Nonmetallic Organic Halide Patents (Class 502/128)
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Patent number: 6274529Abstract: A catalytic system with an increased activity for the (co)polymerization of alpha-olefins comprises a catalyst of the metallocene type, which is capable of polymerizing olefins without aluminoxane, and a weak coordinating compound, which, when used in a polymerization process, enables a higher productivity than an analogous process carried out with the metallocene type catalyst per se.Type: GrantFiled: October 22, 1996Date of Patent: August 14, 2001Assignee: Enichem S.p.A.Inventors: Roberto Fusco, Luca Longo, Antonio Proto, Diego Vigliarolo, Gianfranco Guglielmetti, Liliana Gila
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Patent number: 6255246Abstract: Boratabenzene cocatalysts, especially novel pentafluorophenyl boratabenzenes, are useful cocatalysts or activators with metallocenes. They are less expensive than prior art activators, are soluble and offer more irreversible reactions. Compositions comprise at least one metallocene catalyst and at least one dihydroboratabenzene or anion thereof. Processes include polymerizations with metallocenes in the presence of a boratabenzene cocatalyst.Type: GrantFiled: January 18, 2000Date of Patent: July 3, 2001Assignee: The Dow Chemical CompanyInventors: David D. Devore, Francis J. Timmers, David R. Neithamer
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Patent number: 6225427Abstract: A polyolefin elastomer possessing a unique combination of properties, i.e., high molecular weight (Mw), high Mooney viscosity (ML1+4 at 125° C.), low polydispersity index (Mw/Mn) and low glass transition temperature (Tg), is obtained by a polymerization process employing a particular type of a metallocene catalyst. The polyolefin elastomer is useful for manufacturing a variety of products including rubber articles such as hoses, belts and moldings, polymer blends containing one or more other hydrocarbon polymers and lubricating oils in which the elastomer functions as a viscosity modifier. Also disclosed is a cocatalyst for activating the metallocene procatalyst employing a specific molar ratio of the components of the cocatalyst to the transition metal of the procatalyst.Type: GrantFiled: October 15, 1998Date of Patent: May 1, 2001Assignee: Uniroyal Chemical Company, Inc.Inventors: Willie C. Burton, Xu Wu Feng, Daniel Gillis
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Patent number: 6214759Abstract: The present invention relates to a method for producing a Ti/V supported catalyst useful in polymerization of ethylene and copolymerization of ethylene and &agr;-olefin. The method includes a treatment, by a titanium compound and a vanadium compound, of the magnesium-containing carrier, which is obtained by reaction of an organomagnesium compound of the structure of MgPh2.nMgCl2.mR2O (n=0.37˜0.7; m≧1; R2O=ether; Ph=phenyl) with an organic chloride compound in a mole ratio of organic chloride compound/Mg≧0.5, at −20˜80° C. According to the method for producing the catalyst, it is possible to provide a catalyst which can control the distribution of molecular weight, and when polymerization is performed using this catalyst, it is possible to restrain the inactivation and to secure a sufficient activity. Moreover, the polymer produced by the use of this catalyst proves to have a high bulk density and an adjusted particle size distribution.Type: GrantFiled: April 14, 1999Date of Patent: April 10, 2001Assignee: Samsung General Chemicals Co., Ltd.Inventors: Ho-Sik Chang, Youn-Kyung Kang
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Patent number: 6214950Abstract: A process for preparation of polyolefins using an olefin polymerization catalyst comprising (A) a solid catalyst component and (B) an organometallic compound component. The solid catalyst component (A) is prepared by a process comprising the steps of: (I) obtaining a solid (A-1) by reacting: (i) an organomagnesium component soluble in a hydrocarbon solvent and represented by the formula (M1)&agr;(Mg)&bgr;(R1)p(R2)q(OR3)r; and (ii) an Si—H bond-containing chlorosilane compound represented by the formula: HaSiClbR44−(a+b), in a ratio of from 0.01 to 100 mol (ii) per mol (i); (II) reacting the solid (A-1) with an alcohol (A-2) in a ratio of from 0.05 to 20 mol of the alcohol per mol of C—Mg bonds contained in the solid (A-1), to form a reaction product; and (III) reacting the reaction product with a titanium compound (A-4). The solid catalyst component (A) is adjusted to have an alkoxy group/titanium molar ratio of 2.4 or lower and an alkoxy group/magnesium molar ratio of 0.Type: GrantFiled: September 1, 1999Date of Patent: April 10, 2001Inventor: Nozaki Takashi
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Patent number: 6197901Abstract: Polyalk-1-enes are prepared by polymerization of alk-1-enes with the aid of the compound bis(cyclopentadienyl)-chromium(II) in which the cyclopentadienyl rings may carry inert organic radicals, said compound being adsorbed on an inorganic oxide carrier, by a process in which the polymerization is carried out in the presence of an organometallic compound of a metal of main groups I to III or of a metal hydride, in particular of n-butyl-lithium.Type: GrantFiled: September 23, 1997Date of Patent: March 6, 2001Assignee: BASF AktiengesellschaftInventors: Wolfgang Rohde, Roland Saive, Hans-Helmut Goertz, Guenther Schweier
