Magnesium Compound Patents (Class 502/133)
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Patent number: 6323148Abstract: An ethylene polymerization catalyst and catalyst system which provides an ethylene copolymer which is characterized by desirable ER shift values. The high level ER shift of these polymers produce films having high impact strength. The catalyst is prepared by treating a support material with an agent selected from the group consisting of a compound having the structural formula BX53, where X5 is fluorine, chlorine, bromine, iodine or OR5, where R5 is C1-C6 alkyl; a compound having the structural formula X62 where X6 is fluorine, bromine or iodine; a compound having the structural formula NR6, where R6 is C1-C6 alkyl or OR7, where R7 is C1-C8 alkyl; and a compound having the structural formula Ti(OR8)4, where R8 is C1-C6 alkyl or phenyl to reduced surface hydroxyl group concentration of the support material. The thus treated support material is thereupon contacted with a dialkylmagnesium compound or complex, an alcohol compound or a silane compound and a transition metal compound, in that order.Type: GrantFiled: November 17, 1999Date of Patent: November 27, 2001Assignee: Equistar Chemicals, LPInventor: Mark K. Reinking
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Publication number: 20010039241Abstract: Complexes of magnesium and titanium alkoxides useful as olefin polymerization procatalyst precursors, procatalysts containing the complexes, and their use as a catalyst component for the polymerization of olefin monomers are disclosed. The complexes are prepared by reacting a magnesium alkoxide and a titanium alkoxide in the presence of a clipping agent to form a solid complex. The solid complex then can be used to form a procatalyst by contacting it with a halogenating agent, optionally a tetravalent titanium halide, and optionally an electron donor. The procatalyst then can be converted to an olefin polymerization catalyst by contacting it with a cocatalyst and optionally a selectivity control agent.Type: ApplicationFiled: June 20, 2001Publication date: November 8, 2001Inventor: Robert Charles Job
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Patent number: 6306984Abstract: The present invention relates to a catalyst composition and a method for making the catalyst composition of a polymerization catalyst and a carboxylate metal salt. The invention is also directed to the use of the catalyst composition in the polymerization of olefin(s). In particular, the polymerization catalyst system is supported on a carrier.Type: GrantFiled: September 16, 1999Date of Patent: October 23, 2001Assignee: Univation Technologies, LLCInventors: Agapios K. Agapiou, Chi-I Kuo, David M. Glowczwski, Steve K. Ackerman
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Publication number: 20010023281Abstract: A catalytic composition is obtained by mixing at least one chromium compound with at least one aryloxy compound of an element M selected from the group formed by magnesium, calcium, strontium and barium, with general formula M(RO)2-nXn, where RO is an aryloxy radical containing 6 to 80 carbon atoms, X is a halogen or a hydrocarbyl radical containing 1 to 30 carbon atoms and n is a whole number that can take values of 0 to 2, and with at least one aluminum compound selected from hydrocarbylaluminum compounds (tris(hydrocarbyl)-aluminum, chlorinated or brominated hydrocarbylaluminum compounds) and aluminoxanes. The catalytic composition can be used in an ethylene oligomerization process, in particular to produce 1-hexene.Type: ApplicationFiled: December 26, 2000Publication date: September 20, 2001Inventors: Dominique Commereuc, Sebastien Drochon, Lucien Saussine
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Patent number: 6291385Abstract: The present invention relates to a catalyst for polymerization or copolymerization of an olefin. The catalyst is produced by first reacting a mixture of a magnesium compound and an aluminum compound with an ester compound which has at least one hydroxy group and a silane compound which has at least one alkoxy group, and next reacting with a titanium compound. The catalyst may be used in the polymerization or copolymerization of ethylene and propylene.Type: GrantFiled: March 15, 1999Date of Patent: September 18, 2001Assignee: Samsung General Chemicals Co., Ltd.Inventors: Young-Sub Lee, Youn-Kyung Kang
