Masahisa Okawa, Hideaki Matsuura
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Patent number: 5023223Abstract: A process for producing a highly stereospecific .alpha.-olefin polymer which comprises homopolymerizing or copolymerizing an .alpha.-olefin or copolymerizing an .alpha.-olefin with ethylene by the use of a catalyst system comprising:(A) a solid catalyst component containing a trivalent titanium compound obtained by reducing a titanium compound represented by the following general formula:Ti(OR.sup.1).sub.n X.sub.4-n(R.sup.1 represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen atom and n represents a number satisfying 0<n.ltoreq.Type: GrantFiled: December 11, 1989Date of Patent: June 11, 1991Assignee: Sumitomo Chemical Company, LimitedInventors: Takeshi Ebara, Toshio Sasaki, Kiyoshi Kawai
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Patent number: 5015612Abstract: An olefin polymerization catalyst component subjected to successive preliminary polymerization treatment using each of a straight chain alpha-olefin having 2 to 5 carbon atoms and 3-methyl-1-butene; an olefin polymerization catalyst using the olefin polymerization catalyst component; a process for polymerizing olefin(s) which comprises polymerizing or copolymerizing olefin(s) in the presence of the olefin polymerization catalyst; and a film and an injection-molded article of polypropylene which is prepared by the process are also provided.Type: GrantFiled: September 14, 1989Date of Patent: May 14, 1991Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Mamoru Kioka, Masao Nakano, Kenji Doi, Akinori Toyota
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Patent number: 5006499Abstract: A process for the preparation of a solid catalyst of the Ziegler-Natta type comprises precipitating the solid catalyst in a liquid hydrocarbon medium by reacting (A) a solution of a soluble magnesium alkoxide and (B) a transition metal halide which is a halide of Ti (IV), a halide of V (IV) or a halide of VO (III) in the presence of (C) at least one transition metal alkoxide which is free from halogen and soluble in liquid hydrocarbon. The precipitated solid catalyst consists of spheroidal particles having a mean diameter by mass of from 10 to 70 microns and a narrow particle size distribution such that the ratio of mean diameter by mass to the mean diameter by number is greater than 1.2 and smaller than 2.0.Type: GrantFiled: November 21, 1988Date of Patent: April 9, 1991Assignee: BP Chemicals LimitedInventor: Eric Daire
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Patent number: 5002916Abstract: Supported catalysts component for producing ethylene-propylene elastomers comprising a compound represented by the formula:(1) [V.sub.3 O(RCO.sub.2) (ED).sub.3 ].sub.2. V.sub.2 O.sub.2 X.sub.6, or(2) V.sub.3 O(RCO.sub.2).sub.6 (ED).sub.3wherein R is alkyl, cycloalkyl, aryl and haloalkyl,wherein R is alkyl, cycloalkyl, aryl and haloalkyl,ED is an electron donor selected from alkyl esters of aliphatic and aromatic carboxylic acid, aliphatic ketones, aliphatic amines, aliphatic alcohols, alkyl and cycloalkyl ethers, and mixtures thereof; andX is selected from Cl--, Br--, Fl-- or RCO.sub.2.sup.--.Type: GrantFiled: March 2, 1990Date of Patent: March 26, 1991Assignee: Exxon Chemical Patents Inc.Inventors: Terry J. Burkhardt, William B. Brandley
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Patent number: 4990478Abstract: An olefin polymerization catalyst system comprises a solid, hydrocarbon-insoluble, magnesium-containing, titanium-containing, electron donor-containing component; an alkyl aluminum compound; and organosilane compound selected from the group consisting of branched C.sub.3 -C.sub.10 alkyl-t-butoxydimethoxysilanes.Type: GrantFiled: September 21, 1989Date of Patent: February 5, 1991Assignee: Amoco CorporationInventors: Charles R. Hoppin, Benjamin S. Tovrog
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Patent number: 4990479Abstract: An olefin polymerization catalyst formed from (A) a solid titanium catalyst component containing magnesium, titanium and halogen as essential ingredients, (B) an organoaluminum compound, and (C) an organosilicon compound containing a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group or a derivative derived from any of these groups.A polymerization process which comprises polymerizing or copolymerizing olefins in the presence of the olefin polymerization catalyst to form a homopolyolefin having a high stereoregularity or a copolyolefin having a narrow composition distribution.Type: GrantFiled: June 15, 1989Date of Patent: February 5, 1991Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Naoshi Ishimaru, Mamoru Kioka, Akinori Toyota