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Patent number: 6187883Abstract: The present invention relates to a solid catalyst component for &agr;-olefin polymerization having a narrow particle size distribution of not less than 6.0 in terms of the value of N in a Rosin-Rammler function of particle size distribution and giving a catalytic activity of not less than 10,000 ((g-polymer produced/g-solid catalyst component)/hour) in polymerization. The catalyst component is obtained by a process which comprises reducing a titanium compound with an organomagnesium compound in the presence of an organosilicon compound and an ester to obtain a solid product, then treating the solid product with: (a) a mixture of titanium tetrachloride and an ether, (b) an organic acid halide, and (c) a mixture of titanium tetrachloride and an ether optionally containing an ester.Type: GrantFiled: August 13, 1997Date of Patent: February 13, 2001Assignee: Sumitomo Chemical Company, LimitedInventors: Makoto Satoh, Teruyoshi Kiyota, Akio Imai
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Patent number: 6180554Abstract: The present invention relates to a catalyst system comprising: a) an organoaluminum compound, b) a metal compound selected from subgroups IV to VI of the periodic system, c) a reactivator in a molar ratio of 0.5 to 100 relative to compound b), wherein said reactivator comprises a characterized in that a mono- or dihalocarboxylic acid alkyl ester of the following formula: wherein X is a C1-6 alkyl or C1-6 alkoxy group, Y is Cl, Br or H, Z is Cl or Br and R is a C1-6 alkyl group.Type: GrantFiled: June 22, 1999Date of Patent: January 30, 2001Assignee: Bayer AktiengesellschaftInventors: Martin Hoch, Johannes-Rudolf Jansen, Thomas Essert, Andreas Sattler, J{umlaut over (u)}rgen Schneider
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Patent number: 6177375Abstract: A method for preparing a silica supported, &agr;-olefin polymerization catalyst includes the steps of treating a silica support with an organosilane compound, contacting the silylated silica support with a transition metal compound to form an intermediate, then contacting the resulting intermediate with an alkylmagnesium alkoxide to form the catalyst. The transition metal compound is either a metal chloride or a metal chloroalkoxide, and the transition metal is selected from titanium, vanadium, and zirconium. The alkylmagnesium alkoxide may be selected from butylethylmagnesium butoxide, butylethylmagnesium 2-ethylhexoxide, butyloctylmagnesium ethoxide, or butylmagnesium propoxide. The process steps may be carried out in the presence of an aliphatic organic solvent, such as heptane, with a slurry of solids in the solvent being formed during the process steps.Type: GrantFiled: March 9, 1998Date of Patent: January 23, 2001Assignee: PQ CorporationInventors: Thomas J. Pullukat, Ronald S. Shinomoto
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Patent number: 6177376Abstract: The present invention relates to a process for preparing a metallocene catalyst system, which comprises reacting a metallocene starting compound in a solvent with a compound capable of transferring hydrocarbon radicals and converting the resulting metallocene compound which is &sgr;-substituted by one or more hydrocarbon radicals in solution without isolation into a polymerization-active catalyst system by means of an activator.Type: GrantFiled: January 29, 1998Date of Patent: January 23, 2001Assignee: Targor GmbHInventors: Cornelia Fritze, Hans Bohnen, Frank K{umlaut over (u)}ber
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Patent number: 6147025Abstract: A metallocene catalyst is provided which comprises the product obtained by combining (a) a metallocene procatalyst, preferably one containing a bridging group possessing at least two bulky groups, and (b) a cation-generating cocatalyst. A process for activating a metallocene procatalyst is also provided which comprises combining the metallocene procatalyst with the components of a cation-generating cocatalyst.Type: GrantFiled: December 15, 1997Date of Patent: November 14, 2000Assignee: Uniroyal Chemical Company, Inc,Inventors: Daniel J. Gillis, Richard Karpeles
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Patent number: 6136744Abstract: A cation-generating cocatalyst is provided for activating a metallocene procatalyst. The cocatalyst comprises (1) a metal- and/or metalloid-containing first component, e.g., an aluminum compound, (2) a neutral metal- and/or metalloid-containing second component, e.g., a borane compound, and (3) an anionic metal- and/or metalloid-containing third component, e.g., a metal containing borate.Type: GrantFiled: December 15, 1997Date of Patent: October 24, 2000Assignee: Uniroyal Chemical Company, Inc.Inventors: Daniel J. Gillis, Richard Karpeles
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Patent number: 6136745Abstract: The present invention relates to a high activity catalyst composition for the (co-)polymerisation of ethylene, optionally with an alpha olefin of 3 to 10 carbon atoms, comprising a catalyst precursor and an organoaluminium cocatalyst, wherein the catalyst precursor consists of:(i) a silica carrier material, having from 0.3 to 1.2 mmoles of OH groups per gram of silica,(ii) a dialkylmagnesium compound of the formula RMgR.sup.1, where R and R.sup.1 are the same or different C.sub.2 -C.sub.12 alkyl groups, in an amount comprised between 0.5 to 1.5 mmoles of dialkylmagnesium per gram of silica,(iii) a tetraalkyl orthosilicate, in which the alkyl groups contain from 2 to 6 carbon atoms, in an amount comprised between 0.2 to 0.8 mmoles per gram of silica,(iv) a chlorinated compound (X) having the formula R.sub.n SiCl.sub.4-n, wherein each R is the same or different and is hydrogen or an alkyl group and n is an integer from 0 to 3, in an amount comprised between 0.Type: GrantFiled: July 22, 1998Date of Patent: October 24, 2000Assignee: BP Chemicals LimitedInventors: David John Ashton, Yury Viktor Kissin, Robert Ivan Mink
