Non-metal Material Is Organic Phosphorus-containing Compound Patents (Class 526/139)
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Patent number: 4304684Abstract: A new improved catalyst system for alpha-olefin type polymerizations, includes at least one metal alkyl compound having the formula R'"M in combination with a Group IVB-VIII transition metal compound on a support and at least one hindered Lewis base and one unhindered Lewis base and a Group IA-IIIA metal salt of a sterically hindered carboxylate, alkoxide or aryloxide, wherein R'" is selected from the group consisting of C.sub.1 to C.sub.20 primary alkyl, alkenyl or aralkyl groups, or a hydride, and M is selected from the group consisting of aluminum, gallium, or indium. The improved catalyst system provides polymers having increased isotactic stereoregularity as well as lower catalyst residue.Type: GrantFiled: March 6, 1980Date of Patent: December 8, 1981Assignee: Exxon Research & Engineering Co.Inventor: Arthur W. Langer
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Patent number: 4304890Abstract: A method for producing crystalline copolymers of propylene (major component), ethylene and an .alpha.-olefin having 4 to 12 carbon atoms, superior in any of various practical physical properties such as cold-resistance, transparency, heat-seal temperature, percentage shrinkage, etc. is provided, wherein a catalyst solution obtained by mixing together a titanium trichloride composition (obtained by mixing and milling a titanium trichloride with a mixed reaction product of TiCl.sub.4 with an ether), a dialkylaluminum halide, an electron-donor compound and an inert solvent, is activated in advance of copolymerization, by feeding propylene into the solution under specified feeding conditions, and copolymerization is carried out by feeding propylene and said .alpha.-olefin simultaneously and continuously, while feeding ethylene intermittently into the gas phase part of the polymerization zone containing the solution.Type: GrantFiled: July 8, 1980Date of Patent: December 8, 1981Assignee: Chisso CorporationInventors: Takeshi Suzuki, Hiromasa Chiba
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Patent number: 4301029Abstract: A component of a polymerization catalyst is prepared by reacting an organo-magnesium compound, or a complex with an organo-aluminium compound, with a solid, inorganic oxide, then with a halogenating agent such as silicon tetrachloride or hydrogen chloride, and then reacting the product with a Lewis Base compound, particularly an ester and finally with titanium tetrachloride. The product obtained is combined with an organo-aluminium compound, preferably together with a Lewis Base, and used to polymerize an olefin monomer particularly propylene or mixtures of ethylene and a 1-olefin containing at least 4 carbon atoms. The catalyst system has a high activity, is stereospecific and has a lower proportion of halogen than some other catalyst systems.Type: GrantFiled: January 10, 1980Date of Patent: November 17, 1981Assignee: Imperial Chemical Industries LimitedInventors: Anthony D. Caunt, Paul D. Gavens
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Patent number: 4299936Abstract: A transition metal compound containing at least one .pi.-bonded arene is contacted with an inorganic oxide, hydroxide, oxyhalide, hydroxyhalide or halide. The transition metal compound can be a compound such as titanium(O)ditoluene or TiCl.sub.2.2AlCl.sub.3 durene. The inorganic compound is preferably of high surface area and this may be inherent in the compound or can be achieved by a grinding procedure. The inorganic compound can be treated with a halogen containing compound either before, during or after the contacting with the transition metal compound. The product of the contacting is useful either as catalyst for the polymerization of unsaturated hydrocarbon monomers or as a component of such a catalyst. When used as a component of an olefine polymerization catalyst, the transition metal product can be mixed with an organo-aluminum compound and a Lewis Base compound such as an ester.Type: GrantFiled: August 7, 1978Date of Patent: November 10, 1981Assignee: Imperial Chemical Industries LimitedInventors: John P. Candlin, Keith C. Wilson, Ronald Pearce