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Patent number: 4990477Abstract: A catalyst component (X") obtained by treating an olefin polymerization catalyst (X) formed from (A) a solid titanium catalyst component comprising magnesium, titanium, halogen and an electron donor as essential ingredients, (B) an organoaluminum compound catalyst component, and as required, (C) an electron donor with an alpha-olefin by preliminarily polymerizing the alpha-olefin in an amount of 0.1 to 500 g per gram of the solid titanium catalyst component (A) in the presence of said catalyst (X), and contacting the treated catalyst (X') with at least 0.1 mole, per gram-atom of titaninum in the treated catalyst (X"), of oxygen. A process for producing the olefin polymerization catalyst component. A catalyst (Y) for olefin polymerization formed from [I] the above catalyst component (X"), [II] an organoaluminum compound catalyst component and as required [III] an electron donor. Also provided is a process for polymerizing olefins in the presence of the olefin polymerization catalyst (Y).Type: GrantFiled: September 13, 1989Date of Patent: February 5, 1991Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Mamoru Kioka, Masao Nakano, Akinori Toyota
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Patent number: 4988656Abstract: A solid hydrocarbon-insoluble, alpha-olefin polymerization catalyst component with superior activity, stereospecificity and morphology characteristics comprises the product formed by (A) forming a solution of a magnesium-containing species from a magnesium carbonte or a magnesium carboxylate; (B) precipitating solid particles from such magnesium-containing solution by treatment with a transition metal halide and an organosilane; (C) reprecipitating such solid particles from a mixture containing a cyclic ether; and (D) treating the reprecipitated particles with a transition metal compound and an electron donor.Type: GrantFiled: May 12, 1989Date of Patent: January 29, 1991Assignee: Amoco CorporationInventors: Gregory G. Arzoumanidis, Nicholas M. Karayannis, Habet M. Khelghatian, Sam S. Lee, Bryce V. Johnson
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Patent number: 4988655Abstract: A catalyst useful in the polymerization of olefinic compounds and particularly 4-methyl-1-pentene is disclosed along with its method of preparation and use. The catalyst is prepared by (a) forming a first component by reacting reactants comprising a magnesium dihalide, a phenol, and alkylbenzoate, and a titanium tetrahydrocarbyloxide; (b) reacting the first component with an organoaluminum halide compound to produce a solid product; and (c) then contacting the resulting solid product with an activating liquid comprising titanium tetrachloride and trichlorosilane in a confined zone under pressure of at least 70 psi.Type: GrantFiled: November 30, 1989Date of Patent: January 29, 1991Assignee: Phillips Petroleum CompanyInventors: Kent E. Mitchell, Gil R. Hawley, Don W. Godbehere
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Patent number: 4983561Abstract: A process for producing a trivalent titanium compound-containing solid catalyst for use in the polymerization of olefins which comprises treating, with an ester compound, a solid product obtained by reducing a titanium compound represented by the following general formula: ##STR1## (R.sup.1 represents hydrocarbon group having 1 to 20 carbon atoms, X represents halogen atom, and n represents a number satisfying 0<n.ltoreq.4) with an organomagnesium compound in the presence of an organic silicon compound having Si--O bond, and thereafter treating it with a mixture of an ester compound and titanium tetrachloride.Type: GrantFiled: September 12, 1989Date of Patent: January 8, 1991Assignee: Sumitomo Chemical Company, LimitedInventors: Toshio Sasaki, Eiji Sogabe, Takeshi Ebara