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Patent number: 6133187Abstract: A catalyst comprising a cocatalyst and a catalyst component obtained by contacting a silicon-containing metallocene compound with an inorganic support to chemically bond the metallocene compound to the inorganic support, wherein the silicon-containing metallocene compound has a formula (I): ##STR1## wherein: M is a metal selected from [the group consisting of] group 4, 5, or 6 of the periodic table;each X is independently selected from the group consisting of hydrogen, halogen, C.sub.1 -C.sub.10 alkyl, C.sub.1 -C.sub.10 alkoxy, C.sub.6 -C.sub.10 aryl, C.sub.6 -C.sub.10 aryloxy, C.sub.2 -C.sub.10 alkenyl, C.sub.7 -C.sub.40 arylalkyl, C.sub.7 -C.sub.40 alkylaryl, and C.sub.8 -C.sub.40 arylalkenyl;A.sub.1 and A.sub.2 are independently selected from the group consisting of cyclopentadienyl, substituted cyclopentadienyl, indenyl, fluorenyl, substituted indenyl, and substituted fluorenyl, wherein the substituents are independently C.sub.1 -C.sub.10 linear or branched alkyl, C.sub.5 -C.sub.Type: GrantFiled: October 19, 1998Date of Patent: October 17, 2000Assignee: Repsol Quimica S.A.Inventors: Wilfried Michiels Vega, Pilar Lafuente Canas, Antonio Munoz-Escalona Lafuente, Gerardo Hidalgo Llinas, Jose Sancho Royo, Luis Mendez Llatas
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Patent number: 6066704Abstract: A transition metal complex represented by the formula [1] ##STR1## wherein M is a transition metal atom of the group 4 of the periodic table of elements; Cp is a group having a cyclopentadiene type anionic skeleton; A and G are each a divalent residue containing an atom of the group 15 or 16 of the periodic table of elements and may be the same with or different from each other; X.sup.1, X.sup.2, R.sup.1, R.sup.2, R.sup.3 and R.sup.Type: GrantFiled: June 26, 1998Date of Patent: May 23, 2000Assignee: Sumitomo Chemical Company, LimitedInventors: Hiroaki Katayama, Akio Imai, Hidenori Hanaoka, Norio Kawamura, Akira Miyashita
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Patent number: 6054405Abstract: A catalyst composition for the polymerization of olefins is provided, which comprises the reaction product of a fulvene, a complex of an atom selected from Groups 3-14 and the Lanthanides, and an activating cocatalyst.Type: GrantFiled: December 29, 1997Date of Patent: April 25, 2000Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventor: Timothy Todd Wenzel
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Patent number: 6051522Abstract: A catalyst containing the combination which comprises:(a) an aluminoxane, a compound of the formula R.sub.x NH.sub.4-x, BR'.sub.4, R.sub.x PH.sub.4-x, BR'.sub.4, R.sub.3 CBR'.sub.4 or BR'.sub.3, or a mixture thereof wherein X is an integer from 1 to 4 and the radicals R are identical or different and are a C.sub.1 -C.sub.10 -alkyl or a C.sub.6 -C.sub.18 -aryl or 2 radicals R together with the atom joining them form a ring, and the radicals R' are identical or different and are a C.sub.6 -C.sub.18 -aryl which optionally are substituted by alkyl, haloalkyl or fluorine, and(b) a metallocene of the formula VI ##STR1## in which M.sup.1 is titanium, zirconium, hafnium, vanadium, niobium or tantalum,R.sup.1 is (C.sub.3 -C.sub.20)alkyl, (C.sub.6 -C.sub.14)aryl, (C.sub.4 -C.sub.10)alkoxy, (C.sub.2 -C.sub.10)alkenyl, (C.sub.7 -C.sub.20)arylalkyl, (C.sub.7 -C.sub.20)alkylaryl, (C.sub.6 -C.sub.10)aryloxy, (C.sub.1 -C.sub.10)fluoroalkyl, (C.sub.6 -C.sub.10)halogenoaryl, (C.sub.2 -C.sub.10)alkynyl; a radical --SiR.sup.6.Type: GrantFiled: June 5, 1995Date of Patent: April 18, 2000Assignee: Targor GmbHInventors: Jurgen Rohrmann, Frank Kuber
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Patent number: 6046126Abstract: The present invention provides a novel process for preparing a catalyst, preferably free of electron donor, useful in gas phase polymerization of olefins having a broad polydispersity.Type: GrantFiled: May 12, 1998Date of Patent: April 4, 2000Inventors: Mark Kelly, Dusan Jeremic, Victoria Ker, Charles Russell
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Patent number: 6017842Abstract: Catalyst compositions that are highly tolerant of catalyst poisons comprising a catalytic derivative of a Group 4 metallocene metal complex and an Group 13 metal compound according to the formula R.sup.1.sub.2 M"(NR.sup.2.sub.2),wherein R.sup.1 and R.sup.2 independently each occurrence is a hydrocarbyl, silyl, halocarbyl, halohydrocarbyl, hydrocarbyl-substituted silyl, halocarbyl-substituted silyl, or halohydrocarbyl-substituted silyl group, said R.sup.1 and R.sup.2 having from 1 to 30 carbon, silicon, or mixtures of carbon and silicon atoms, andM" is a Group 13 metal,the molar ratio of complex to Group 13 compound being from 1:0.1 to 1:100.Type: GrantFiled: July 18, 1997Date of Patent: January 25, 2000Assignee: The Dow Chemical CompanyInventors: Robert K. Rosen, James C. Stevens