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Patent number: 4296222Abstract: A process for the manufacture of poly-.alpha.-olefins by polymerizing .alpha.-olefins by means of a catalyst system comprising (1) a titanium-containing component obtained from (1.1) a compound of the formula TiCl.sub.3.1/3AlCl.sub.3 and (1.2) an organic electron donor, containing phosphorus, nitrogen and/or oxygen atoms, which has been milled with the compound of the formula TiCl.sub.3.1/3AlCl.sub.3 (1.1), in order to form a complex compound, the milling being carried out without assistants or additives in a vibratory ball mill under specific acceleration conditions and at a temperature which is from 4.degree. to 10.degree. C. below the temperature at which the particles of the material being ground begin to agglomerate, and (2) an aluminum-containing component, in which process the titanium-containing component (1) of the catalyst system used is one which has been treated, after milling and before polymerization, with (i) titanium tetrachloride and (ii) an ether and/or an ester.Type: GrantFiled: March 24, 1977Date of Patent: October 20, 1981Assignee: BASF AktiengesellschaftInventors: Gerhard Staiger, Klaus Bronstert
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Patent number: 4295991Abstract: A titanium trichloride catalyst component containing a minor amount of prepolymerized alpha-olefin and useful in the polymerization of alpha-olefins is produced by reducing titanium tetrachloride with an organoaluminum compound at low temperatures and then treating the resulting reduced solids product with about 1 to 1,000 wt. % alpha-olefin so as to obtain a prepolymerized titanium trichloride reduced solid. The prepolymerized reduced solid can thereafter be activated to a highly active prepolymerized titanium trichloride by treating the prepolymerized reduced solid with a halogenated hydrocarbon and a Lewis base complexing agent or titanium tetrachloride and a Lewis base complexing agent. The prepolymerized reduced solid and the prepolymerized activated titanium trichloride manifests substantially no evidence of friability upon being subjected to mechanical shearing forces.Type: GrantFiled: September 26, 1978Date of Patent: October 20, 1981Assignee: Exxon Research & Engineering Co.Inventor: Harry J. Wristers
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Patent number: 4287091Abstract: Polymerization, catalysts, and preparation thereof comprising milling magnesium metal, an organic halide, and titanium tetrahalide or the milled product in the presence of at least one of magnesium oxide, a triaryl phosphite, a polymeric material, titanium tetrahalide, vanadium tetrahalide, silicon tetrahalide, and an aluminum trihalide. The milled catalyst component can be heat treated prior to activation. The milled titanium catalyst component is activated with an organoaluminum activator producing a catalyst for olefin polymerization.Type: GrantFiled: August 3, 1979Date of Patent: September 1, 1981Assignee: Phillips Petroleum Co.Inventor: Charles M. Selman
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Patent number: 4285833Abstract: A catalyst consisting of (a) a cobalt compound, (b) an aluminium organic compound, (c) water and (d) a phosphite, characterized in that the phosphite is a compound corresponding to the formula (1): ##STR1## in which R represents a C.sub.3 -C.sub.20 alkyl radical, andR.sub.1 represents hydrogen or a C.sub.1 -C.sub.6 alkyl radical.Said catalyst can be used for polymerizing butadiene.Type: GrantFiled: March 19, 1980Date of Patent: August 25, 1981Assignee: Bayer AktiengesellschaftInventors: Manfred Beck, Gottfried Pampus
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Patent number: 4279776Abstract: A catalyst system prepared by mixing components (A), (B) and (C):(A) a solid titanium component prepared from an organo-magnesium compound, a silicon halide compound and/or an aluminum halide compound, an electron donor and TiCl.sub.4,(B) an organoaluminum activator, and(C) an electron donor.Type: GrantFiled: April 14, 1980Date of Patent: July 21, 1981Assignee: Sumitomo Chemical Company, LimitedInventors: Akinobu Shiga, Yoshiharu Fukui, Katsumi Hanji, Toshio Sasaki, Masahisa Okawa, Hideaki Matsuura, Yasuharu Yamada
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Patent number: 4277590Abstract: A new improved catalyst system for alpha-olefin type polymerizations includes a metal alkyl cocatalyst having the formula T.sub.n MR'.sub.3-n in combination with a Group IVB-VIII transition metal compound on a support and a Lewis base wherein n is equal to one or two, T is equal to R.sub.3 DCH.sub.2, and wherein D is selected from the group consisting of Si, Ge or Sn, R is methyl or ethyl, and R' is selected from the group consisting of C.sub.1 to C.sub.8 primary alkyl or aralkyl groups including unhindered branched groups and M is selected from the group consisting of aluminum, gallium, or indium. The improved catalyst system provides both increased polymerization activity and polymers having a high degree of isotactic stereoregularity as well as lower catalyst residue.Type: GrantFiled: February 15, 1980Date of Patent: July 7, 1981Assignee: Exxon Research & Engineering Co.Inventor: Arthur W. Langer, Jr.