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Patent number: 4980329Abstract: Disclosed is a component for a catalyst for the polymerization of alpha-olefins to stereoregular polymers having narrow molecular weight distribution. The product is formed by the reaction of a solid catalyst-forming component comprising (1) a Ti compound having at least one Ti-halogen bond and (2) optionally, an electron-donor compound, supported on an anhydrous Mg dihalide in active form, with certain amounts of an organic compound (AH) containing at least one active hydrogen atom, in the presence of a liquid medium which is inert with respect to the Ti compound and the other components of the catalyst component, and which has a dielectric constant greater than 2 at 20.degree. C.Catalysts comprising the reaction product of the solid catalyst component prepared as above described, with an Al-alkyl compound and an electron-donor compound are also disclosed.Type: GrantFiled: May 15, 1989Date of Patent: December 25, 1990Assignee: Himont IncorporatedInventors: Pier C. Barbe, Enrico Albizzati, Umberto Giannini, Giovanni Baruzzi, Luciano Noristi
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Patent number: 4978648Abstract: Catalysts for the polymerization of olefins, particularly alpha-olefin of the formula CH.sub.2 .dbd.CHR in which R is an alkyl radical with 1-6 carbon atoms or an aryl radical, obtained by the reaction of:(a) an Al-alkyl compound;(b) an ether containing at least two ether groups which can form complexes with anhydrous magnesium dichloride, under standard conditions of reaction, in an amount less than 60 mmol per 100 g Mg dichloride; and(c) a solid catalyst component comprising an anhydrous magnesium dihalide in active form and having supported thereon a titanium compound containing at least a Ti-halogen bond and an electron-donor compound which is at least 70 mole % extractable with Al-triethyl, under standard conditions of extraction, component wherein the solid, after extraction, has a surface area of more than 20 m.sup.2 g.Type: GrantFiled: September 27, 1989Date of Patent: December 18, 1990Assignee: Himont IncorporatedInventors: Pier C. Barbe, Luciano Noristi, Raimondo Scordamaglia, Luisa Barino, Enrico Albizzati, Umberto Giannini, Giampiero Morini
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Patent number: 4970187Abstract: A method for producing a olefin polymer, which comprises polymerizing or copolymerizing olefins in the presence of a catalyst comprising:(A) a solid catalyst component obtained by thermally reacting (a.sub.1) a magnesium compound of the formula Mg(OR.sup.1).sub.n (OR.sup.2).sub.2-n wherein each of R.sup.1 and R.sup.2 which may be the same or different is an alkyl group, and aryl group or an aralkyl group, and n is 2.gtoreq.n.gtoreq.0, (a.sub.2) a titanium compound of the formula Ti(OR.sup.3).sub.4 wherein R.sup.3 is an alkyl group, an aryl group or an aralkyl group and (a.sub.3) a silicon compound of the formula Si(OR.sup.4).sub.4 wherein R.sup.4 is an alkyl group, an aryl group or an aralkyl group and contacting and treating (a) the resulting thermal reaction product with (b) a halogen-containing titanium compound and (c) an electron donative compound, and(B) an organometallic compound of a metal of Groups I-III of the Periodic Table.Type: GrantFiled: November 9, 1989Date of Patent: November 13, 1990Assignee: Mitsubishi Kasei CorporationInventors: Yoshinori Suga, Eiji Tanaka, Yasuo Maruyama
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Patent number: 4962167Abstract: A process for preparing an ultra-high molecular weight polyethylene by the polymerization of ethylene using a catalyst comprising a solid catalyst component and an organometallic compound, characterized in that said solid catalyst component is a product obtained by contacting the following [A] and [B] together:[A] the reaction product of a magnesium dihalide and a titanium compound represented by the general formula Ti(OR).sub.4 wherein R is a hydrocarbon group having 1 to 20 carbon atoms;[B] the reaction product of an aluminum trihalide and a silicon compound represented by the general formula Si(OR').sub.4 wherein R' is a hydrocarbon group having 1 to 20 carbon atoms.Type: GrantFiled: November 14, 1988Date of Patent: October 9, 1990Assignee: Nippon Oil Company, LimitedInventors: Takeichi Shiraishi, Wataru Uchida, Kazuo Matsuura