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Patent number: 5990034Abstract: An olefin polymerization catalyst comprising (A) a solid catalyst component and (B) an organometallic compound component. The solid catalyst component (A) is prepared by a process comprising the steps of:(I) obtaining a solid (A-1) by reacting:(i) an organomagnesium component soluble in a hydrocarbon solvent and represented by the formula (M.sup.1).sub..alpha. (Mg).sub..beta. (R.sup.1).sub.p (R.sup.2).sub.q (OR.sup.3).sub.r ; and(ii) an Si--H bond-containing chlorosilane compound represented by the formula: H.sub.a SiCl.sub.b R.sup.4.sub.4-(a+b), in a ratio of from 0.01 to 100 mol (ii) per mol (i);(II) reacting the solid (A-1) with an alcohol (A-2) in a ratio of from 0.05 to 20 mol of the alcohol per mol of C--Mg bonds contained in the solid (A-1), to form a reaction product; and(III) reacting the reaction product with a titanium compound (A-4). The solid catalyst component (A) is adjusted to have an alkoxy group/titanium molar ratio of 2.4 or lower and an alkoxy group/magnesium molar ratio of 0.15 or lower.Type: GrantFiled: December 5, 1997Date of Patent: November 23, 1999Assignee: Asahi Kasei Kogyo Kabushiki KaishaInventor: Takashi Nozaki
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Patent number: 5972823Abstract: The invention is directed to a catalyst composition suitable for addition reactions of ethylenically and acetylenically unsaturated monomers comprising a metal oxide support having covalently bound to the surface thereof directly through the oxygen atom of the metal oxide an activator anion that is also ionically bound to a catalytically active transition metal cation compound. The invention includes a preparation process for the invention catalyst composition exemplified by reacting a Lewis acid, such as trisperfluorophenyl boron with residual silanol groups of a silica support, preferably then reacting with a Lewis base such as diethylaniline, so as to prepare a silica bound anionic activator that when combined with a suitable transition metal compound will protonate it so as to form the ionic catalyst system. Use of the invention catalyst to polymerize alpha-olefins is exemplified.Type: GrantFiled: July 14, 1997Date of Patent: October 26, 1999Assignee: Exxon Chemical Patents IncInventor: John Flexer Walzer, Jr.
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Patent number: 5968865Abstract: A composition containing a magnesium component, a titanium component, a halide and a 1,2-dialkoxybenzene, wherein at least one alkoxy group has at least two carbon atoms, and the manufacture of the composition are taught by the present invention. The compositions are useful as Ziegler-Natta catalysts in the production of olefin polymers.Type: GrantFiled: December 10, 1997Date of Patent: October 19, 1999Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Stanley Edward Wilson, Robert Converse Brady, III
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Patent number: 5968868Abstract: A catalyst useful for the alkylation of isoalkanes is disclosed along with a process therefor the same. The catalyst comprises a reaction product resulting from mutual contact of a zirconium halide and a magnesium halide and/or a magnesium oxyhalide. The process for the alkylation of isoalkanes with alkenes is carried out in the presence of a catalyst comprising a reaction product resulting from mutual contact of a zirconium halide and a magnesium halide and/or a magnesium oxyhalide at a temperature of room temperature--150.degree. C. and a pressure of atmospheric--5 MPa.Type: GrantFiled: July 3, 1997Date of Patent: October 19, 1999Assignee: Nippon Oil Co., Ltd.Inventors: Yoshio Tajima, Fuyuki Aida, Mitsuo Matsuno
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Patent number: 5962361Abstract: A method of making a solid, substantially dry olefin polymerization procatalyst precursor is disclosed whereby a solid precursor containing magnesium and titanium is formed in a slurry or solution, the solid then is separated from the solution and then dried at a temperature above 50.degree. C. for over an hour. Solid, substantially dry olefin polymerization procatalyst precursors made by the method also are disclosed, whereby the precursors are easier to handle, have better flowability, reduced clumpness and provide catalysts that can be used to produce polymers having improved extrudability, less filter clogging, less "talc"-like polymer particles of <10 micron in size and reduced polymer product segregation in storage.Type: GrantFiled: October 14, 1998Date of Patent: October 5, 1999Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventor: Michael Philip Zum Mallen
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Patent number: 5922631Abstract: Olefin polymerization catalysts are described that comprise the reaction product of (a) a metallocene and/or a Ziegler-Natta catalyst compound (TICl.sub.4, etc.,) and (b) a liquid clathrate composition formed from (i) an aluminoxane, (ii) an organic, inorganic or organometallic compound, and (iii) an aromatic solvent. These liquid clathrates are obtained by the reaction, in aromatic solvents, of aluminoxanes such as, methylaluminoxane, with organic, inorganic or organometallic compounds that form stable clathrates with the aluminoxane and the solvent.Type: GrantFiled: April 18, 1997Date of Patent: July 13, 1999Assignee: Albemarle CorporationInventor: Samuel A. Sangokoya