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Patent number: 4276192Abstract: Polymerization catalyst preparation comprising milling magnesium metal, an organic halide and titanium tetrahalide in the presence of a triaryl phosphite and an aluminum trihalide but in the absence of a complexing diluent. The titanium catalyst component is activated with an organoaluminum activator producing a catalyst for olefin polymerization. In one embodiment, the titanium catalyst component is milled in the presence of magnesium oxide. In another embodiment, the milled titanium catalyst component is subjected to heat treatment.Type: GrantFiled: July 6, 1979Date of Patent: June 30, 1981Assignee: Phillips Petroleum CompanyInventors: Charles M. Selman, Lawrence M. Fodor
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Patent number: 4263168Abstract: A component of a polymerization catalyst is prepared by reacting an organo-magnesium halide with a solid, inorganic oxide, then reacting the product with a Lewis Base compound, particularly an ester and finally with titanium tetrachloride. After reacting the organo-magnesium halide with the inorganic oxide it may be treated with a halogenating agent before it is reacted with the Lewis Base compound. The product obtained is combined with an organo-aluminium compound preferably together with a Lewis Base and used to polymerize an olefine monomer. The catalyst has a high activity, is stereospecific and has a lower proportion of halogen than some other catalyst systems.Type: GrantFiled: March 27, 1979Date of Patent: April 21, 1981Assignee: Imperial Chemical Industries LimitedInventors: Malcolm P. Rochefort, Paul D. Gavens
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Patent number: 4260707Abstract: A catalyst comprising(a) a reaction mixture formed by reacting M(RCO.sub.2).sub.3 with AlR.sub.3.sup.1,(b) AlR.sub.3.sup.2 and/or HAlR.sub.2.sup.2 and(c) a Lewis acidwherein M denotes a trivalent rare earth element with an atomic number of 57 to 71, R denotes a saturated or unsaturated, straight chain or branched chain alkyl group having 1 to 20 C-atoms which may be substituted one or more times with cycloalkyl having 5 to 7-atoms and/or phenyl, the carboxyl group being attached to a primary, secondary or tertiary C-atom; a cycloalkyl group having 5 to 7 ring carbon atoms, which may be substituted one or more times with alkyl groups having from 1 to 5 C-atoms; or an aromatic group having from 6 to 10 ring carbon atoms, which may be substituted one or more times with alkyl groups having 1 to 5 C-atoms, and R.sup.1 and R.sup.2 are identical or different, straight chain or branched chain alkyl groups having from 1 to 10 C-atoms. Said catalyst may be used for polymerizing diene monomers in solution.Type: GrantFiled: February 1, 1980Date of Patent: April 7, 1981Assignee: Bayer AktiengesellschaftInventors: Gerd Sylvester, Josef Witte, Gunter Marwede
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Patent number: 4260706Abstract: Olefin polymerization catalysts are prepared by depositing an organophosphoryl chromium product and an aluminum acetyl acetonate on an inorganic support material, and heating the support material in a non-reducing atmosphere at a temperature above about 300.degree. C. up to the decomposition temperature of the support material.Type: GrantFiled: June 21, 1979Date of Patent: April 7, 1981Assignee: National Petro Chemicals Corp.Inventors: Louis J. Rekers, Stanley J. Katzen, Jerome H. Krekeler
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Patent number: 4260711Abstract: In the polymerization of 1-olefins using a solid catalyst component composed of a titanium trichloride and an activator component composed of a trialkylaluminum, the stereospecificity of the catalyst is increased by replacing a portion of the trialkylaluminum in the activator component with a dialkylaluminum dialkylphosphate.Type: GrantFiled: April 21, 1980Date of Patent: April 7, 1981Assignee: Hercules IncorporatedInventor: Richard V. Cartwright
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Patent number: 4259466Abstract: A titanium trichloride-catalyzed process for stereospecific polymerization of alpha-olefins, particularly propylene, to produce polymers of relatively high bulk density comprises employing as the TiCl.sub.3 catalyst component, used with an aluminum alkyl cocatalyst, a 0.1 to 30 millimicron fraction of a TiCl.sub.3 composition produced by(a) reacting TiCl.sub.4 with a complexing agent in a molar ratio of from 1:0.3 to 1:2;(b) reacting an organo-aluminum compound with a complexing agent in a molar ratio of at most 1:0.25;(c) reducing the complexed TiCl.sub.4 with the complexed organo-aluminum compound over a period of less than one hour at a temperature within the range 60.degree. to 110.degree. C. to produce TiCl.sub.3 particles having an average particle size of from 50 to 500 .mu.m;(d) subjecting the TiCl.sub.3 particles to a treatment to reduce the average particle size thereof to less than 50 .mu.m, and(e) classifying the TiCl.sub.Type: GrantFiled: November 8, 1979Date of Patent: March 31, 1981Assignee: Shell Oil CompanyInventors: Andras G. T. G. Kortbeek, Adrianus A. Van Der Nat