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Patent number: 4960741Abstract: A process of the Ziegler-Natta type is prepared using a preactivated support containing (A) from 80 to 95 mol % of magnesium chloride and (B) 5 to 20 mol % of at least one electron donor compound which contains no labile hydrogen and no ester function; the preactivated support consisting of spherical particles having a mass average diameter, Dm of 10 to 100 microns and a particle size distribution Dm/Dn of less than 2. The catalyst is prepared by (i) treating the preactivated support with at least one electron donor compound containing labile hydrogen, (ii) treating the resulting activated support with at least one ester of an aromatic acid, (iii) impregnating the treated support with titanium tetrachloride and (iv) after washing the impregnated catalyst activating it with titanium tetrachloride. The catalyst has a high titanium content and a high activity when used to polymerize olefins.Type: GrantFiled: February 22, 1989Date of Patent: October 2, 1990Assignee: BP Chemicals LimitedInventors: Jean-Claude A. Bailly, Stylianos Sandis
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Patent number: 4960744Abstract: A catalyst composition for the polymerization of propylene comprising a catalytic solid comprising a titanium halide and a magnesium halide and isoprenyl aluminum associated therewith and the process of polymerizing propylene using such catalyst.Type: GrantFiled: October 8, 1985Date of Patent: October 2, 1990Assignee: AtochemInventors: Laurent Duranel, Roger Spitz
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Patent number: 4952649Abstract: A solid titanium catalyst component (A) of a catalyst system useful in the polymerization of olefins or copolymerization of two or more olefins or one or more olefins and a diene is prepared by contacting a liquid hydrocarbon solution of (i) a magnesium compound, such as magnesium chloride, with (ii) a liquid titanium compound, such as TiCl.sub.4, or a solution of a titanium compound in a hydrocarbon solvent, to form a solid product. The solid product is formed in the presence of (D) an electron donor, e.g. methyl formate, acetic acid, acetic anhydride, acetone, methyl ether, butyl Cellosolve, dimethyl carbonate, methyl silicate. The solid product is also contacted with a polycarboxylic acid ester, e.g. diethyl methylsuccinate. The polymerization or copolymerization of the olefin is carried out in the presence of the solid titanium catalyst (A) and (B) an organometallic compound of a Group I to III metal and (C) an organic silicon compound having an Si--O--C bond.Type: GrantFiled: March 11, 1988Date of Patent: August 28, 1990Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Mamoru Kioka, Norio Kashiwa
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Patent number: 4950630Abstract: A method for the production of a catalyst component for use in the polymerization of an olefin, which method comprises causing a magnesium-containing solid obtained by contact of (A) magnesium metal, (B) a halogenated hydrocarbon represented by the general formula, RX [wherein R stands for an alkyl, aryl, or cycloalkyl group having 1 to 20 carbon atoms and X stands for a halogen atom], and (C) a compound of the general formula, X.sub.n.sup.1 M(OR.sup.1).sub.m-n [wherein X.sup.1 stands for a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms, M stands for a boron, carbon, aluminum, silicon, or phosphorus atom, R.sup.1 stands for a hydrocarbon group having 1 to 20 carbon atoms, and m stands for the valency of said atom M, providing that m>n.gtoreq.0 is satisfied], to contact (d) a halogen-containing alcohol and then contact (E) an electron donor type compound and (F) a titanium compound.Type: GrantFiled: November 18, 1988Date of Patent: August 21, 1990Assignee: Toa Nenryo Kogyo, K.K.Inventors: Masahide Murata, Masafumi Imai, Hiroyuki Furuhashi, Kouji Maruyama, Hiroshi Ueno
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Patent number: 4948771Abstract: A catalyst composition comprising:(i) a complex comprised of V.sub.2 X.sub.3 (ED).sub.m and AlCl.sub.2 R.sub.2 whereinX=Cl, Br, or I, or mixtures thereofED=an electron donor, which is an ether, a phosphine, a ketone, an isocyanide, or an ester, said electron donor having 2 to 20 carbon atomsR=an alkyl having up to 14 carbon atomsm=an integer from 3 to 6,said complex impregnated into an inorganic oxide support;(ii) sufficient trialkylaluminum compound adsorbed on the inorganic oxide support to provide a molar ratio of adsorbed trialkylaluminum compound to vanadium of about 2.5:1 to about 10:1;(iii) a halocarbon promoter; and(iv) a hydrocarbyl aluminum cocatalyst.Type: GrantFiled: December 7, 1988Date of Patent: August 14, 1990Assignee: Union Carbide Chemicals and Plastics Company Inc.Inventor: Francis G. Stakem
