Contains Non-transition Elemental Metal, Hydride Thereof, Or Carbon To Non Transition Metal Atom Bond Patents (Class 526/132)
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Patent number: 5629398Abstract: A process for effectively producing a cyclic olefin polymer and a cyclic olefin/alpha-olefin copolymer without opening the cyclic olefin, is disclosed. Further, a novel cyclic olefin/alpha-olefin copolymer prepared by the above-mentioned process, compositions and molded articles comprising the novel copolymer, are also disclosed. In the process for producing a cylcic olefin based polymer according to the present invention, homopolymerization of a cyclic olefin or copolymerization of a cyclic olefin and an alpha-olefin is effected in the presence of a catalyst comprising, as main ingredients, the following Compounds (A) and (B), and optionally Compound (C):(A) a transition metal compound;(B) a compound capable of forming an ionic complex when reacted with a transition metal compound; and(C) an organoaluminum compound.Type: GrantFiled: June 5, 1992Date of Patent: May 13, 1997Assignee: Idemitsu Kosan Co., Ltd.Inventors: Takuji Okamoto, Junichi Matsumoto, Masami Watanabe, Hiroshi Maezawa
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Patent number: 5625016Abstract: This invention is a solution process for the preparation of high molecular weight ethylene-.alpha.-olefin-diolefin copolymers comprising contacting ethylene, one or more .alpha.-olefin monomer, and optionally one or more diene monomer, with a catalyst system at a polymerization temperature at or above about 80.degree. C., ethylene, one or more .alpha.-olefin monomer, and optionally one or more diene monomer, with a catalyst system comprising an unbridged Group 4 metal compound having a bulky monocyclopentadienyl ligand, a uninegative bulky Group 15 ligand and two uninegative, activation reactive ligands and a catalyst activator compound. The process can be advantageously practiced a reaction temperature of at least 80.degree. C., most preferably above 100.degree. C., to achieve high number average molecular weight polymer having high .alpha.-olefin monomer and diene monomer contents with high diene conversion rates.Type: GrantFiled: October 20, 1995Date of Patent: April 29, 1997Assignee: Exxon Chemical Patents, Inc.Inventors: Rinaldo S. Schiffino, Donna J. Crowther
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Patent number: 5602219Abstract: Transparent cycloolefin copolymers having a high tensile strength are obtained by polymerization of a polycyclic olefin, ethylene and, if desired, an acyclic olefin and/or a monocylcic olefin in the presence of a catalyst system which comprises a cocatalyst and an asymmetrical metallocene compound of the formula ##STR1## in which R.sup.16 is cyclopentadienyl and R.sup.17 is indenyl.Type: GrantFiled: May 22, 1995Date of Patent: February 11, 1997Assignee: Hoechst AktiengesellschaftInventors: Michael Aulbach, Michael-Joachim Brekner, Frank K uber, Frank Osan, Thomas Weller, J urgen Rohrmann
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Patent number: 5599887Abstract: This invention provides a chromium catalyst system that comprises[a] a support that comprises silica, wherein said support has a surface area to pore volume relationship as follows0.5.ltoreq.Pore volume.ltoreq.f(SA)wherein said f(SA) is(1.14.times.10.sup.-7)(SA).sup.3 -(1.19.times.10.sup.-4)(SA).sup.2 +(3.19.times.10.sup.-2)(SA)+0.20;and[b] a hexavalent chromium compound;wherein the surface concentration of said hexavalent chromium on said support is from 0.25 to 1 hexavalent chromium atoms per square nanometer.Another embodiment of this invention provides a process to homopolymerize ethylene, or copolymerize ethylene with a comonomer, said process comprises polymerizing ethylene with the above chromium catalyst composition.Type: GrantFiled: May 25, 1995Date of Patent: February 4, 1997Assignee: Phillips Petroleum CompanyInventors: Rickey D. Badley, Kent W. Rollmann, Max P. McDaniel
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Patent number: 5596054Abstract: There are disclosed a transition metal compound of the general formula RMX.sub.a-1 L.sub.b (R is as a .pi. ligand, a fused polycyclic cyclopentadienyl group in which at least one of many-membered rings to which cyclopentadienyl groups are fusedly bonded is a saturated ring, M is a transition metal, X is a .sigma. ligand, L is a Lewis base, a is the valency of M, and b is 0, 1 or 2); a polymerization catalyst for styrene, etc. comprising the above transition metal, preferably further comprising an oxygen atom containing compound ionic compound or organoboron compound and optionally a Lewis base; and a process for producing a polymer of a compound containing an ethylenically unsaturated double bond or an acetylenic polymer, especially a syndiotactic polystyrene by using the above polymerization catalyst. The catalyst is particularly effectivive for producing highly syndiotactic polystyrene minimized in residual metals amounts at a low cost in enhanced efficiency.Type: GrantFiled: March 10, 1995Date of Patent: January 21, 1997Assignee: Idemitsu Kosan Co., Ltd.Inventor: Mizutomo Takeuchi