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Patent number: 6288182Abstract: A catalyst composition has a catalyst component which includes a metallocene transition metal compound, a magnesium compound, a hydroxyl containing compound, and a polymeric material. The catalyst component may also include asilicon compound and an aluminum compound. The catalyst component is combined with a cocatalyst and used in olefin polymerization.Type: GrantFiled: October 12, 1999Date of Patent: September 11, 2001Assignee: Saudi Basic Industries CorporationInventors: Orass Hamed, Akhlaq Moman, Atieh Abu-Raqabah
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Patent number: 6268306Abstract: A polymerization catalyst obtained by contacting metallic magnesium with an aromatic halide, RX, under conditions effective to obtain a first reaction product and solid residual products is disclosed. The first reaction product is then separated from the solid residual products. A silane compound containing an alkoxy or aryloxy group is added to the first reaction product between −20° C. to 20° C. to obtain a precipitate which is purified to obtain a second reaction product. Subsequently, the second reaction product is contacted with a halogenized titanium compound, such as, titanium tetrachloride, to obtain a further reaction product. The polymerization catalyst is obtained by purifying the further reaction product. In the aromatic halide, R represents an aromatic group containing from 6 to 20 carbon atoms and X represents a halide. An electron dopor such as dibutyl phthalate may also be present during the titanium addition.Type: GrantFiled: March 13, 2000Date of Patent: July 31, 2001Assignee: DSM N.V.Inventors: Vladimir A Zakharov, Gennadii D. Bukatov, Sergei A. Sergeev
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Patent number: 6235671Abstract: A heterogeneous catalyst for olefin polymerization is prepared by spray drying a mixture of a metallocene catalyst, a cocatalyst and a hydrotalcite. It Preferred hydrotalcites are magnesium-aluminum hydroxy carbonates. The catalysts are very active for ethylene polymerization. The hydrotalcite used in this invention are generally defined by the formula: (Mg1−x Alx(OH)2)n+An−x/n·m H2O wherein X is from 0 to 0.5, m is from 0 to 20 and An− is an anion having a charge of n. Preferred hydrotalcites are those in which the anion A is a carbonate and which have been dried of adsorbed water.Type: GrantFiled: April 14, 1999Date of Patent: May 22, 2001Assignee: Nova Chemicals (International) S.A.Inventors: Ian McKay, Alison Ciupa, P. Scott Chisholm
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Patent number: 6228793Abstract: The present invention provides a solid catalyst component for polymerization of olefins prepared by allowing a magnesium compound, a titanium compound and an electron donor compound to come in contact with each other, and having a value that a parameter of S1/S2 determined by Raman spectroscopic analysis is not less than 0.5 and not more than 10, wherein S1 and S2 are the values determined by Raman spectroscopic analysis, and S1 is a value of peak area of the strongest peak appeared in the range from 360 to 520 cm−1 and S2 is a value of peak area of the strongest peak appeared in the range from 160 to 340 cm−1. A catalyst comprising the solid catalyst component, an organic aluminum compound and an organic silicon compound is superior in hydrogen response and can produce a polymer of olefins having a high stereoregularity in a high yield.Type: GrantFiled: April 28, 1999Date of Patent: May 8, 2001Assignee: Toho Titanium Co., Ltd.Inventors: Motoki Hosaka, Isa Nishiyama
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Patent number: 6221803Abstract: A process for preparing a Ziegler-Natta catalyst, which process comprises: (i) mixing in a hydrocarbon solvent a dialkyl magnesium compound of general formula MgR1R2 with a chlorinating agent soluble in the hydrocarbon solvent under conditions to precipitate controlledly a magnesium dichloride derivative, wherein R1 and R2 are each independently a C1 to C10 alkyl group, and the chlorinating agent is obtainable from the reaction between an alcohol of general formula R3OH and an alkyl aluminum chloride of general formula R4nAlCl3−n, in which R3OH is a cyclic or branched C3 to C20 alcohol, each R4 is independently a C2 to C8 alkyl and n is 1 or 2; (ii) removing unwanted reducing species by washing or reaction; and (iii) titanating the magnesium dichloride derivative with a chlorinated titanium compound to produce the Ziegler-Natta catalyst.Type: GrantFiled: April 22, 1999Date of Patent: April 24, 2001Assignee: Fina Research, S.A.Inventor: Dominique Marie Vereecke