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Patent number: 4258168Abstract: In an alpha-olefin polymerization process using a transition metal halide-aluminum alkyl catalyst system, addition of minor, effective amounts of alkyl orthoformates, thiophosphates and borates decreases the amount of low molecular weight or amorphous polymer produced.Type: GrantFiled: June 16, 1976Date of Patent: March 24, 1981Assignee: Standard Oil Company (Indiana)Inventors: Nicholas M. Karayannis, Sam S. Lee
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Patent number: 4258161Abstract: Propylene is polymerized in the presence of a catalytic system of the type which comprises a solid titanium trichloride-based complex serving as a catalyst, said complex having an atomic ratio of aluminum to titanium in the range of below 0.15:1 and containing a complexing agent, and an organic aluminium compound of the general formula, AlR.sub.n.sup.1 Cl.sub.3-n wherein R.sup.1 represents an n-propyl group or an n-hexyl group and n is a value of 1.95-2.10. The catalytic system may further comprise an electron-donor compound as a third catalytic component.Type: GrantFiled: January 22, 1979Date of Patent: March 24, 1981Assignee: Mitsubishi Chemical Industries Ltd.Inventors: Genjiro Kakogawa, Masayoshi Hasuo, Yoshinori Suga, Hisashi Kitada, Yumito Uehara
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Patent number: 4256866Abstract: In an alpha-olefin polymerization process using a transition metal halide-aluminum alkyl catalyst system, addition of minor, effective amounts of a sterically hindered 5- or 6-membered cyclic ether decreases the amount of low molecular weight or amorphous polymer produced.Type: GrantFiled: June 16, 1976Date of Patent: March 17, 1981Assignee: Standard Oil Company (Indiana)Inventors: Nicholas M. Karayannis, Sam S. Lee
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Patent number: 4252930Abstract: Titanium trichloride for use as a component of a Ziegler polymerization catalyst is modified in order to enhance the activity and/or stereospecificity of the catalyst in the polymerization of olefins, especially propylene, by heating the titanium trichloride with phosphorus oxytrichloride in an aromatic hydrocarbon diluent for several hours in the absence of the organo aluminium component of the catalyst. Ball milling, or shearing, during the modification reaction is not required. The use of aromatic hydrocarbon gives unexpected improvement compared with any other hydrocarbon diluent and the modification reaction gives improved results compared with addition of the titanium trichloride, phosphorus oxytrichloride and the organo aluminium component to the reactor at the beginning of a batch polymerization.Type: GrantFiled: March 30, 1976Date of Patent: February 24, 1981Inventors: Derek K. Jenkins, Anthony V. Butcher, Donald G. Timms
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Patent number: 4252670Abstract: A component of a polymerization catalyst is prepared by reacting an organo-magnesium compound, or a complex with an organo-aluminium compound, with an halogenating agent such as silicon tetrachloride or hydrogen chloride, and then reacting the product with a Lewis Base compound, particularly an ester and finally with titanium tetrachloride. The product obtained is combined with an organo-aluminium compound preferably together with a Lewis Base and used to polymerize an olefine monomer. The catalyst has a high activity and is stereospecific.Type: GrantFiled: March 26, 1979Date of Patent: February 24, 1981Assignee: Imperial Chemical Industries LimitedInventors: Anthony D. Caunt, Paul D. Gavens
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Titanium chloride propylene polymerization catalyst and process for polymerizing propylene therewith
Patent number: 4251389Abstract: Titanium chloride catalysts having improved activity to polymerize propylene are prepared by treating TiCl.sub.4 with an aluminum alkyl and treating the resulting titanium chloride catalysts with carbon dioxide and a Lewis base such as di(n-butyl) ether at an elevated temperature.Type: GrantFiled: January 14, 1980Date of Patent: February 17, 1981Assignee: Gulf Oil CorporationInventors: Ronald E. Gilbert, Rajindar K. Kochhar -
Patent number: 4250283Abstract: A titanium trihalide component of an olefine polymerization catalyst is prepared by reacting together a titanium tetrahalide and an organo-aluminium compound, and treating the solid reaction product with a hydrocarbon solution of an alkyl aluminium dihalide. It is preferred that the solid reaction product is treated with a complexing agent, particularly an ether such as di-isoamyl ether before contacting with the alkyl aluminium dihalide. The titanium trihalide can then be used together with an organo-metallic compound to polymerize an olefine monomer, particularly propylene. The catalyst system may include further components in addition to the titanium trihalide and organo-metallic compound.Type: GrantFiled: February 12, 1975Date of Patent: February 10, 1981Assignee: Imperial Chemical Industries LimitedInventors: Anthony D. Caunt, James F. R. Jaggard
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Patent number: 4247418Abstract: The catalyst system disclosed herein comprises a combination or a chelate of a hydrocarbyl lithium compound with a bicyclic amine compound bridged together through nitrogen in each cyclic ring by means of 1-4, preferably 2-4 carbon atoms and each cyclic ring having at least one nitrogen and at least one other heteroatom in its cyclic structure selected from the class consisting of NR, O, S and PR. This catalyst system is particularly useful in the polymerization of vinyl compounds such as ethylene, propylene, styrene, butadiene, etc. The process for the polymerization of conjugated dienes produces polymers of excellent properties. For example, with butadiene-1,3 and other appropriate conditions, polybutadiene with high percentages of syndiotactic crystalline structure may be produced.Type: GrantFiled: October 18, 1979Date of Patent: January 27, 1981Assignee: The Firestone Tire & Rubber CompanyInventors: Adel F. Halasa, James E. Hall