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Patent number: 5596052Abstract: Amorphous propylene polymers are disclosed having the following characteristics:(a) intrinsic viscosity [.eta.]>1 d1/g;(b) %(r)-%(m)>0, wherein % (r) is the % of syndiotactic diads and %(m) is the % of isotactic diads;(c) less than 2% of the CH.sub.2 groups contained in sequences (CH.sub.2).sub.n, with n.gtoreq.2;(d) Bernoullianity index (B)=1.+-.0.2.These propylene polymers, which are in addition endowed with a narrow molecular weight distribution, can be obtained directly from the polymerization reaction of propylene as sole product and, therefore, do not require to be separated.Type: GrantFiled: March 25, 1996Date of Patent: January 21, 1997Assignee: Montell Technology Company bvInventors: Luigi Resconi, Enrico Albizzati
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Patent number: 5596055Abstract: There is disclosed a process for producing a styrenic polymer, especially, syndiotactic polystyrene, which comprises polymerizing a styrenic monomer by the use of a (a) transition metal compound, a (b) coordination complex compound comprising an anion in which a plurality of racicals are bonded to a metal and a cation or a Lewis acid, a (c) alkylating agent (alkyl group-containing aluminum, magnesium or zinc compound) and a (d) reaction product between a straight-chain alkylaluminum having at least two carbon atoms and water (alkylaluminoxane). The above process is capable of simplifying the production process and producing high-performance styrenic polymer having a high degree of syndiotactic configuration in high catalytic activity without deteriorating the catalyst activity, increasing the amounts of residual metals in the objective polymer or leaving the decomposition products of the alkylaluminum therein, thereby curtailing the production cost of the objective polymer.Type: GrantFiled: March 30, 1995Date of Patent: January 21, 1997Assignee: Idemitsu Kosan Co., Ltd.Inventors: Yoshiaki Aoyama, Norio Tomotsu
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Patent number: 5596053Abstract: Diene polymers having a high content of trans-1,4 addition and two distinct melting points in the ranges of 30.degree. C. to 50.degree. C. and 70.degree. C. to 130.degree. C. are prepared by polymerizing a 1,3-diene monomer in a hydrocarbon solvent in the presence of a catalyst composition comprising (a) a carboxylated nickel oxy borate compound; (b) an orKanoaluminum compound; (c) a triaryloxy phosphorus compound and (d) a carboxylic acid preferably a fluorinated carboxylic acid. The resultant polymers are useful as additives to tire rubbers to improve processability by reducing compound Mooney viscosity and reducing the shrinkage of various compound stocks.Type: GrantFiled: May 31, 1995Date of Patent: January 21, 1997Assignee: Bridgestone/Firestone, Inc.Inventors: Jung W. Kang, Jason T. Poulton
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Patent number: 5594078Abstract: A catalyst system comprising a bridged fluorenyl-containing metallocene, an unbridged metallocene, and a suitable cocatalyst and the use of such catalyst systems to produce olefin polymers. Also novel olefin polymers produced by those processes.Type: GrantFiled: September 13, 1994Date of Patent: January 14, 1997Assignee: Phillips Petroleum CompanyInventors: M. Bruce Welch, Rolf L. Geerts, Syriac J. Palackal, Ted M. Pettijohn
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Patent number: 5591815Abstract: A polymer having a repeating unit of ##STR1## and a method for preparing it through Zr-catalyzed polymerization of methylenecyclopropane is disclosed.Type: GrantFiled: November 6, 1995Date of Patent: January 7, 1997Assignee: Northwestern UniversityInventors: Tobin J. Marks, Xinmin Yang, Li Jia
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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: 5583189Abstract: In accordance with the present invention, there is provided catalyst systems and processes for preparing such catalyst systems comprising reacting a metallocene compound, a solid organoaluminoxy product, and an organometal compound. Further there is provided processes for the polymerization of olefins using the catalyst systems.Type: GrantFiled: May 16, 1995Date of Patent: December 10, 1996Assignee: Phillips Petroleum CompanyInventors: Rolf L. Geerts, Syriac J. Palackal, Ted M. Pettijohn, Robert M. Infield
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Patent number: 5578690Abstract: There is disclosed a method for synthesizing polyolefins having a silyl group at one terminus, said method comprising reacting(A) a monomer selected from the group consisting of ethylene and a combination of ethylene and an .alpha.-olefin; and(B) a silane having the formulaR.sup.2 R.sup.3 R.sup.4 SiHwherein R.sup.2, R.sup.3 and R.sup.4 each represents a monovalent group selected from the group consisting of hydrogen, alkyl having 1 to 4 carbon atoms, aryl, alkylaryl, arylalkyl, alkoxy having 1-4 carbon atoms, phenoxy, fluorinated alkyl having 3 to 6 carbon atoms, a dialkylamino group in which the alkyl groups contain 1 to 4 carbon atoms and a diorganopolysiloxane chain containing 1 to 10 siloxane units, said reaction taking place in the presence of(C) a catalyst comprising a metallocene compound.Type: GrantFiled: April 28, 1995Date of Patent: November 26, 1996Assignee: Northwestern UniversityInventors: Tobin J. Marks, Peng-Fei Fu