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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: 6211106Abstract: A catalyst composition for preparing high-syndiotacticity polystyrene polymers which comprises: (a) a titanium complex represented by the following formula of TiR′1R′2R′3R′4 or TiR′1R′2R′3, wherein R′1, R′2, R′3, and R′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 represented by the following formula: wherein R1-R13 are, independently, alkyl group, aryl group, silyl group, halogen atom, or hydrogen atom; Ra and Rb are, independently, alkyl group, aryl group, alkoxy, aryloxy group, cyclopentadienyl group, hydrogen atom, or halogen atom; and Xa is a Group IIA element and Xb is a Group IIIA element.Type: GrantFiled: June 18, 1998Date of Patent: April 3, 2001Assignee: Industrial Technology Research InstituteInventors: Jing-Cherng Tsai, Yi-Chun Chen, Sheng Te Yang, Meei-Hwa Wang, Shian-Jy Wang
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Patent number: 6207607Abstract: Disclosed is the homogenous reaction at 40-200° C. of MgX12−nR1OH (where n=2.0-6.4) with TiX24 and a higher (C6-C20) alkyl ester of a carboxylic acid, optionally in the presence of a solvent. In such a completely homogenous reaction, no carrier appears. In order to obtain a product in the liquid stage, the molar ratio between the ester and the MgX12.nR1OH should be at least 0.8/j wherein j is the number of carboxyl groups in the ester. If the ester has two carboxyl groups, for instance, j is 2 and the molar ratio should be at least 0.8/2, that is, 0.4.Type: GrantFiled: December 23, 1998Date of Patent: March 27, 2001Assignee: Borealis A/SInventors: Thomas Garoff, Timo Leinonen, Sirpa Ala-Huikku
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Patent number: 6200923Abstract: A novel soluble composition containing magnesium, titanium, a halogen and a carboxylic acid ester has been invented. The composition has mainly the composition according to Formula (I): (MgX32)xTiX44(R(COOR′)n)y (I) wherein X3 is a halogen, X4 is a halogen, R(COOR′)n is a carboxylic acid higher alkyl ester containing at least 8·n carbon atoms, wherein R is an n-valent substituted or unsubstituted C1-C34 hydrocarbon group, R′ is a C1-C20 alkyl group, and n is an integer from 1 to 4, x is between 0.5 and 4.0, and y is between 0.8/n and 2.4/n.Type: GrantFiled: November 30, 1998Date of Patent: March 13, 2001Assignee: Borealis Technology OyInventors: Thomas Garoff, Timo Leinonen, Sirpa Ala-Huikku
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Patent number: 6156691Abstract: In catalyst systems of the Ziegler-Natta type modified during their preparation and comprising as active constituentsa) a titanium-containing solid component which is obtained by reacting a compound of titanium with a compound of magnesium, a halogen, an inorganic oxide as support, a C.sub.1 -C.sub.8 -alkanol and a carboxylic ester as electron donor compound,and also as cocatalystb) an aluminum compound andc) if desired, a further electron donor compound,the titanium-containing solid component a) is prepared by first, in a first stage, admixing an inorganic oxide as support with a solution of a chlorine-free compound of magnesium in an inert solvent, stirring this mixture for from 0.5 to 5 hours at from 10 to 120.degree. C. and subsequently reacting it while stirring continually in an inert solvent with a C.sub.1 -C.sub.8 -alkanol in an at least 1.Type: GrantFiled: September 12, 1997Date of Patent: December 5, 2000Assignee: BASF AktiengesellschaftInventors: Stephan Huffer, Ulrich Moll, Ian David McKenzie, Franz Langhauser, Peter Kolle, Roland Hingmann, Gunther Schweier, Rainer Hemmerich, Jurgen Kerth
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Patent number: 6143684Abstract: The invention relates to solid catalyst components for the polymerization of olefins CH.sub.2 .dbd.CHR, in which R is hydrogen or a hydrocarbyl radical with 1-12 carbon atoms, comprising Ti, Mg, halogen and an electron donor compound selected from cyanoesters of formula (1): ##STR1## wherein R.sub.1 is a C.sub.1 -C.sub.20 linear or branched alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, alkylcycloalkyl, aryl, arylalkyl or alkylaryl group; n is 0, 1, 2 or 3; R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are independently selected from hydrogen or C.sub.1 -C.sub.20 linear or branched alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, alkylcycloalkyl, aryl, arylalkyl or alkylaryl groups; two or more of R.sub.2 and R.sub.3, and R.sub.4 and R.sub.5, can be joined to form a cycle. Said catalyst components when used in the polymerization of olefins are characterized by an excellent response to hydrogen and capability to produce polymers with broad Molecular Weight Distribution.Type: GrantFiled: September 3, 1998Date of Patent: November 7, 2000Assignee: Montell Technology Company B.V.Inventors: Giampiero Morini, Yuri V. Gulevich, Giulio Balbontin