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Patent number: 5922632Abstract: Catalysts component of the (co)polymerization of alpha-olefins CH.sub.2 .dbd.CHR, wherein R is hydrogen or an alkyl radical having from 1 to 8 carbon atoms, comprising a product of the composition:VCL.sub.y.z(b)wherein (b) represents an organic compound selected from alkyl, aryl and acyl halides, y is a number higher than 2 and lower than 4, and preferably comprised between 2.5 and 3.5 and z is a number higher than zero and lower than or equal to 2, and preferably between 0.002 and 1. Components can be obtained as products of the reaction, carried out at temperatures higher than 10.degree. C., between VCl.sub.4 and the compound (b). Particularly preferred among compounds (b) are benzoyl chloride, p-methoxybenzoyl chloride and p-chloro benzoyl chloride. From the components of the invention, either supported or not, catalysts having high activity particularly useful for the production of ethylene polymers showing broad molecular weight distribution can be prepared.Type: GrantFiled: September 25, 1997Date of Patent: July 13, 1999Assignee: Montell Technology Company b.v.Inventors: Umberto Zucchini, deceased, Tiziano Dall'Occo, Antonella Angelini
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Patent number: 5914375Abstract: An catalyst composition for preparing high-syndiotacticity polystyrene polymers which comprises: (a) a titanium complex represented by the following formula of TiR'.sub.1 R'.sub.2 R'.sub.3 R'.sub.4 or TiR'.sub.1 R'.sub.2 R'.sub.3, wherein R'.sub.1, R'.sub.2, R'.sub.3, and R'.sub.4 are, independently, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a hydrogen atom, or a halogen atom; (b) a cyclopentadienyl complex of silicon (Si), germanium (Ge), or tin (Sn) represented by the following formula: ##STR1## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.Type: GrantFiled: August 4, 1997Date of Patent: June 22, 1999Assignee: Industrial Technology Research InstituteInventors: Jing-Cheng Cheng Tsai, Shian-Jy Wang, Shu-Ling Peng, Mickey Sue
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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: 5856258Abstract: The subject invention involves a method of preparing and the constrained geometry catalyst thereby prepared of the general formula Ar'R4(O)Ar"R'.sub.4 M(CH.sub.2 Ph).sub.2 where Ar' is a phenyl or naphthyl group; Ar" is a cyclopentadienyl or indenyl group, R and R' are H or alkyl substituents (C.ltoreq.10) and M is Ti, Zr or Hf. The synthetic method involves a simple alkane elimination approach which permits a "one-pot" procedure. The catalyst, when combined with a cocatalyst such as Pb.sub.3 C.sup.+ B(Ar.sub.3.sup.F).sub.4 BAr.sub.3.sup.F or methyl alumoxane where Ar.sup.F is a fluoroaryl group, is an effective catalyst for the polymerization of .alpha.-olefins such as ethylene, propylene and styrene.Type: GrantFiled: October 15, 1997Date of Patent: January 5, 1999Assignee: Northwestern UniversityInventors: Tobin J. Marks, You-Xian Chen
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Patent number: 5851945Abstract: The invention addresses Group 5 metal compounds suitable as polymerization catalysts characterized by comprising one Group 15 element polyanionic ancillary ligand and three single or multidentate univalent ligands comprising Group 14-16 elements bound to the Group 5 metal, but excluding cyclopentadienyl ligands. The invention Group 5 metal compounds can be generically represented by the chemical symbols(1) ?RJ!MR'.sub.3, and(2) ?(RJ)Zn(Q)!MR'.sub.2where M is a Group 5 transition metal, preferably vanadium; J is a Group 15 heteroatom ligand covalently bound to M, preferably nitrogen; R is a substituted or unsubstituted aryl, hydrocarbyl or organometalloid group covalently bound to J; each R' is, independently, a uninegative ligand, e.g.Type: GrantFiled: February 7, 1997Date of Patent: December 22, 1998Assignee: Exxon Chemical Patents Inc.Inventors: Howard William Turner, Vincent John Murphy
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Patent number: 5821189Abstract: A catalyst for the (co)polymerization of ethylene is obtained by a process comprising the contact of the following components (A), (B), (C) and (D) in the respective molar ratios (1):(0.5-2):(0-25):(0-15):(A): a bivalent arene of titanium having the formulaTi (.eta..sup.6 -arene)(AlR.sub.x X.sub.4-x).sub.2 ;wherein: "arene" indicates benzene, or benzene substituted with from 1 to 6 C.sub.1 -C.sub.10 alkyl groups;each X independently represents a chlorine, bromine or fluorine atom;R is a C.sub.1 C.sub.10 alkyl group, linear or branched; "x" is a number varying from 0.5 to 2.Type: GrantFiled: May 19, 1995Date of Patent: October 13, 1998Assignee: Enichem S.p.A.Inventors: Fausto Calderazzo, Guido Pampaloni, Francesco Masi, Andrea Vallieri
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Patent number: 5763547Abstract: A supported catalyst composition comprising a complex of a Group 4 metal cyclopentadienyl derivative reacted with silica treated with an aluminoxane demonstrates improved reactivity, especially for incorporating long chain alpha-olefins and also shows improved resistance to catalyst poisoning. The supported catalyst composition is adapted to produce homogeneous polymers, copolymers, terpolymers, etc., for example, homogeneous polyethylene, homogeneous poly(ethylene-octene) copolymers and the like. The invention further includes the process of preparing the supported catalyst compositions and a process for preparing olefinic polymers using these catalyst compositions.Type: GrantFiled: April 1, 1996Date of Patent: June 9, 1998Assignee: The Dow Chemical CompanyInventors: Brian W. S. Kolthammer, John C. Tracy, Robert S. Cardwell, Robert K. Rosen