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Patent number: 5559199Abstract: There is provided a process for producing a cyclic olefin copolymer by copolymerizing (A) ethylene and (B) a particular cyclic olefin in the presence of (C) a metallocene catalyst and (D) a small amount of an .alpha.-olefin having 3 to 20 carbon atoms. According to the said process, said copolymer can be produced at a high activity and its molecular weight can be controlled in a wide range. The copolymer produced by the said process has excellent properties inherent to the cyclic olefin copolymer.Type: GrantFiled: April 21, 1995Date of Patent: September 24, 1996Assignees: Mitsui Petrochemical Industries, Ltd., Hoechst AktiengesellschaftInventors: Yoshiharu Abe, Toshihiro Sagane, Akinori Toyota
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Patent number: 5552504Abstract: A film including semi-crystalline cycloolefin copolymers which have a content of catalyst residues of <100 ppm and their use as capacitor films, reproduction films, film keyboards and film switches, substrates for liquid crystal displays and packaging films.Type: GrantFiled: February 14, 1994Date of Patent: September 3, 1996Assignee: Hoechst AktiengesellschaftInventors: Cynthia Bennett, Michael-Joachim Brekner, Jochen Coutandin, Otto Herrmann-Schoenherr, Frank Osan
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Patent number: 5541271Abstract: A polyolefin having superior particle properties such as an extremely high bulk density, a large average particle diameter and a narrow particle size distribution, and having a narrow molecular weight distribution, is obtained in high yield, by polymerizing an olefin, using a catalyst comprising a solid catalyst component and an organometallic compound, the solid catalyst component being obtained by reacting a) a silicon oxide and/or an aluminum oxide, the reaction product of an organomagnesium compound and a compound of the general formula Me(OR).sub.n X.sub.Z-n, and a titanium compound, in the presence of ROH, and further reacting the resulting reaction product with a compound of the general formula AlR.sub.q X.sub.3-q.Type: GrantFiled: January 30, 1995Date of Patent: July 30, 1996Assignee: Nippon Oil Company, LimitedInventors: Akira Sano, Shiraishi Takeichi, Kunihiro Suzuki, Mitsuo Okamoto, Katsumi Usui, Hiroyuki Shimizu, Kazuo Matsuura
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Patent number: 5534606Abstract: A rigid single- or multilayer non-oriented or mono- or biaxially oriented film in which at least one layer comprises a cycloolefin copolymer, wherein the cycloolefin copolymer has an intrinsic E modulus (E.sub.i) which has the following dependence on the glass transition temperature T.sub.g :E.sub.i =(0.0025[GPa/.degree.C.].times.T.sub.g [.degree.C.])+B[GPa]where B=2.93-3.19 and T.sub.g is the glass transition temperature.Type: GrantFiled: February 14, 1994Date of Patent: July 9, 1996Assignee: Hoechst AktiengesellschaftInventors: Cynthia Bennett, Michael-Joachim Brekner, Otto Herrmann-Schoenherr, Frank Osan
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Patent number: 5534473Abstract: A catalyst system comprising a bridged fluorenyl-containing metallocene, an unbridged metallocene, and a suitable cocatalyst and the use of such catalyst systems to produce olefin polymers. Also novel olefin polymers produced by those processes.Type: GrantFiled: June 5, 1995Date of Patent: July 9, 1996Assignee: Phillips Petroleum CompanyInventors: M. Bruce Welch, Rolf L. Geerts, Syriac J. Palackal, Ted M. Pettijohn
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Patent number: 5519100Abstract: 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 catalyst. 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. Polymerizations using this catalyst system are reproducible and controllable.Type: GrantFiled: February 4, 1992Date of Patent: May 21, 1996Assignee: Fina Technology, Inc.Inventors: John A. Ewen, Michael J. Elder
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Patent number: 5519099Abstract: A catalyst composition is disclosed for catalyzing the polymerization and copolymerization reactions of ethylene monomers, with or without another olefin monomer. The catalyst composition comprises a metallocene compound represented by the the formula of (C.sub.5 R.sub.n H.sub.5-n)(L)MXY or the formula of (C.sub.5 R.sub.n H.sub.5-n)(L)MX.sup.+ A.sup.- ; wherein: (a) C.sub.5 R.sub.n H.sub.5-n is a substituted or unsubstituted cyclopendadienyl group; (b) L is tetrapyrazolyl borate, hydrotrispyrazolyl borate, dihydrotrispyrazolyl borate or hydrotris-3,5-dimethyl; (c) M is Group IIIB, Group IVB, or Group VB transitional metal; (d) X is a C.sub.1 to C.sub.4 alkyl or alkenyl group, an aromatic group, an alkylaryl, a halogen, a hydrogen, or a silane group; (e) Y, which can the same as or different from X, is a C.sub.1 to C.sub.4 alkyl or alkenyl group, an aromatic group, an alkylaryl, a halogen, a hydrogen, or a silane group; and (f) A.sup.- is non-coordinated or loosely coordinated bulky anion. Examples of the (C.Type: GrantFiled: June 7, 1995Date of Patent: May 21, 1996Assignee: Industrial Technology Research InstituteInventors: Shian-Jy Wang, Yi-Chun Chen, Shu-Hua Chan, Jing-Cherng Tsai, Yu-Hwa E. Sheu