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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: 6103655Abstract: Procedure for the preparation of a solid carrier for olefin polymerization catalysts, comprising the steps:a) impregnating a silica with Mg-chloride solubilized in ethylbenzoate, in the presence of further electron donors,b) optionally drying the impregnated silica obtained in (a) and impregnating it with a solution of Mg-alkyls in SiCl.sub.4 at a temperature from -10 to 20.degree. C. and subsequently treating the obtained slurry at a temperature from 40.degree. C. to reflux temperature, optionally adding a further amount of electron donors,c) drying the obtained carrier.The carrier which is obtained according to the above procedure is advantageously used for the preparation of supported catalysts for the polymerization of olefins.Type: GrantFiled: February 13, 1998Date of Patent: August 15, 2000Assignee: Borealis GmbHInventors: Luciano Luciani, Wolfgang Neissl, Norbert Hafner
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Patent number: 6051666Abstract: A method for polymerizing at least one olefin by contacting at least one olefin with a polymerization catalyst and an organometallic compound containing a metal from group 1, 2, 12 or 13 of the Periodic System of Elements under effective polymerization conditions. The polymerization catalyst is obtained by contacting metallic magnesium with an aromatic halide, RX, under conditions effective to obtain a first reaction product and solid residual products. The first reaction product is then separated from the solid residual products. A silane compound containing an alkoxy or aryloxy group is added to the first reaction product between -20.degree. C. to 20.degree. C. to obtain a precipitate which is purified to obtain a second reaction product. Subsequently, the second reaction product is contacted with a halogenized titanium compound, such as titanium tetrachloride, to obtain a further reaction product. The polymerization catalyst is obtained by purifying the further reaction product.Type: GrantFiled: October 9, 1997Date of Patent: April 18, 2000Assignee: DSM N.V.Inventors: Vladimir A. Zakharov, Gennadii D. Bukatov, Sergei A. Sergeev
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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: 6001766Abstract: Catalyst compositions for homopolymerization and copolymerization of ethylene which comprise two transition metal compounds, one of them a cyclopentadienyl complex of a transition metal and another a non-metallocene derivative of a transition metal are described. The catalysts are activated by alkylalumoxanes that are soluble in non-aromatic hydrocarbons. Bimetallic catalysts of this invention are suitable for the manufacture of ethylene homopolymers and copolymers with broad bimodal molecular weight distributions. The alkyl alumoxanes have at least one [AR(R)--O--] repeating group in which R is an alkyl group of at least two carbon atoms.Type: GrantFiled: December 24, 1997Date of Patent: December 14, 1999Assignee: Mobil Oil CorporationInventors: Yury V. Kissin, Robert I. Mink, Thomas E. Nowlin
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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: 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: 5965478Abstract: A solid catalyst component for polymerization of olefins prepared by reacting a titanium halide, a diester of aromatic dicarboxylic acid and a dialkoxymagnesium having a bulk density of at least 0.25 g/ml and an average particle size of 1 to 100 .mu.m. The average rate of temperature rise from the temperature at which the titanium halide is allowed to come in contact with the dialkoxymagnesium to the temperature at which the reaction is initiated is in a range of from 0.5 to 20.degree. C./min. Such catalyst can further comprise an organic aluminum compound and an organic silicon compound. The use of said catalyst makes it possible to efficiently obtain a polyolefin having a high stereoregularity, a high bulk density and excellent particle properties.Type: GrantFiled: August 13, 1997Date of Patent: October 12, 1999Assignee: Toho Titanium Co., Ltd.Inventors: Kenji Goto, Motoki Hosaka, Akira Saito, Tetsuo Ohtsuka
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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: 5948869Abstract: Catalytic composition effective in the selective hydrogenation of olefinic double bonds prepared by the reaction between:(A) at least one bis(cyclopentadienyl)Titanium derivative having the general formula (I) (C.sub.5 H.sub.5).sub.2 Ti(R) (R.sub.1) wherein R and R.sub.1, the same or different, are halogens; the above compound (I) being solid or dispersed in one or more non-solvent diluents;(B) at least one organo derivative having general formula (II) M(R.sub.2) (R.sub.3) wherein M is selected from Zinc and Magnesium, and R.sub.2 and R.sub.3, the same or different, are selected from C.sub.1 -C.sub.16 alkyls;(C) at least one modifier.Type: GrantFiled: June 26, 1997Date of Patent: September 7, 1999Assignee: Enichem S.p.A.Inventors: Andrea Vallieri, Claudio Cavallo, Gian Tommaso Viola