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Patent number: 5756609Abstract: An olefin homogeneous polymerization catalyst demonstrating increased activity is formed from a cyclopentadienyl metallocene component, a salt of a compatible cation and a non-coordinating anion, and a C.sub.3 -C.sub.6 trialkylaluminum, preferably triisobutylaluminum. A homogeneous polymerization process comprises controlling polymerization activity with such catalyst by controlling the aluminum/metal (Al/M) molar ratio to a minimal level within the effective range of Al/M ratios.Type: GrantFiled: October 17, 1996Date of Patent: May 26, 1998Assignee: Amoco CorporationInventor: Steven A. Cohen
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Patent number: 5744678Abstract: An oligomerization catalyst according to the invention comprises a nickel compound (A); an organophosphoric compound (B); an organoaluminum compound (C); and a compound of the group consisting of carbon-halogen bond-containing compounds, oxoacid and salts thereof, sulfonic acid and derivatives thereof, and compounds of any of the formulae QX.sup.4.sub.n, QR.sub.n, QR'.sub.n, QX.sup.4.sub.1 R.sub.m, QX.sup.4.sub.1 R'.sub.m, QR.sub.1 R'.sub.m, Q.sup.1 (BR.sub.4).sub.p and R"(BR.sub.4) wherein Q is an element of the group consisting of Mg, Ti, Zr, B and Sn, Q.sup.1 is an element of the group consisting of Li, Na, K, Ca and Zn, X.sup.4 is a halogen or hydrogen atom, R is a C.sub.1 -C.sub.12 hydrocarbon group, R' is a C.sub.1 -C.sub.12 oxygen-containing hydrocarbon group, R" is a C.sub.1 -C.sub.20 hydrocarbon group or an ammonium group, n is a valence of Q, l, m is a natural member that satisfied n=l+m, and p is a valence of Q.sup.1. This catalyst is useful for the production of alpha-olefinic oligomers.Type: GrantFiled: November 1, 1996Date of Patent: April 28, 1998Assignee: Nippon Oil Co., Ltd.Inventors: Fuyuki Aida, Takashi Nakano, Yoshio Tajima, Kazuo Matsuura
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Patent number: 5733835Abstract: It has been determined that 1,3-butadiene monomer can be polymerized into cis-1,4-polybutadiene rubber utilizing a cobalt-based catalyst system which is comprised of (a) an organocobalt compound, (b) a trialkylaluminum compound and (c) hexafluoro-2-propanol. The use of this catalyst system results in extremely fast rates of polymerization. The molecular weight of the cis-1,4-polybutadiene rubber made utilizing this cobalt-based catalyst system can be regulated by conducting the polymerization in the presence of 1,5-cyclooctadiene. This present invention more specifically discloses a catalyst system which is particularly useful for polymerizing 1,3-butadiene monomer into cis-1,4-polybutadiene, said catalyst system being comprised of (a) an organocobalt compound, (b) a trialkylaluminum compound and (c) hexafluoro-2-propanol.Type: GrantFiled: August 5, 1996Date of Patent: March 31, 1998Assignee: The Goodyear Tire & Rubber CompanyInventor: Kenneth Floyd Castner
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Patent number: 5728641Abstract: According to the present invention there are provided a catalyst component, a catalyst using the catalyst component and a process using the catalyst, for the preparation of olefin polymers high in molecular weight and relatively wide in molecular weight distribution, using an extremely small amount of a modified organoaluminum compound such as methylaluminoxane and in high yield. The catalyst component is prepared by contacting at least the following constituents (1), (2), (3) and (4) with one another:(1) a compound represented by the general formula Me.sup.1 R.sup.1.sub.p (OR.sup.2).sub.q X.sub.4-p-q where R.sup.1 and R.sup.2 are each independently a hydrocarbon group having 1 to 24 carbon atoms, X is a halogen atom, Me is Zr, Ti or Hf, p and q are each an integer in the ranges of 0.ltoreq.p.ltoreq.4 and 0.ltoreq.q.ltoreq.4, provided 0.ltoreq.p+q.ltoreq.4;(2) at least one compound selected from the group consisting of compounds represented by the following general formulas 1 to 4:General formula 1: Me.sup.Type: GrantFiled: June 21, 1995Date of Patent: March 17, 1998Assignee: Nippon Oil Company, LimitedInventors: Fuyuki Aida, Yoshio Tajima, Kazuo Matsuura
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Patent number: 5728784Abstract: Process for the preparation of crystalline vinylaromatic polymers with a predominantly syndiotactic structure which comprises polymerizing vinylaromatic monomers, alone or mixed with at least one other monomer, in the presence of a catalytic system essentially consisting of:a) a complex of titanium or zirconium selected from those having general formula:MR.sub.1 R.sub.2 R.sub.3 R.sub.4, A.sub.1 MR.sub.1 R.sub.2 R.sub.3, A.sub.1 A.sub.2 MR.sub.1 R.sub.2 (I)b) a co-catalyst selected from an alkylalumoxane and a compound of boron having formula (II):BX.sub.1 X.sub.2 X.sub.3 (II)or one of its salts;c) a derivative of tin having general formula:SnR.sub.5 R.sub.6 R.sub.7 R.sub.Type: GrantFiled: November 27, 1996Date of Patent: March 17, 1998Assignee: Enichem S.p.A.Inventors: Riccardo Po', Nicoletta Cardi, Roberto Santi
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Patent number: 5726115Abstract: A catalyst composition comprising a bis-amide compound represented by the formula ##STR1## wherein M is zirconium, hafnium or titanium; each N is a three coordinate nitrogen atom; each e is Si, Ge or Sn; each Z is, independently, a hydride or R; each R is, independently, a hydrocarbyl one or more carbon atoms of which may be substituted by an element selected from Si, O, P, N and S; L is a neutral Lewis base and m is a number from 0 to 2; or a dimer thereof and a second component. Preferably the second component is a compound which is capable of providing a bulky and labile anion ?A!.sup.-, which anion is substantially non-coordinating under the reaction conditions and contains at least one boron atom. Also provided is a process for oligomerizing or co-oligomerizing alpha olefins in the presence of this catalyst composition.Type: GrantFiled: March 11, 1996Date of Patent: March 10, 1998Assignee: Shell Oil CompanyInventors: Andrew David Horton, Jan De With