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Patent number: 5512643Abstract: A process for preparing syndiotactic vinylidene aromatic polymers comprising contacting one or more vinylidene aromatic monomers with a catalyst comprising a Group 4 metal complex in the +3 oxidation state and a polyalkylaluminoxane cocatalyst.Type: GrantFiled: August 11, 1995Date of Patent: April 30, 1996Assignee: The Dow Chemical CompanyInventors: Thomas H. Newman, Karen K. Borodychuk
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Patent number: 5510434Abstract: There are disclosed a catalyst for producing an aromatic vinyl compound polymer which catalyst comprises a contact product between an (A) trivalent titanium compound and a (B) compound represented by the general formula (II) or (III)R.sup.1.sub.k M.sup.1 L.sup.2.sub.m (II)R.sup.1.sub.k M.sup.1 X.sup.2.sub.l L.sup.2.sub.m (III)a (C) an ionic compound comprising a noncoordinate anion and a cation, an aluminoxane or an organoboron compound; and optionally a (D) Lewis acid, and a process for producing an aromatic vinyl compound polymer having a high degree of syndiotactic configuration which process comprises polymerizing (a) an aromatic vinyl compound or (b) an aromatic vinyl compound together with an olefin or a diolefin in the presence of the above catalyst.Type: GrantFiled: November 23, 1994Date of Patent: April 23, 1996Assignee: Idemitsu Kosan Co., Ltd.Inventor: Mizutomo Takeuchi
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Patent number: 5502124Abstract: This invention relates to processes using non-Group 4 transition metal compositions useful as olefin polymerization catalysts, wherein the transition metal is in a high oxidation state. The invention further relates to design of new ligand systems and methods of preparing and using the same. Compositions useful as catalyst precursors are neutral transition metal complexes comprising the unique ligand systems of the invention. The inventive compositions may be activated to a catalytic state by ion-exchange reagents or by Lewis acids.Type: GrantFiled: May 19, 1995Date of Patent: March 26, 1996Assignee: Exxon Chemical Patents Inc.Inventors: Donna J. Crowther, Richard A. Fisher, Jo Ann M. Canich, Gregory G. Hlatky, Howard W. Turner
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Patent number: 5496781Abstract: In accordance with the present invention, there is provided catalyst systems and processes for preparing such catalyst systems comprising reacting a metallocene compound, a solid organoaluminoxy product, and an organometal compound. Further there is provided processes for the polymerization of olefins using the catalyst systems.Type: GrantFiled: May 16, 1994Date of Patent: March 5, 1996Assignee: Phillips Petroleum CompanyInventors: Rolf L. Geerts, Syriac J. Palackal, Ted M. Pettijohn, Robert M. Infield
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Patent number: 5489659Abstract: A catalyst component for use in the polymerization of .alpha.-olefins, comprising a compound represented by the following general formula [I]: ##STR1## wherein R.sup.1 s represent a hydrogen atom, a C.sub.1-6 hydrocarbon group or a C.sub.1-12 hydrocarbon group containing silicon; each of R.sup.2 and R.sup.3 independently represents a divalent group selected from the group consisting of a hydrocarbon group having 3 to 30 carbon atoms and a silicon-containing hydrocarbon group having 1 to 30 carbon atoms and 1 to 6 silicon atoms, provided that at least one of R.sup.2 and R.sup.3 is said silicon-containing hydrocarbon group; Q represents a C.sub.1-20 divalent hydrocarbon group, a silylene group, a silylene group with a C.sub.1-20 hydrocarbon group, a germylene group, or a germylene group with a C.sub.1-20 hydrocarbon group; X and Y represent H, a halogen, a C.sub.1-20 hydrocarbon group, or a C.sub.Type: GrantFiled: February 18, 1994Date of Patent: February 6, 1996Assignee: Mitsubishi Chemical CorporationInventors: Toshihiko Sugano, Toru Wada, Tomohiko Takahama
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Patent number: 5461127Abstract: A polymerization catalyst comprising a polycation complex (A) represented by the following Formula, [(CUHC).sub.n MX.sub.m ].sup.j+ .multidot.([Y].sup.-)j; [(CUHC): a cyclic unsaturated hydrocarbon group], more particularly, a polymerization catalyst comprising the reaction product of a transition metal compound and an ionic compound (b) capable of forming an ionic complex when reacted with a transition metal compound, and the above-mentioned compound (b), is disclosed.Type: GrantFiled: September 22, 1993Date of Patent: October 24, 1995Assignee: Idemitsu Kosan Co., Ltd.Inventors: Shoji Naganuma, Masami Watanabe
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Patent number: 5459213Abstract: A catalyst system and process for the polymerization of cyclic olefins, such as dicyclopentadiene, are disclosed. The catalyst system contains a transition metal hydrotrispyrazolylborate complex having the formula:Tp--M--L.sub.3wherein Tp is a hydrotrispyrazolylborate ligand, M is tungsten or molybdenum, and L is independently a ligand selected from the group consisting of oxo, phenoxy, alkoxy, and halides, provided that at least one L is a halide, and a co-catalyst.Type: GrantFiled: March 15, 1994Date of Patent: October 17, 1995Assignee: Shell Oil CompanyInventor: Donald R. Kelsey