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Patent number: 4946816Abstract: In a solid hydrocarbon-insoluble, alpha-olefin polymerization catalyst component with superior activity, stereospecificity and morphology characteristics comprising the product formed by (A) forming a solution of a magnesium-containing species from a magnesium alkyl (or hydrocarbyl) carbonate or a magnesium carboxylate; (B) precipitating solid particles from such magnesium-containing toluene-based solvent by treatment with a transition metal halide and an organosilane; (C) reprecipitating such solid particles from a mixture containing a cyclic either; and (D) treating the reprecipitated particles with a transition metal compound and an electron donor, the morphology of such component is modified by incorporating a morphology-affecting amount of C.sub.8 -C.sub.10 aromatics within the toluene-based solvent in Step B, Step A, in Step C prior to addition of ether, or combinations thereof.Type: GrantFiled: August 21, 1989Date of Patent: August 7, 1990Assignee: Amoco CorporationInventors: Steven A. Cohen, Gregory G. Arzoumanidis, Nicholas M. Karayannis, Habet M. Khelghatian, Sam S. Lee
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Patent number: 4935394Abstract: This invention provides new supported catalyst compositions for the polymerization of 1-olefins, together with processes for preparing and using the catalysts. The catalyst compositions include two catalyst components. The first catalyst component is formed by reacting a halogen-containing compound of the formula: H.sub.a M.sup.1 X.sup.1.sub.b R.sup.1.sub.(c-b-a) wherein M.sup.1 is boron, carbon, silicon or mixtures thereof; X.sup.1 is Cl, Br or mixtures thereof; R.sup.1 is a hydrocarbyl or alkoxy radical; with a mixture produced by contacting a finely divided porous inorganic oxide support in an inert solvent with a solution made by combining a magnesium dihydrocarbyloxide dissolved in an inert solvent, and of the formula: Mg(OR.sup.2).sub.2 wherein R.sup.2 is a hydrocarbyl radical, with a transition metal hydrocarbyloxide of the formula: M.sup.2 (OR.sup.3).sub.y wherein M.sup.2 is a transition metal from Group IVB, VB, and VIB of the Periodic Table; and R.sup.3 is a hydrocarbyl radical.Type: GrantFiled: August 19, 1988Date of Patent: June 19, 1990Assignee: Exxon Chemical Patents Inc.Inventor: Main Chang
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Patent number: 4931517Abstract: A process for the polymerization of ethylene comprises bringing ethylene or ethylene and at least one .alpha.-olefin in contact with a catalyst comprising a metallocene compound of a transition metal selected from Groups IVB, VB and VIB, an aluminoxane and a silicon compound having an Si-O-C bond for polymerization. The use of the silicon compound having an Si-O-C bond in the catalysis by a combination of a metallocene compound and an aluminoxane results in the production of ethylene polymers having a lower melt flow rate (MFR) than those produced similarly except for the silicon compound not being used.Type: GrantFiled: August 12, 1988Date of Patent: June 5, 1990Assignee: Mitsubishi Petrochemical Company LimitedInventor: Takashi Fujita
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Patent number: 4927797Abstract: The present invention provides a catalyst system that exhibits unprecedented catalyst efficiencies and control of desired properties in the polymer product. The catalyst system includes a Toho-type, new generation titanium catalyst in combination with an electron donor described by the formula: ##STR1## wherein R.sub.1 is a bulky, basic alkyl or cycloalkyl group containing at least one secondary or tertiary carbon atom; R.sub.2 and R.sub.3 are alkyl or aryl groups; and R.sub.4 is an alkyl group with a primary carbon atom attached to the silicon atom. The system has a catalyst efficiency of at least about 30 kg/g-cat.2h as the Al/Si mole ratio varies from 20-200 in the system. The system easily achieves efficiencies over 60 kg/g-cat.2h. The system also exhibits good control over the xylene solubles, melt flow and molecular weight distribution of the polymer product.Type: GrantFiled: December 2, 1988Date of Patent: May 22, 1990Assignee: Fina Technology, Inc.Inventor: John A. Ewen