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Patent number: 5707914Abstract: A process for the polymerization of olefinic hydrocarbons is carried out in the presence of a catalyst comprising a catalyst component derived from reacting a compound of the formula Me.sup.1 R.sup.1.sub.n X.sup.1.sub.4-n, a compound of the formula Me.sup.2 R.sup.2.sub.m X.sup.2.sub.z-m, an organocyclic compound having two or more conjugated double bonds and a carrier of inorganic or polymeric material, and a modified organoaluminum compound having Al--O--Al bonds, the resulting polyolefins having a relatively wide molecular weight distribution, a relatively narrow composition distribution and increased bulk density.Type: GrantFiled: June 5, 1995Date of Patent: January 13, 1998Assignee: Nippon Oil Co., Ltd.Inventors: Naoki Kataoka, Yosuke Numao, Takashi Seki, Yoshio Tajima, Kazuo Matsuura
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Patent number: 5693583Abstract: A catalyst composition for copolymerizing ethylene and alpha-olefins is prepared by treating a silica carrier, in a non-polar hydrocarbon solvent, with a dialkyl magnesium compound, a halogen-containing compound and titanium tetrachloride, to form a catalyst precursor and activating the precursor with dimethylaluminum chloride.Also disclosed is a process for copolymerizing ethylene and alpha-olefins in the presence of the catalyst of the invention. The polymer products have multimodal molecular weight distributions unlike unimodal molecular weight distributions of polymers prepared with similar catalyst precursors but activated with different alkylaluminum activators, e.g., triethylaluminum or trimethylaluminum.Type: GrantFiled: February 11, 1997Date of Patent: December 2, 1997Assignee: Mobil Oil CorporationInventors: Robert O. Hagerty, Per K. Husby, Yury V. Kissin, Robert I. Mink, Thomas E. Nowlin
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Patent number: 5670439Abstract: A vanadium-containing catalyst system particularly suited to the polymerization of olefin polymers. The catalyst system includes a supported, first catalyst component prepared by contacting silica with hexaalkyldisilazane and thereupon with (1) a compound or complex which includes at least one carbon to magnesium covalent bond and (2) a compound which includes at least one carbon to Group 13 metal covalent bond. The sequence of contact of the silica with compound or complex (1) and compound (2) is optional. However, unless the compound or complex (1) and the compound (2) contact the silica simultaneously, the product of this contact is next contacted with whichever of compound (1) or (2) does not initially contact the silica. The product of the step of contacting with compounds (1) and (2) is washed and then contacted with a vanadium compound which includes at least one halogen atom. Finally, the product of the vanadium compound contacting step is contacted with an alcohol.Type: GrantFiled: January 5, 1996Date of Patent: September 23, 1997Assignee: Quantum Chemical CorporationInventors: Linda N. Winslow, Raghu K. Menon
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Patent number: 5644009Abstract: An catalyst composition for preparing high-syndiotacticity polystyrene polymers which comprises: (a) a titanium complex represented by the following formula of TiR'.sub.1 R'.sub.2 R'.sub.3 R'.sub.4 or TiR'.sub.1 R'.sub.2 R'.sub.3, wherein R'.sub.1, R'.sub.2, R'.sub.3, and R'.sub.4 are, independently, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a hydrogen atom, or a halogen atom; (b) a cyclopentadienyl complex of silicon (Si), germanium (Ge), or tin (Sn) represented by the following formula: ##STR1## wherein R.sub.1, R.sub.2, R.sub.3, and R.sub.Type: GrantFiled: November 27, 1995Date of Patent: July 1, 1997Assignee: Industrial Technology Research InstituteInventors: Jing-Cherng Tsai, Shian-Jy Wang, Shu-Ling Peng, Mickey Sue
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Patent number: 5614457Abstract: This invention is for a catalyst system for polymerization of olefins using an ionic metallocene catalyst with aluminum alkyl. The metallocene catalyst is an ion pair formed from a neutral metallocene compound and an ionizing compound. The invention can be used in any method of producing ionic metallocene catalysts. Use of aluminum alkyl with an ionic metallocene catalyst eliminates the need for using methylaluminoxane (MAO). Catalysts produced by the method of this invention have high activity. The invention reduces catalyst poisons which cause low activity, no activity or uncontrolled polymerizations. Polymerization using this catalyst system are reproducible and controllable.Type: GrantFiled: May 24, 1995Date of Patent: March 25, 1997Assignee: Fina Technology, Inc.Inventors: John A. Ewen, Michael J. Elder