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Patent number: 5945366Abstract: A solid catalyst component (A1) for polymerization of olefins prepared by contact with a solid component (d) obtained by allowing (1) a solid component (a) obtained by allowing (i) a dialkoxymagnesium or diaryloxymagnesium, (ii) a titanium compound and (iii) a diester of aromatic dicarboxylic acid to come in contact with one another and (2) a solid component (b) obtained by allowing (i) a dialkoxymagnesium or diaryloxymagnesium, (ii) a titanium compound, (iii) a diester of aromatic dicarboxylic acid and (iv) a polysiloxane to come in contact with one another, to come in contact with each other, or a solid catalyst component (A2) for polymerization of olefins prepared by allowing said solid component (a) and (3) a solid component (d) obtained by allowing (i) a dialkoxymagnesium or diaryloxymagnesium, (ii) a titanium compound, (iii) a diester of aromatic dicarboxylic acid, (iv) a polysiloxane and (v) an aluminum compound to come in contact with one another, to come in contact with each other.Type: GrantFiled: April 21, 1997Date of Patent: August 31, 1999Assignee: Toho Titanium Co., Ltd.Inventors: Takuo Kataoka, Hidetoshi Umebayashi, Kenji Goto
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Patent number: 5936049Abstract: Disclosed is a process for preparing a solid titanium catalyst component, comprising contacting (a) a liquid magnesium compound, (b) a liquid titanium compound, (c) an electron donor and (d) a solid divalent metallic halide. In this process, the solid divalent metallic halide is one having a crystalline structure of the cadmium chloride type. The contact of the component (a) with the component (b) is preferably carried out in the presence of the solid divalent metallic halide (d). According to this process, there can be obtained a solid titanium catalyst component capable of polymerizing olefins with an extremely high activity and capable of producing polyolefins of high stereoregularity when .alpha.-olefins of 3 or more carbon atoms are polymerized.Type: GrantFiled: April 7, 1997Date of Patent: August 10, 1999Assignee: Mitsui Chemicals, Inc.Inventors: Shinichi Kojoh, Masao Nakano
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Patent number: 5932510Abstract: The present invention provides a solid catalyst component (A) obtained by allowing a dialkoxymagnesium or diaryloxymagnesium, a titanium compound, a diester of phthalic acid and a cyclic or chain polysiloxane to come in contact with one another.Further, the present invention provides a catalyst for polymerization of olefins prepared from the foregoing solid catalyst component (A), an organic aluminum compound and an organic silicon compound.Type: GrantFiled: May 1, 1997Date of Patent: August 3, 1999Assignee: Toho Titanium Co., Ltd.Inventors: Motoki Hosaka, Kenji Goto, Takuo Kataoka, Hayashi Ogawa
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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: 5919723Abstract: A supported catalyst for the (co)polymerization of alpha-olefins is obtained by putting the following products in contact with each other:(A) a metallocene derivative of a metal selected from the group consisting of transition metals and lanthanides, which is in itself capable of promoting the polymerization of alpha-olefins in the presence of or also without suitable activators;(B) an active support containing magnesium, halogen, titanium and smaller quantities of tin;(C) an organometal derivative of aluminium of which at least 50% of the aluminium atoms are bound to at least one alkyl carbon atom.Components (A) and (B) are preferably interacted first to obtain a supported metallocene derivative, which is then put in contact with (C) to obtain the desired catalyst. Alternatively, (B) and (C) are interacted and subsequently put in contact with (A).Type: GrantFiled: December 30, 1996Date of Patent: July 6, 1999Assignee: Enichem S.p.A.Inventors: Federico Milani, Antonio Labianco, Bruno Pivotto