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Patent number: 4246384Abstract: Magnesium metal is contacted with an organic halide in the absence of an ether or other complexing diluent to produce a magnesium reducing agent for converting titanium tetrahalide to titanium trihalide. In a first embodiment, the magnesium metal, organic halide, and titanium tetrahalide are introduced into a mill and milled. In a second embodiment, the organic halide is metered dropwise onto the magnesium metal in the absence of any extraneous diluent, and the resulting magnesium reducing agent is thereafter added to a titanium tetrahalide and milled. In a third embodiment, an organic halide containing the titanium tetrahalide is metered dropwise onto magnesium metal in the absence of any extraneous diluent. In each instance the resulting titanium trihalide catalyst component is contacted with an organoaluminum compound activator and used for the polymerization of olefins, preferably the polymerization of propylene.Type: GrantFiled: November 8, 1978Date of Patent: January 20, 1981Assignee: Phillips Petroleum CompanyInventor: Charles M. Selman
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Patent number: 4243782Abstract: A reaction product of a transition metal compound, for example titanium tetrachloride, and an organo-compound of a non-transition metal, for example an aluminium dialkyl halide, is treated with a sulphur containing organic compound, in an amount of up to 2.00, preferably up to 1.50 molar relative to the transition metal compound. The mixture is heated to a temperature in the range from 60.degree. C. up to 160.degree. C. Before treating with the sulphur compound, the reaction product can be heated to a temperature of up to 160.degree. C. The Lewis Base compound is a sulphone, a sulphonamide or a fused-ring heterocyclic compound such as phenoxathiin. The product obtained can be used as a component of an olefine polymerization catalyst.Type: GrantFiled: June 16, 1976Date of Patent: January 6, 1981Assignee: Imperial Chemical Industries LimitedInventors: Ashley D. Bye, Alan B. Newton
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Patent number: 4242479Abstract: A process for polymerizing ethylene or copolymerizing ethylene with an .alpha.-olefin in the presence of a catalyst comprising: (A) a solid catalyst ingredient obtained by contacting (1) a solid reaction product prepared by reacting (a) a reaction product of an aluminum trihalide with an organic compound containing an Si--O bond and/or an ether compound and (b) a magnesium alcoholate with (2) a tetravalent titanium compound containing at least one halogen atom or further (3) an electron donor compound, and (B) an organo-aluminum compound.Type: GrantFiled: December 22, 1977Date of Patent: December 30, 1980Assignee: Showa Yuka Kabushiki KaishaInventors: Yoshihisa Yokota, Teruo Hosokawa, Kiichiro Sakashita
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Patent number: 4237029Abstract: A catalyst system is made up of a catalyst and a cocatalyst. The catalyst component is made by intensely mixing a titanium trihalide component with triaryl phosphite and aluminum trihalide adjuvants. The cocatalyst is an organoaluminum compound. An example of such a system is a ball milled mixture of TiCl.sub.3..sup.1/ 3AlCl.sub.3, triphenyl phosphite, and aluminum trichloride as the catalyst and diethylaluminum chloride as the cocatalyst. Such catalyst systems give both high productivity and low solubles in the polymerization of propylene. The catalytic activity and/or stereospecificity of the catalyst can be enhanced by heat treatment at a moderate temperature subsequent to milling the mixture.Type: GrantFiled: January 29, 1979Date of Patent: December 2, 1980Assignee: Phillips Petroleum CompanyInventor: Lawrence M. Fodor
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Patent number: 4235747Abstract: Polymerization performance of organoaluminum reduced, electron donor complexed, brown solid, beta titanium trichloride catalyst component is improved in terms of polymer particle size by contacting said brown solid with at least one aluminum alkyl and at least one alpha-olefin in amounts and under conditions such that a low yield, polyalphaolefin structure is formed around the brown solid.Type: GrantFiled: April 19, 1979Date of Patent: November 25, 1980Assignee: Standard Oil Company (Indiana)Inventor: Linus K. Leung
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Patent number: 4235984Abstract: .alpha.-Olefin polymers of high stereoregularity are prepared by polymerizing the .alpha.-olefin with a catalyst prepared by mixing components (A), (B) and (C):(A) a solid titanium component prepared from an organo-magnesium compound, a silicon halide compound and/or an aluminum halide compound, an electron donor and TiCl.sub.4,(B) an organoaluminum activator, and(C) an electron donor.Type: GrantFiled: February 12, 1979Date of Patent: November 25, 1980Assignee: Sumitomo Chemical Company, LimitedInventors: Akinobu Shiga, Yoshiharu Fukui, Katsumi Hanji, Toshio Sasaki, Masahisa Okawa, Hideaki Matsuura, Yasuharu Yamada