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Patent number: 5594079Abstract: A method for producing a stereoregular polyolefin in the presence of a catalyst comprising a transition metal compound and an organometallic compound, which comprises polymerizing at least one olefin in the presence of a catalyst system comprising:(A) a solid catalyst component comprising Mg, Ti, halogen and an electron donative compound,(B) at least one member selected from the group consisting of organometallic compounds of metals of Groups IA, IIA, IIB, IIIB and IVB of the Periodic Table,(C) an electron donative compound, and(D) a boron compound of the formula R.sup.1.sub.n BX.sub.3-n wherein R.sup.1 is a hydrocarbon group and/or a halogenated hydrocarbon group, X is a halogen atom, and 0.ltoreq.n.ltoreq.3.Type: GrantFiled: February 14, 1996Date of Patent: January 14, 1997Assignee: Tosoh CorporationInventors: Daiji Hara, Masahiro Adachi, Mitsuhiro Mori
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Patent number: 5587439Abstract: The present invention is directed to a supported metallocene catalyst useful in the polymerization of .alpha.-olefins which is obtained by tethering a metallocene catalyst component to the surface of a particulate, functionalized copolymeric support material.Type: GrantFiled: May 12, 1995Date of Patent: December 24, 1996Assignee: Quantum Chemical CorporationInventor: Anthony-J. DiMaio
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Patent number: 5585447Abstract: This catalyst has the general formula VX.sub.3, mAIX.sub.3, nZ, wherein X is a halogen atom, Z is at least one at least partially halogenated, branched or unbranched, saturated hydrocarbon, m is between 0.1 and 10, and n is between 1 and 300. To prepare it, a vanadium halide VX.sub.2 and/or VX.sub.3 is coground with an aluminum halide AlX.sub.3, and then at least one halogenated hydrocarbon Z is added to the mixture obtained in proportions corresponding to the chosen values of m and n. The invention also relates to the (co)polymerization of alpha-olefins at 20.degree.-350.degree. C. in the presence of a catalyst system comprising at least one catalyst as defined above and at least one organometallic activator.Type: GrantFiled: August 14, 1995Date of Patent: December 17, 1996Assignee: ECP-Enichem Polymeres France S.A.Inventors: Emmanuel Adisson, Karel Bujadoux, Michel Fontanille, Alain Deffieux
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Procatalyst composition for homo- and copolymerization of alpha olefins, its preparation and its use
Patent number: 5583083Abstract: A procatalyst composition which is suitable for the homo- and copolymerization of alpha olefins together with an organometallic cocatalyst compound and which is prepared by treating an inorganic carrier with a component system containing a complex of a magnesium halide and a tetraalkyl titanate, and a chlorinating compound which does not contain a transition metal compound. In order to raise the Mg:Ti ratio, the component system additionally contains an organomagnesium compound.Type: GrantFiled: July 10, 1995Date of Patent: December 10, 1996Assignee: Neste OyInventors: Sirpa Ala-Huikku, Marjaana Lommi -
Patent number: 5561092Abstract: This invention is for a catalyst system comprising a neutral metallocene compound, an aluminum alkyl and a Lewis acid. The Lewis acid must be of sufficient acidity to ionize a neutral metallocene compound to form a cationic metallocene catalyst. The ligands of the Lewis acid should not be reactive with the metallocene cation. Any metallocene catalyst compound having two cyclopentadienyl rings, substituted or unsubstituted, attached to a transition metal which can be ionized by a Lewis acid would be useful in this invention. The invention is also for the process of making the catalyst system and the process for using the catalyst system in polymerization of olefins. The metallocene is contacted with the Lewis acid. The aluminum alkyl is contacted with the olefin. The two mixtures are contacted with each other under polymerization conditions.Type: GrantFiled: March 30, 1993Date of Patent: October 1, 1996Assignee: Fina Technology, Inc.Inventors: John A. Ewen, Michael J. Elder
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Patent number: 5474961Abstract: Metallocene catalyst systems for the polymerization of C.sub.2 -C.sub.10 -alkenes are obtainable by deactivation of a preactivated metallocene catalyst system which contains, as active components, a metallocene complex of a metal of subgroup IV or V of the Periodic Table and an oligomeric alumoxane compound and, if required, subsequent reactivation.Type: GrantFiled: March 8, 1994Date of Patent: December 12, 1995Assignee: BASF AktiengesellschaftInventors: Rueger Schlund, Meinolf Kersting, Klaus-Dieter Hungenberg
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Patent number: 5416053Abstract: A process for the production of polyethylenes or EPRs comprising contacting a mixture comprising ethylene, one or more alpha-olefins, and, optionally, a diene, under polymerization conditions, with a catalyst system comprising:(A) a catalyst precursor comprising:(i) a vanadium compound, which is the reaction product of(a) VX.sub.3 wherein each X is independently chlorine, bromine, or iodine; and(b) an electron donor, which is a liquid, organic Lewis base in which VX.sub.3 is soluble;(ii) a modifier having the formula BX.sub.3 or AlR.sub.(3-a) X.sub.a wherein each R is independently alkyl having 1 to 14 carbon atoms; each X is as defined above; and a is 0, 1, or 2; and(iii) a support for said vanadium compound and modifier,said catalyst precursor being in an independent or prepolymerized state,(B) a cocatalyst consisting of a compound having the formula AlR.sub.(3-a) X.sub.Type: GrantFiled: June 28, 1993Date of Patent: May 16, 1995Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Xinlai Bai, Kevin J. Cann