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Patent number: 5891817Abstract: 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 an alkyl group containing a primary carbon atom attached to the silicon 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; R.sub.1 and R.sub.4 are the same or different. R.sub.1 and R.sub.4 are preferably chosen from the group consisting of n-propyl, n-butyl and methyl; most preferably n-propyl and n-butyl with R.sub.1 and R.sub.4 being the same or, alternatively, most preferably, R.sub.1 is methyl and R.sub.4 is C.sub.3 or higher. The system has a catalyst efficiency of over 30 kg/g-cat.multidot.h as the Si/Ti mole ratio varies from 4-20 in the system. The system easily achieves efficiencies over 30 kg/g-cat.Type: GrantFiled: June 7, 1995Date of Patent: April 6, 1999Assignee: Fina Technology, Inc.Inventors: Edwar S. Shamshoum, David John Rauscher
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Patent number: 5851946Abstract: The invention relates to the use of intramolecularly stabilized organometallic compounds as components in coordination catalyst systems, corresponding coordination catalyst systems and processes for the preparation of polymers by coordination polymerization of unsaturated hydrocarbons by catalysed metathesis of alkenes and alkynes using such coordination catalyst systems.Type: GrantFiled: September 25, 1995Date of Patent: December 22, 1998Assignee: Merck Patent Gesellschaft mit Beschrankter HaftungInventors: Ludwig Pohl, Eike Poetsch, Hans-Ludwig Hirsch, Herbert Schumann, Karin Weiss
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Patent number: 5834393Abstract: A supported catalyst component comprising (a) a support material, an organometal compound, and (b) an activator compound comprising b.1) a cation which is capable of reacting with a transition metal metallocene compound to form a catalytically active transition metal complex, and b.2) a compatible anion having up to 100 nonhydrogen atoms and containing at least one substituent comprising an active hydrogen moiety; a supported catalyst comprising the supported catalyst component and a transition metal compound; process for making the same; an addition polymerization process using the supported catalyst; complex compounds, and a method for preparing the same.Type: GrantFiled: March 4, 1996Date of Patent: November 10, 1998Assignee: The Dow Chemical CompanyInventors: Grant Berent Jacobsen, Peter Wijkens, Johann T. B. H. Jastrzebski, Gerard Van Koten
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Patent number: 5824618Abstract: A catalyst component is disclosed for use in the homo- or copolymerization of olefinic hydrocarbons. The catalyst component is comprised of a first compound of the formula M.sup.1 (OR.sup.1).sub.p R.sup.2.sub.q X.sup.1.sub.4-p-q, M.sup.1 being titanium a second compound of the formula M.sup.2 (OR.sup.3).sub.m R.sup.4.sub.n X.sup.2.sub.z-m-n, with M.sup.2 being a metal of Groups Ia-IIIa or IIb of the Periodic Table, and a third compound which is an organocyclic compound having two or more conjugated double bonds. A process is also disclosed for the production of hydrocarbon polymers in which the above catalyst component is combined with a modified organoaluminum compound to form a catalyst composition capable of providing controlled molecular weight, wide distribution thereof and other desirable qualities in the polymer product.Type: GrantFiled: June 6, 1995Date of Patent: October 20, 1998Assignee: Nippon Oil Co., Ltd.Inventors: Yoshio Tajima, Naoki Kataoka, Yosuke Numao, Takashi Seki, Kazuo Matsuura
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Patent number: 5777050Abstract: A process is disclosed for the homopolymerization of ethylene or copolymerization of ethylene with one or more .alpha.Type: GrantFiled: September 15, 1997Date of Patent: July 7, 1998Assignee: DSM N.V.Inventors: Nicolaas H. Friederichs, Johannus A. M. van Beek, Rutgerus A. J. Postema, Joseph A. J. Hahnraths
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Patent number: 5767031Abstract: This invention relates to a process for making a catalyst in which a metallocene is included in the synthesis of a Ziegler-Natta catalyst and a process for using the catalyst in the polymerization of olefins, specifically, propylene, to produce a polymer product with broad polydisperisty.The catalyst may be synthesized by:1) selecting a solid component comprising a magnesium dialkoxide;2) adding a chlorinating agent;3) adding a titanating agent;4) adding a metallocene prior to step 2), after step 2), prior to step 3) or after step 3) and5) adding an aluminum alkyl cocatalyst.Type: GrantFiled: June 7, 1995Date of Patent: June 16, 1998Assignee: Fina Technology, Inc.Inventors: Edwar S. Shamshoum, David John Rauscher, Christopher G. Bauch