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Patent number: 4228253Abstract: A process for making crystalline polymers or copolymers of alpha-olefins containing 3 to 8 carbon atoms, such as polypropylene, by polymerization with a catalyst consisting of a combination of titanium chloride and an organic aluminum compound, in the presence of a stereospecificity additive.This stereospecificity additive is a cyclic polyether of the crown ether type, which may contain sulphur atoms and/or nitro radicals; this additive may be used together with an activator.The process produces polymers or copolymers with a high isotacticity index, while keeping catalyst activity sufficiently high.Type: GrantFiled: June 13, 1979Date of Patent: October 14, 1980Assignee: Ato ChimieInventor: Gilbert Marie
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Patent number: 4228252Abstract: A process for making crystalline polymers or copolymers of alpha-olefins containing 3 to 8 carbon atoms, such as polypropylene, by polymerization with a catalyst consisting of a combination of titanium chloride and an organic aluminum compound, in the presence of a stereospecificity additive.This stereospecificity additive has the formula:R.sub.1 --O--(C.sub.p H.sub.2p)--S--R.sub.2,where:R.sub.1 and R.sub.2 are alkyl radicals containing 1 to 4 carbon atoms or are linked together to form a divalent --(C.sub.m H.sub.2m)--radical, andp and m are integers each with a value of 1 to 6;this additive may be used in the presence of an activator.Type: GrantFiled: June 13, 1979Date of Patent: October 14, 1980Assignee: Ato ChimieInventor: Gilbert Marie
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Patent number: 4224182Abstract: A new catalyst system for alphaolefin type polymerizations, includes at least one hindered alkyl metal amide compound having the formula R'.sub.2 YNR.sub.2 in combination with a Group IVB-VIII transition metal compound on a support and at least one Lewis base wherein R is selected from the group consisting of C.sub.4 to C.sub.20 bulky alkyl, cycloalkyl, aralkyl, aryl and substituted aryl groups or R.sub.2 N is a hindered cyclic amide group; R' is selected from the group consisting of C.sub.1 to C.sub.20 primary alkyl, secondary alkyl, tertiary alkyl, neopentyl alkyl, branched alkyl, cycloalkyl or aralkyl groups, and Y is selected from the group consisting of aluminum, gallium or indium. The catalyst system provides polymers having increased isotactic stereoregularity as well as lower catalyst residue.Type: GrantFiled: March 7, 1979Date of Patent: September 23, 1980Assignee: Exxon Research & Engineering Co.Inventors: Arthur W. Langer, Jr., John J. Steger, Terry J. Burkhardt
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Patent number: 4224181Abstract: A new improved Ziegler type catalyst system for alpha-olefin type polymerization includes R'.sub.3 Y or R'.sub.2 YX and mixtures thereof, at least one Group IVB -VIII transition metal halide and an alkyl metal compound selected from R'.sub.2 YNR.sub.2 and R'XYNR.sub.2, wherein Y is Al, Ga or In and at least one Lewis base. The improved catalyst system provides increased polymerization activity without significantly affecting the crystallinity of the polymer.Type: GrantFiled: March 7, 1979Date of Patent: September 23, 1980Assignee: Exxon Research & Engineering Co.Inventor: Arthur W. Langer, Jr.
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Patent number: 4223117Abstract: A process for the polymerization of olefins in the presence of a catalyst comprising a titanium compound and/or vanadium compound supported on a solid carrier and an organoaluminum compound, characterized in that said solid carrier comprises a solid product obtained by the reaction of an organomagnesium compound or a reaction mixture resulting from the organomagnesium compound and at least one compound selected from the group consisting of magnesium hydroxide, calcium hydroxide, zinc hydroxide and aluminum hydroxide, with an aluminum halogenide and/or silicon halogenide, whereby there are produced olefine polymers in an extremely large amount per unit weight of catalyst.Type: GrantFiled: April 10, 1978Date of Patent: September 16, 1980Assignee: Sumitomo Chemical Company, LimitedInventors: Takezo Sano, Akio Kobayashi, Yasuharu Yamada
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Patent number: 4215014Abstract: A new improved catalyst system for alpha-olefin type polymerizations includes a metal alkyl cocatalyst having the formula T.sub.n MR'.sub.3-n in combination with a Group IVB-VIII transition metal compound on a support and a Lewis base wherein n is equal to one or two, T is equal to R.sub.3 DCH.sub.2, and wherein D is selected from the group consisting of Si, Ge or Sn, R is methyl or ethyl, and R' is selected from the group consisting of C.sub.1 to C.sub.8 primary alkyl or aralkyl groups including unhindered branched groups and M is selected from the group consisting of aluminum, gallium, or indium. The improved catalyst system provides both increased polymerization activity and polymers having a high degree of isotactic stereoregularity as well as lower catalyst residue.Type: GrantFiled: June 18, 1979Date of Patent: July 29, 1980Assignee: Exxon Research & Engineering Co.Inventor: Arthur W. Langer, Jr.