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Patent number: 5457171Abstract: Catalyst systems for the polymerization of C.sub.2 -C.sub.10 -alkenes contain, as active components, a metallocene complex of a metal of subgroup IV or V of the Periodic Table, an oligomeric alumina compound and a cyclic boron compound of the general formula IV ##STR1## where R.sup.18 to R.sup.20 are each C.sub.1 -C.sub.10 -alkyl which may be monosubstituted to trisubstituted by halogen, C.sub.6 -C.sub.15 -aryl or C.sub.1 -C.sub.10 -alkoxy,C.sub.4 -C.sub.7 -cycloalkyl which may be monosubstituted to trisubstituted by halogen, C.sub.1 -C.sub.10 -alkyl or C.sub.1 -C.sub.10 -alkoxy,C.sub.1 -C.sub.10 -alkoxy which may be monosubstituted to trisubstituted by halogen, C.sub.1 -C.sub.10 -alkyl or C.sub.6 -C.sub.15 -aryl, or C.sub.6 -C.sub.15 -aryl which may be monosubstituted to pentasubstituted by halogen, C.sub.1 -C.sub.10 -alkyl or C.sub.1 -C.sub.10 -alkoxy.Type: GrantFiled: August 3, 1994Date of Patent: October 10, 1995Assignee: BASF AktiengesellschaftInventors: Franz Langhauser, Martin Lux, Rolf Muelhaupt, David Fischer
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Patent number: 5438093Abstract: Solution and RIM polymerization of cycloolefins containing at least one norbornene moiety is carried out in the presence of a methathesis catalyst system and an activator, particularly a chlorosilane activator, to obtain faster reaction with higher conversions at lower mold temperatures. The methathesis catalyst system includes an organoammonium molybdate or tungstate catalyst and an alkylaluminum or an alkylaluminum halide cocatalyst. The chlorosilane activator is used at a level of 0.05 to 10 millimoles per mole of the cycloolefin monomers. The polymers of cycloolefins can be impact modified and/or flame-retarded.Type: GrantFiled: June 26, 1992Date of Patent: August 1, 1995Assignee: B. F. Goodrich CompanyInventors: Paul T. Stricharczuk, Robert J. Minchak, Timothy J. Kettering, Dennis J. Janda, Glen R. Gribble, Jr.
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Patent number: 5436305Abstract: Fluorenyl-containing metallocenes are disclosed along with methods for making the metallocenes. Also disclosed are methods for using the metallocenes as polymerization catalysts. In addition, polymers resulting from such polymerizations are disclosed.Type: GrantFiled: July 23, 1991Date of Patent: July 25, 1995Assignee: Phillips Petroleum CompanyInventors: Helmut G. Alt, Syriac J. Palackal, Konstantinos Patsidis, M. Bruce Welch, Rolf L. Geerts, Eric T. Hsieh, Max P. McDaniel, Gil R. Hawley, Paul D. Smith
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Patent number: 5428098Abstract: A fiber-reinforced cycloolefin polymer material comprises 1 to 99% by weight of reinforcing fibers, in particular glass fibers, and 99 to 1% by weight of a cycloolefin copolymer which is built up froma) at least one (polycyclo)olefin which is derived from norbornene, for example tetracyclododecene, and b) at least one olefin which is chosen from monocycloolefins having 4 to 12 C atoms (VII) and/or the group of acyclic olefins VIII ##STR1## in which R.sup.9, R.sup.10, R.sup.11 and R.sup.12 are identical or different and are a hydrogen atom or a C.sub.1 -C.sub.8 -alkyl radical. VII is preferably ethylene. The monomer units of the (polycyclo)olefin in the cycloolefin copolymer molecule are in each case separated by monomer units of the cyclic olefins VII and/or of the acyclic olefins of the formula VIII.Type: GrantFiled: January 27, 1994Date of Patent: June 27, 1995Assignee: Hoechst AktiengesellschaftInventors: Michael-Joachim Brekner, Horst-Tore Land, Frank Osan
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Patent number: 5428120Abstract: A process for preparing syndiotactic vinylidene aromatic polymers comprising contacting one or more vinylidene aromatic monomers with tri n-propyl aluminum chain transfer agent under Ziegler-Natta polymerization conditions.Type: GrantFiled: October 8, 1993Date of Patent: June 27, 1995Assignee: The Dow Chemical CompanyInventors: Thomas H. Newman, Karen K. Borodychuk
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Patent number: 5416178Abstract: In the case of Ziegler catalysts based on a metallocene as the transition metal component and an aluminoxane as the activator, preactivation of the metallocene with the aluminoxane results in a considerable increase in the activity of the catalyst system. Furthermore, 1-olefin polymers of a high degree of isotacticity and having compact, spherical particles, a very narrow particle size distribution and a high bulk density are obtained by means of a catalyst system of this type.Type: GrantFiled: August 22, 1991Date of Patent: May 16, 1995Assignee: Hoechst AktiengesellschaftInventors: Andreas Winter, Walter Spaleck
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Patent number: 5414180Abstract: Organic aluminoxy compounds are prepared by reacting an organo boronic acid with a trihydrocarbyl aluminum compound. The resulting products are suitable as components for catalyst systems for the polymerization of olefins.Type: GrantFiled: July 14, 1993Date of Patent: May 9, 1995Assignee: Phillips Petroleum CompanyInventors: Rolf L. Geerts, Tara G. Hill