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Patent number: 5759940Abstract: The present invention relates to components of catalysts for the polymerization of olefins comprising the product that can be obtained by bringing a compound of a transition metal M, containing at least one M--.pi. bond, into contact with an olefinic prepolymer obtained by polymerization of one or more olefins with a coordination catalyst comprising a compound of Ti or V supported on a magnesium halide.Type: GrantFiled: March 27, 1995Date of Patent: June 2, 1998Assignee: Montell Technology Company BVInventors: Mario Sacchetti, Stefano Pasquali, Gabriele Govoni
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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: 5733842Abstract: An improved catalyst carrier is formed by a process that comprises the use of ceramic particle components with particle sizes chosen to ensure that a desired degree of porosity is obtained without recourse to the use of organic burnout materials.Type: GrantFiled: February 10, 1997Date of Patent: March 31, 1998Assignee: Norton Checmical Process Products CorporationInventors: William H. Gerdes, Donald J. Remus, Thomas Szymanski
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Patent number: 5696044Abstract: A method is proposed for producing a deposited catalyst for the polymerization of ethylene and copolymerization of ethylene with .delta.-olefins which involves the reaction of a solution of an organomagnesium compound of composition MgPh.sub.2.nMgCl.sub.2.mR.sub.2 O (wherein n=0.37-0.7; m.gtoreq.2, R.sub.2 O is a simple ether, Ph is C.sub.6 H.sub.5) with a carbon tetrachloride, at a molar ratio of CCl.sub.4 /Mg.gtoreq.0.5 and a temperature of -20.degree. to 60.degree. C.Type: GrantFiled: December 18, 1996Date of Patent: December 9, 1997Assignee: Institut Kataliza Iment G.K. Boreskova Sibirskogo Otdelenia Rossiiskoi Akademii NaukInventors: Vladimir Alexandrovich Zakharov, Sergei Iyanovich Makhtarulin, Sergei Andreevich Sergeev, Tatyana Borisovna Mikenas, Valentin Evgenievich Nikitin, Ljudmila Gennadievna Echevskaya, Angelina Dmitrievna Khmelinskaya
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Patent number: 5691264Abstract: Components of bimetallic catalysts for the polymerization of olefins comprising a compound of a transition metal M selected from Ti, V, Zr and Hf containing at least one M-.pi. bond, a compound of Ti or V not containing metal-.pi. bonds and a support comprising a magnesium halide. The catalysts obtained from the components of the invention are particularly suitable for gas-phase polymerization processes.Type: GrantFiled: June 6, 1995Date of Patent: November 25, 1997Assignee: Spherilene S.p.A.Inventors: Mario Sacchetti, Stefano Pasquali, Gabriele Govoni
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Patent number: 5670587Abstract: There are disclosed a catalyst for producing an aromatic vinyl compound-based polymer composition which catalyst comprises (A) at least two different transition metal compounds each having one .pi.-ligand and (B) an ionic compound comprising a noncoordinate anion and a cation and/or an aluminoxane, and (C) a Lewis acid to be used as the case may be; and a process for producing an aromatic vinyl compound-based polymer composition having a high degree of syndiotactic configuration in its aromatic vinyl chains which process comprises polymerizing an (a) aromatic vinyl compound and (b) an olefinic compound and/or a diolefinic compound in the presence of the above catalyst.Type: GrantFiled: January 23, 1996Date of Patent: September 23, 1997Assignee: Idemitsu Kosan Co., Ltd.Inventors: Mizutomo Takeuchi, Hajime Shouzaki, Norio Tomotsu, Masahiko Kuramoto
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Patent number: 5648309Abstract: A Ziegler catalyst in which the transition metal component has been prepared by reacting a transition metal compound of titanium, zirconium, vanadium or chromium with a gel-like dispersion of a magnesium alcoholate is used for the preparation of poly-1-olefins, in particular polyethylene. The co-catalyst used is an organoaluminum compound. The polymers are obtained in a high to very high yield, and it is possible to control the particle size distribution of the polymers.Type: GrantFiled: March 6, 1995Date of Patent: July 15, 1997Assignee: Hoechst AktiengesellschaftInventor: Ludwig Bohm