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Patent number: 4211670Abstract: An improved titanium trichloride catalyst component is prepared by treating a crude titanium trichloride composition with two different electron donor compounds via successive treatment with first one of the donor compounds and then with the other. The treated composition provides greater stereospecificity in the polymerization and copolymerization of propylene.Type: GrantFiled: January 25, 1979Date of Patent: July 8, 1980Assignee: Hercules IncorporatedInventor: Edwin J. Vandenberg
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Patent number: 4210735Abstract: Process for the polymerization of .alpha.-olefins in the presence of an activator selected from among the organic compounds of metals of groups Ia, IIa, IIb and IIIa of the Periodic Table and a solid catalytic element prepared by(a) reducing TiCl.sub.4 by means of a reducing metal selected from among the metals of groups Ia, IIa, IIb, IIIa of the Periodic Table so as to prepare a double chloride of titanium and the reducing metal(b) treating the double chloride thus prepared by means of a complexant(c) reacting the double chloride thus treated with TiCl.sub.4(d) separating the solid catalytic element thus prepared.Type: GrantFiled: October 12, 1972Date of Patent: July 1, 1980Assignee: Solvay & Cie.Inventors: Jean-Pierre Hermans, Paul Henrioulle
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Patent number: 4210738Abstract: Solid catalytic complexes are useful for stereospecific polymerization of .alpha.-olefins to solid crystalline polymers. The complexes are formed by reducing TiCl.sub.4 with an alkylaluminum, treating thus-obtained reduced solid with a complexing agent and contacting the resultant with TiCl.sub.4. They have a specific surface greater than 75 m.sup.2 /g.Type: GrantFiled: March 21, 1972Date of Patent: July 1, 1980Assignee: Solvay & Cie.Inventors: Jean P. Hermans, Paul Henrioulle
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Patent number: 4197387Abstract: Phosphorus oxytrichloride modified titanium trichloride polymerization catalysts of improved efficiency and/or isotacticity are obtained when the modification reaction is carried out in the presence of methylene chloride.Type: GrantFiled: December 22, 1978Date of Patent: April 8, 1980Assignee: Dart Industries Inc.Inventors: John L. H. Allan, Birendra K. Patnaik
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Patent number: 4192774Abstract: A process for the preparation of an active TiCl.sub.3 catalyst which comprises:(a) reacting TiCl.sub.4 with a complexing agent in a molar ratio of from 1:0.3 to 1:2;(b) reacting an organo-aluminum compound with a complexing agent in a molar ratio of at most 1:0.25;(c) reducing the complexed TiCl.sub.4 with the complexed organo-aluminum compound over a period of less than one hour at a temperature within the range 60.degree. to 110.degree. C. to produce TiCl.sub.3 particles having an average particle size of from 50 to 500 .mu.m;(d) subjecting the TiCl.sub.3 particles to a treatment to reduce the average particle size thereof to less than 50 .mu.m, and(e) classifying the TiCl.sub.3 particles to separate a fraction having an average particle size of from 0.1 to 30 .mu.m.Type: GrantFiled: January 18, 1979Date of Patent: March 11, 1980Assignee: Shell Oil CompanyInventors: Andras G. T. G. Kortbeek, Adrianus A. van der Nat
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Patent number: 4192775Abstract: Olefin polymerization catalysts are prepared by depositing an organophosphoryl chromium product and an aluminum acetyl acetonate on an inorganic support material, and heating the support material in a non-reducing atmosphere at a temperature above about 300.degree. C. up to the decomposition temperature of the support material.Type: GrantFiled: July 17, 1978Date of Patent: March 11, 1980Assignee: National Petro Chemicals CorporationInventors: Louis J. Rekers, Stanley J. Katzen, Jerome H. Krekeler
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Patent number: 4189553Abstract: Compositions exhibiting high catalytic activity in the polymerization of .alpha.-olefins, particularly higher olefins, are provided by reacting a trivalent titanium halide complex such as an alcohol complex of titanium trichloride, an organomagnesium component such as a hydrocarbon soluble complex of dialkyl magnesium and an alkyl aluminum and halide source such as a hydrogen halide or an alkyl aluminum halide. Polymerization processes employing this catalyst composition do not require conventional catalyst removal steps in order to provide polymers having suitable color and other physical characteristics.Type: GrantFiled: June 2, 1978Date of Patent: February 19, 1980Assignee: The Dow Chemical CompanyInventor: Donald F. Birkelbach
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Patent number: 4189557Abstract: A process for the manufacture of homopolymers and copolymers of .alpha.-monoolefins by polymerizing the monomer or monomers by means of a Ziegler-Natta catalyst comprising (I) a titanium trichloride component and (II) an aluminum-alkyl component, wherein the titanium trichloride component (I) employed is obtained by (1) in a first stage moistening a suitable conventional catalyst component, consisting entirely or substantially of titanium trichloride, with a hydrocarbon mixture comprising a liquid alkane hydrocarbon and a liquid benzene hydrocarbon and (2) in a second stage drying the catalyst component, moistened with the hydrocarbon mixture, under an inert gas, with constant mechanical mixing, within a certain period, at a temperature which is from 5.degree. to 50.degree. C. above the boiling point of the highest-boiling hydrocarbon present in the hydrocarbon mixture which has been used to moisten the component.Type: GrantFiled: April 28, 1978Date of Patent: February 19, 1980Assignee: BASF AktiengesellschaftInventors: Peter Klaerner, Klaus Bronstert, Gerhard Staiger