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Patent number: 4918037Abstract: A catalyst component for polymerization catalyst of .alpha.-olefines, the polymerization catalyst comprising an organoaluminum compound, an electron donor, as well as the solid catalyst component which is obtained when a compound containing magnesium reacts with a titanium halogen compound. A method for producing the catalyst component is also provided. The catalyst component is manufactured by reacting with a titanium halogen compound in the presence of an internal electron donor, a solid catalyst component which has been produced by the steps of(a) reacting a magnesium alkyl compound with a chlorinating compound,(b) dissolving the chlorinated magnesium alkyl compound in alcohol, after possible washing,(c) adding into the solution, magnesium silicate which has not been calcinated,(d) adding the mixture obtained in step (c) into a cold medium, to precipitate the magnesium compound into and onto the magnesium silicate carrier, and(e) separating the thus-obtained solid carrier component.Type: GrantFiled: March 8, 1989Date of Patent: April 17, 1990Assignee: Neste OyInventor: Hanneli Seppanen
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Process for the production of polyethylene with a broad and/or bimodal molecular weight distribution
Patent number: 4918038Abstract: A process for the production of an ethylene homopolymer or copolymer comprising passing ethylene with or without at least one alpha-olefin comonomer having 3 or more carbon atoms into contact with a mixed catalyst system, under polymerization conditions, said mixed catalyst system comprising:(a) the reaction product of (i) a vanadium halide having the formula VX.sub.3 wherein X is chlorine, bromine, or iodine and each X is alike or different; (ii) a modifier having the formula BX.sub.3 or AlR.sub.(3-a) X.sub.a and (iii) an electron donor(b) one of the following:(i) a complex having the formula ZrMg.sub.b X.sub.c (ED).sub.d ; or(ii) a vanadium oxy compound having the formula VOX.sub.3, VOX.sub.2, VOX, or VO.sub.2 X wherein X is as defined above, or VO(OR).sub.3(c) a hydrocarbyl aluminum cocatalyst; and(d) a halocarbon promoter having the formula R.sub.e CX.sub.Type: GrantFiled: October 29, 1987Date of Patent: April 17, 1990Assignee: Union Carbide Chemicals and Plastics Company Inc.Inventors: Sari-Beth Samuels, Frederick J. Karol -
Patent number: 4914069Abstract: Solid catalyst components for use in the polymerization of olefins and having improved activity and selectivity are prepared by:(a) halogenating a magnesium compound containing at least one aryloxy, alkyl carbonate or alkyloxy group with a first halide of tetravalent titanium and a first electron donor;(b.sub.1) contacting the resulting halogenated product with a second halide of tetravalent titanium; and(c) washing a resulting treated halogenated product with an inert hydrocarbon liquid, wherein a second electron donor is used in step (a) or step (b.sub.1) and in that the product of step (b.sub.1) is contacted in a step b.sub.2 with a third halide of tetravalent titanium at a temperature of 40.degree. to 140.degree. C. and thereafter the treated product is washed in step (c).Type: GrantFiled: August 8, 1988Date of Patent: April 3, 1990Assignee: Shell Oil CompanyInventors: Robert C. Job, Steven M. Nestlerode
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Patent number: 4904628Abstract: Catalysts for the polymerization of alpha-olefins, which comprise the product of the reaction between:(a) a metallorganic compound of Al;(b) an electron-donor compound reactive towards MgCl.sub.2 but which is not completely complexed with AlEt.sub.3, at the equivalent point of a potentiometric titration under standard conditions;(c) a solid comprising a halogenated Ti compound and an electron-donor belonging to particular classes of compounds and being extractable with AlEt.sub.3 for at least 70% by mols from the solid, the surface area of which after extraction is higher than 20 m.sup.2 /g.The present invention refers to new supported components of catalysts for the polymerization of olefins CH.sub.2 .dbd.CHR, in which R is an alkyl with 1-4 carbon atoms or an aryl, and of mixtures of such olefins with each other and/or with ethylene, and to the catalysts obtained from such components.Type: GrantFiled: January 28, 1988Date of Patent: February 27, 1990Assignees: Montedison S.p.A., Mitsui Petrochemical Ind.Inventors: Enrico Albizzati, Sandro Parodi, Pier C. Barbe