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Patent number: 5391661Abstract: There are disclosed a catalyst well suited for producing a styrenic polymer having a high degree of syndiotactic configuration which comprises a transition-metal compound such as pentamethylcyclopentadienyltrimethyltitanium and a coordination complex compound comprising an anion in which a plurality of radicals are bonded to a metal and a quaternary ammonium salt, the compound being exemplified by orthocyano-N-methylpyridinium tetra(pentafluorophenyl)borate, or comprises an alkylating agent such as triisobutylaluminum in addition to the above two compounds; and a process for producing a styrenic polymer having a high degree of syndiotactic configuration by polymerizing a styrenic monomer using the aforementioned catalyst. Consequently, a styrenic polymer having a high degree of syndiotactic configuration can be produced effectively without the use of an expensive aluminoxane required in a large amount if used.Type: GrantFiled: February 2, 1993Date of Patent: February 21, 1995Assignee: Idemitsu Kosan Co., Ltd.Inventors: Shoji Naganuma, Masami Watanabe, Norio Tomotsu
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Patent number: 5378777Abstract: There is disclosed a process for producing a styrenic polymer or copolymer each having syndiotactic configuration which comprises polymerizing a styrenic monomer represented by the general formula (I) ##STR1## such as phenylstyrene and trimethylsilylstyrene, or copolymerizing at least two styrenic monomers of the formula (I) or at least one styrenic monomer of the formula (I) with at least one styrenic monomer other than the styrenic monomer of the formula (I) in the presence of a catalyst comprising as principal ingredients(A) a transition metal compound derived from a group IVB metal of the Periodic Table such as pentamethylcyclopentadienyltrimethyltitanium and (B) a compound producing an ionic complex by the reaction with the above transition metal compound such as tri(n-butyl)ammonium tetra(pentafluorophenyl)borate. The aforementioned process enables efficient production of a styrenic polymer or copolymer excellent in heat resistance and mechanical strength.Type: GrantFiled: August 23, 1993Date of Patent: January 3, 1995Assignee: Idemitsu Kosan Co., Ltd.Inventors: Masami Watanabe, Shuji Machida
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Bulk polymerization using specific metallocene catalysts for the preparation of cycloolefin polymers
Patent number: 5371158Abstract: Bulk polymerization using specific metallocene catalysts for the preparation of cycloolefin polymersPolymers of polycyclic olefins, such as, for example, norbornene or tetracyclododecene, or copolymers of polycyclic olefins with cycloolefins and/or 1-olefins are obtained without ring opening, in high space-time yield, with a high cycloolefin incorporation rate and at industrially favorable polymerization temperatures, by bulk polymerization in which a catalyst is used which comprises an aluminoxane and a stereorigid chiral metallocene compound of an element from groups IVb to VIb, where the hydrocarbon radicals forming the sandwich structure are different.Type: GrantFiled: July 2, 1993Date of Patent: December 6, 1994Assignee: Hoechst AktiengesellschaftInventors: Michael-Joachim Brekner, Frank Osan, Jurgen Rohrmann, Martin Antberg -
Patent number: 5359102Abstract: A transition metal compound represented by the formula ##STR1## (wherein each of A.sup.1, A.sup.2, A.sup.3 and A.sup.4 is a cyclopentadienyl group, an indenyl group, a fluorenyl group or their derivative; A.sup.5 is a hydrocarbondiylidene group having 4 to 30 carbon atoms; a pair of A.sup.1 and A.sup.2 as well as a pair of A.sup.3 and A.sup.4 is respectively bonded to the identical carbon atom in A.sup.5 to form a crosslinking structure; each of R.sup.1 and R.sup.2 is a halogen atom, a hydrogen atom, an alkyl group or a silicon-containing alkyl group having 1 to 10 carbon atoms, an aryl group, an alkylaryl group, an arylalkyl group or a halogenated aryl group having 6 to 20 carbon atoms; R.sup.1 and R.sup.2 may be identical or different; each of M.sup.1 and M.sup.2 is titanium, zirconium or hafnium; and M.sup.1 and M.sup.2 may be mutually identical or different), and a method for polymerizing an olefin in the presence of this compound and a co-catalyst.Type: GrantFiled: October 8, 1992Date of Patent: October 25, 1994Assignee: Mitsui Toatsu Chemicals, IncorporatedInventors: Norihide Inoue, Tetsunosuke Shiomura, Masahiro Kouno, Yoshiho Sonobe, Kazumi Mizutani
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Patent number: 5330947Abstract: This invention relates to a catalyst system using a boron alkyl in combination with an aluminum alkyl as a co-catalyst, a process for making the catalyst system and a process using the catalyst system for polymerization of olefins, especially .alpha.-olefins, such as propylene. While both boron alkyls and aluminum alkyls are known as co-catalysts separately, use of a boron alkyl with an aluminum alkyl as co-catalysts in olefin polymerization resulted in an unexpected increase in polymer yield. An increase in yield is accomplished without any increase in the amount of aluminum residue in the polymer product. The preferred boron alkyl is triethyl boron. The preferred aluminum alkyl is TEAl.Type: GrantFiled: October 15, 1991Date of Patent: July 19, 1994Assignee: Fina Technology, Inc.Inventors: Edwar S. Shamshoum, David J. Rauscher, Shabbir A. Malbari