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Patent number: 4189556Abstract: In an alpha-olefin polymerization process using a transition metal halide-aluminum alkyl catalyst system, addition of minor, effective amounts of aromatic amines or amine N-oxides substituted with electron withdrawing groups decreases the amount of low molecular weight or amorphous polymer produced.Type: GrantFiled: June 16, 1976Date of Patent: February 19, 1980Assignee: Standard Oil Company (Indiana)Inventors: Nicholas M. Karayannis, Sam S. Lee
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Patent number: 4187385Abstract: Polymerization of ethylene or .alpha.-olefins using a catalyst comprising a titanium component obtained by copulverizing the starting titanium component of Ziegler catalysts and organoaluminum compound with a small amount of ethylene or .alpha.-olefins, and an organoaluminum component. The titanium catalyst component can be modified by subjecting the copulverized titanium component to a contact with an inert organic solvent or its mixture with a modifier (1) an oxygen-, sulphur-, phosphor-, nitrogen- or silicon- containing organic compound, (2) a combination of such an organic compound and an aluminum halide, (3) an organoaluminum compound or (4) a Lewis acid.Type: GrantFiled: May 16, 1977Date of Patent: February 5, 1980Assignee: Mitsui Toatsu Chemical, Inc.Inventors: Tetsuya Iwao, Heizo Sasaki, Akira Ito, Masahiro Kono
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Patent number: 4184028Abstract: Olefin polymerization catalysts are prepared by depositing an organophosphoryl chromium product and an aluminum compound on an inorganic support material, and heating the support material in a non-reducing atmosphere at a temperature above about 300.degree. C. up to the decomposition temperature of the support material.Type: GrantFiled: June 29, 1977Date of Patent: January 15, 1980Assignee: National Petro Chemicals CorporationInventors: Louis J. Rekers, Stanley J. Katzen, Jerome H. Krekeler
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Patent number: 4182811Abstract: A catalyst for the (co)polymerization of ethylene, .alpha.-olefines, conjugated and non-conjugated dienes, a method of preparation, and a mode of using same. The catalyst contains from 0.1 to 50 wt.% of a compound of a transition metal of the IV-VIII Groups chemically combined and distributed over the surface and within the volume of a rubber-like polymeric carrier containing from 1 to 50 wt.% of electron-donor and/or electron-acceptor groups and is in the form of a gel which is swellable, but insoluble in the reaction medium.A co-catalyst comprising an organic compound of a metal of Groups I-III is employed chemically combined and/or non-combined with the catalyst.The catalyst is prepared by mixing the metal compound with said carrier swollen or dissolved in a solvent, and by extracting the resulting compound with a solvent.(Co)polymerization is effected in a solvent such as a hydrocarbon or a hologenated hydrocarbon derivative at a temperature not exceeding 200.degree. C.Type: GrantFiled: February 27, 1978Date of Patent: January 8, 1980Inventors: Jury N. Bocharov, Viktor A. Kabanov, Marina A. Martynova, Valery G. Popov, Vladimir I. Smetanjuk, Viktor V. Fedorov
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Patent number: 4182816Abstract: A titanium trihalide is ground with an organic Lewis Base compound which contains at least one phosphorus atom, and optionally at least one nitrogen atom, and a titanium tetrahalide, the Lewis Base and the titanium tetrahalide being used in amounts of 5 to 75, preferably 5 to 50%, molar and 1 to 50, preferably 5 to 30% molar respectively relative to the titanium trihalide. The materials are conveniently milled together and the milled product can be used as a component of an olefine polymerization catalyst and when such catalysts are used to polymerize propylene a high activity is achieved together with satisfactory stereospecificity.Type: GrantFiled: June 14, 1978Date of Patent: January 8, 1980Assignee: Imperial Chemical Industries LimitedInventors: Anthony D. Caunt, Michael S. Fortuin, Ian G. Williams
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Patent number: 4176219Abstract: In the production of 1,2-polybutadiene by contacting 1,3-butadiene with a catalyst composed of (A) a cobalt compound, (B) an organic phosphine compound, (C) trialkylaluminum and (D) water in an amount of 0.25 to 1.5 moles per mole of said trialkylaluminum, the addition of (E) at least one compound selected from the group consisting of allyl halides, alkyl-substituted allyl halides, benzyl halides, alkyl-substituted benzyl halides, and tertiary aliphatic halides to the reaction system enables the molecular weight of the objective 1,2-polybutadiene to be regulated to any desired value without causing any change in microstructure and degree of crystallization of the product and also without deteriorating so much the polymerization activity.Type: GrantFiled: May 30, 1978Date of Patent: November 27, 1979Assignee: Japan Synthetic Rubber Co., Ltd.Inventors: Kenya Makino, Tsunezo Ishikawa, Koei Komatsu