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Patent number: 5627117Abstract: Disclosed in an olefin polymerization catalyst comprising a transition metal compound having at least two transition metals in which at least one of said metals is bonded to a ligand having a cyclopentadienyl skeleton, at least one of said metals is selected from Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and lanthanoid metals and at least on of the others is selected from the specific transition metals; and an organoaluminum oxy-compound or an organoboron compound. Corresponding to the kind of the metal combined with said metal selected from Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and lanthanoid metals, the olefin polymerization catalyst exhibit a property to give polymers having a wide molecular weight distribution in spite of the catalyst system using one kind of a transition metal compound, or to give polymers having high molecular weight and be excellent in the polymerization activity at low polymerization temperature.Type: GrantFiled: December 27, 1994Date of Patent: May 6, 1997Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Teruaki Mukaiyama, Makoto Mitani, Kunihiro Oouchi
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Patent number: 5604172Abstract: A process is provided for preparing a shape-shifted catalyst component comprising (1) contacting a dihydrocarbyloxide magnesium compound with carbon dioxide in the presence of a slurrying agent to form a slurry of a carboxylated dihydrocarbyloxide magnesium compound; (2) adding a filler to the slurry either before or after the carboxylation of step (1); (3) spray drying the slurry of step (2) to evaporate the slurrying agent and to produce solid particles of the carboxylated dihydrocarbyloxide magnesium compound incorporating the filler; and, optionally, (4) heating the solid particles to remove carbon dioxide to produce a shape-shifted dihydrocarbyloxide magnesium compound component. A catalyst system using the component and a polymerization process employing the catalyst system are also provided.Type: GrantFiled: February 2, 1996Date of Patent: February 18, 1997Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Burkhard E. Wagner, Daniel P. Zilker, Jr., Robert J. Jorgensen
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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: 5500396Abstract: A process to make a small, discrete, spherical magnesium dihalide alcohol adduct is provided. This process comprises: contacting a magnesium dihalide and an alcohol in a high-viscosity liquid that consists of hydrocarbons, to obtain a dispersion; heating and agitating the dispersion to obtain a molten dipersion; cooling the molten dispersion to form said small, discrete, spherical magnesium dihalide alcohol adduct.Type: GrantFiled: February 9, 1995Date of Patent: March 19, 1996Assignee: Phillips Petroleum CompanyInventor: Joel L. Martin
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Patent number: 5468704Abstract: Disclosed is a catalyst for the polymerization of olefins, which includes the product of the reaction between an Al-alkyl compound and a solid catalyst component containing a magnesium halide in active form, a titanium compound and an electron-donor selected from the 1,3-diketones of formula: ##STR1## wherein the radicals R are the same or different, the radicals R.sup.I are the same or different, and R and R.sup.I are C.sub.1 -C.sub.20 alkyl, C.sub.3 -C.sub.20 cycloalkyl, C.sub.6 -C.sub.12 aryl, C.sub.7 -C.sub.20 arylalkyl or alkylaryl radicals or hydrogen, with the proviso that at least one of the R radicals is not hydrogen and can be bonded with the other R radical to form a cyclic structure, and at least one of the R.sup.I radicals, which are not bonded to one another to form a cyclic structure, is a branched alkyl, cycloalkyl or aryl radical, or is bonded to one or both R radicals to form a cyclic structure.Type: GrantFiled: September 30, 1994Date of Patent: November 21, 1995Assignee: Montell North America Inc.Inventors: Giampiero Morini, Enrico Albizzati, Umberto Giannini, Raimondo Scordamaglia, Luisa Barino
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Patent number: 5468703Abstract: Disclosed is a titanium catalyst component for ethylene polymerization obtained by contacting [A] a solid magnesium aluminum complex containing magnesium, halogen, aluminum and an alkoxy group and/or alcohol having at least 6 carbon atoms, with [B] a tetravalent titanium compound. The solid magnesium aluminum complex [A] is obtained by contacting (a-1) a magnesium solution formed from a halogen-containing magnesium compound, an alcohol having at least 6 carbon atoms and a hydrocarbon solvent, with (a-2) an organoaluminum compound. Also disclosed is a process for ethylene polymerization comprising polymerizing ethylene or copolymerizing ethylene with an .alpha.-olefin having 3 to 20 carbon atoms in the presence of a catalyst for ethylene polymerization comprising [I] the above-mentioned titanium catalyst component for ethylene polymerization and [II] an organoaluminum compound catalyst component.Type: GrantFiled: October 4, 1993Date of Patent: November 21, 1995Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Mamoru Kioka, Tsuneo Yashiki