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Patent number: 5324801Abstract: Chemically homogeneous cycloolefin copolymers of polycyclic olefins, such as, for example, norbornene or tetracyclododecene, with cycloolefins and/or acyclic olefins are obtained without ring opening and in a high space-time yield if a catalyst system is used which comprises an aluminoxane and a stereorigid metallocene compound of an element from groups IVb to VIb, of the formula ##STR1## the part of the metallocene molecule formed by M.sup.1 and the substituents R.sup.16 -R.sup.17 having C.sub.1 -symmetry or being in the meso-form.Type: GrantFiled: August 9, 1993Date of Patent: June 28, 1994Assignee: Hoechst AktiengesellschaftInventors: Michael-Joachim Brekner, Frank Osan, Jurgen Rohrmann, Martin Antberg
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Patent number: 5310834Abstract: Mixed catalyst compositions comprised of a first supported chromium-containing catalyst component and a second supported chromium-containing catalyst component and which additionally have one or more metallic or non-metallic catalytic agents associated therewith are provided. The additional metallic or non-metallic elements associated with the catalyst components can be aluminum, titanium, zirconium, boron, phosphorous or combinations thereof. The pore volume of the silica supports used for the first and second catalyst components differs by at least 0.3 cc/g. The mixed catalyst compositions of the invention are useful for the preparation of polyolefins. They are particularly useful of polymerization of ethylene in particle form polymerizations to produce high density polyethylene blow molding resins having good processability and physical properties. The improved particle form polymerization process and products obtained thereby using the above-described mixed catalyst compositions are also described.Type: GrantFiled: December 16, 1992Date of Patent: May 10, 1994Assignee: Quantum Chemical CorporationInventors: Stanley J. Katzen, Thomas J. Pullukat, Michael W. Lynch, Louis J. Rekers
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Patent number: 5272229Abstract: There are disclosed a process for producing a styrene polymer having a high degree of syndiotactic configuration at a reduced cost and an enhanced efficiency, and a catalyst to be used therefore which comprises (A) a specific transition-metal compound, (B) a specific coordination complex compound and (C) a compound having an alkyl group.The catalyst according to the present invention is inexpensive compared with the conventional catalyst containing aluminoxane as the major ingredient, and exhibits a high activity in polymerizing a styrenic monomer into styrene polymer with a high degree of syndiotacticity as well as a high yield and conversion rate.Type: GrantFiled: December 2, 1991Date of Patent: December 21, 1993Assignee: Idemitsu Kosan Co., Ltd.Inventors: Norio Tomotsu, Mizutomo Takeuchi, Masahiko Kuramoto
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Patent number: 5241025Abstract: This invention relates to catalyst systems, and a method for using such system, for the enhanced production of homo and copolymer products of olefin, diolefin and/or acetylenically unsaturated monomers. This invention catalyst system comprises a Group III-A element compound for improving the productivity of an olefin polymerization catalyst which is the reaction product of a metallocene of a Group IV-B transition metal and an ionic activator compound comprising a cation capable of donating a proton which will irreversibly react with at least one ligand contained in the Group IV-B metal compound and an anion which is bulky, labile and noncoordinateable with the Group IV transition metal cation produced upon reaction of the metallocene and activator compound to form the catalyst component of the catalyst system.Type: GrantFiled: October 2, 1992Date of Patent: August 31, 1993Assignee: Exxon Chemical Patents Inc.Inventors: Gregory G. Hlatky, Howard W. Turner
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Patent number: 5229342Abstract: A complex alkoxide compound containing magnesium, titanium and boron species comprises the reaction product of elemental magnesium, titanium tetraalkoxide, an alkyl borate ester and alkanol at elevated temperature in an inert diluent. This complex alkoxide compound is contacted with a tetravalent titanium halide, a halohydrocarbon and an electron donor to form an olefin polymerization procatalyst. Contact of the procatalyst with an organoaluminum cocatalyst and a selectivity control agent produces a high activity catalyst for the polymerization of lower .alpha.-olefins to polymer product of good properties in good catalyst productivity.Type: GrantFiled: June 24, 1992Date of Patent: July 20, 1993Assignee: Shell Oil CompanyInventor: Robert C. Job
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Patent number: 5229476Abstract: A method for producing a stereospecific polyolefin in the presence of a catalyst comprising a transition metal compound and an organometallic compound, wherein a catalyst system is used which comprises: (A) a solid catalyst component prepared by reacting a homogeneous solution containing (i-1) magnesium and a hydroxylated organic compound, (i-2) an oxygen-containing organic compound of titanium and/or (i-3) an oxygen-containing organic compound of silicon and an oxygen-containing organic compound of aluminum and/or a boron compound, with (ii) at least one aluminum halide compound to obtain a solid product, and further reacting to this solid product (iii) an electron-donative compound, (iv) a titanium halide compound, and (v) ethylene and/or an .alpha.-olefin having at least 3 carbon atoms, (B) at least one member selected from the group consisting of organometallic compounds of Groups IA, IIA, IIB, IIIB and IVB of the Periodic Table, and (C) an electron-donative compound.Type: GrantFiled: August 23, 1991Date of Patent: July 20, 1993Assignee: Tosoh CorporationInventors: Daiji Hara, Mitsuhiro Mori, Yozo Kondo
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Patent number: 5227440Abstract: The invention is a supported catalyst system including an inert support material, a Group IV B transition metal component and an alumoxane component which may be employed to polymerize olefins to produce a high molecular weight polymer.Type: GrantFiled: August 28, 1991Date of Patent: July 13, 1993Assignee: Exxon Chemical Patents Inc.Inventors: Jo Ann M. Canich, Gary F. Licciardi
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Patent number: 5225500Abstract: Syndiospecific catalysts and processes for the syndiotactic propagation of a polymer chain derived from an ethylenically unsaturated monomer which contains 3 or more carbon atoms or is a substituted vinyl compound. The catalysts comprise an unbalanced metallocene cation, characterized by a cationic metallocene ligand having sterically dissimilar ring structures joined to a positively charged coordinating transition metal atom, and a stable noncoordinating counter anion for the metallocene cation. One of said ring structures is a substituted or unsubstituted cyclopentadienyl ring and the other of the ring structures is a substituted cyclopentadienyl group which is sterically different from the first cyclopentadienyl group. A structural bridge between cyclopentadienyl groups imparts stereorigidity to the catalyst. The catalyst is contacted with a C.sub.Type: GrantFiled: April 24, 1992Date of Patent: July 6, 1993Assignee: Fina Technology, Inc.Inventors: Michael J. Elder, Abbas Razavi, John A. Ewen
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Patent number: 5162466Abstract: Methylene bridged derivatives of novel cyclopentadienyl dicarbollide complexes of titanium, zirconium and hafnium display high activity as ethylene polymerization catalysts in the absence of a cocatalyst.Type: GrantFiled: December 31, 1991Date of Patent: November 10, 1992Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Frederick J. Karol, Sun-Chueh Kao, Robert C. Brady, III
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Patent number: 5162464Abstract: A process for producing a polyolefin, which comprises polymerizing at least one olefin in the presence of a catalyst system comprising (A) a solid catalyst component (A) obtained by reacting to a uniform solution containing (i) at least one member selected from the group consisting of metallic magnesium and an organic hydroxide compound, and an oxygen-containing organic magnesium compound, and (ii) at least one oxygen containing organic titanium compound, (iii) at least one organic aluminum compound, (iv) at least one boron compound having an alkoxy group, and (v) at least one aluminum halide compound; and (B) at least one catalyst component (B) selected from the group consisting of organic metal compounds of metals of Groups Ia, IIa, IIb, IIIb and IVb of the Periodic Table.Type: GrantFiled: July 8, 1991Date of Patent: November 10, 1992Assignee: Tosoh CorporationInventors: Morihiko Sato, Mitsuhiro Mori, Yozo Kondo
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Patent number: 5153157Abstract: This invention relates to catalyst systems, and a method for using such system, for the enhanced production of homo and copolymer products of olefin, diolefin and/or acetylenically unsaturated monomers. This invention catalyst system comprises a Group III-A element compound for improving the productivity of an olefin polymerization catalyst which is the reaction product of a metallocene of a Group IV-B transition metal and an ionic activator compound comprising a cation capable of donating a proton or which will irreversibly react with at least one ligand contained in the Group IV-B metal compound and an anion which is bulky, labile and noncoordinateable with the Group IV transition metal cation produced upon reaction of the metallocene and activator compound to form the catalyst component of the catalyst system.Type: GrantFiled: March 20, 1990Date of Patent: October 6, 1992Assignee: Exxon Chemical Patents Inc.Inventors: Gregory G. Hlatky, Howard W. Turner