Boron Compound Is Halogen-containing Patents (Class 526/133)
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Patent number: 4501866Abstract: A method for preparing high cis-1,4 polybutadiene by a continuous process which involves the continuous polymerization of 1,3-butadiene in solution under adiabatic conditions is provided. The method comprises the steps of: (I) feeding continuously to a single agitated polymerization reactor: (a) a monomer stream comprising 1,3-butadiene in a hydrocarbon solvent; (b) a preformed .pi. allyl catalyst stream formed by admixing a carboxylated metal oxy borate compound represented by the formulae (RCOOMO).sub.3 B or (ROCOOMO).sub.2 B-OR' wherein R and R' are alkyl radicals containing from 7 to 17 carbon atoms and M is nickel or cobalt, an organo aluminum compound, an alcohol, a small amount of 1,3-butadiene and a hydrocarbon solvent; and (c) a cocatalyst stream comprising a boron trifluoride complex with an alcohol; and (II) withdrawing continuously from said reactor high cis-1,4 polybutadiene at the same rate as said monomer, preformed catalyst and cocatalyst streams are fed to the reactor.Type: GrantFiled: July 23, 1984Date of Patent: February 26, 1985Assignee: The Firestone Tire & Rubber CompanyInventors: David M. Roggeman, Shrikant R. Malani, Jung W. Kang
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Patent number: 4487844Abstract: A catalyst system is provided comprising a titanium catalyst component produced by contacting a benzenediazonium tetrafluoroborate with a titanium tetrahalide such as titanium tetrachloride and a cocatalyst. Preferred cocatalysts are organoaluminum compounds. The catalyst system of this invention is broadly suitable for this polymerization of 1-olefins and is particularly suited for the production of high molecular weight ethylene polymers.Type: GrantFiled: August 22, 1983Date of Patent: December 11, 1984Assignee: Phillips Petroleum CompanyInventors: Robert M. Parlman, Charles M. Selman
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Patent number: 4471066Abstract: A catalyst useful for polymerizing olefins which comprises a solid catalyst component [A] and an organometallic component [B], the solid catalyst component [A] being obtained by reacting (1) an organometallic compound with (2) a transition metal compound selected from the group consisting of a titanium compound, a vanadium compound, a mixture of a titanium compound and a vanadium compound and a mixture of a titanium compound and a zirconium compound, in the presence of (3) a solid reaction product of (a) an organomagnesium compound of the formulaM.sub..alpha. MgR.sub.p X.sub.q.D.sub.rwherein.alpha., p, q and r each independently is 0 or a number greater than 0,p+q=m.alpha.+20.ltoreq.q/(.alpha.Type: GrantFiled: February 3, 1983Date of Patent: September 11, 1984Assignee: Asahi Kasei Kogyo Kabushiki KaishaInventors: Hisaya Sakurai, Yoshihiko Katayama, Tadashi Ikegami, Masayasu Furusato
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Patent number: 4456547Abstract: A catalyst for polymerizing olefins is the product resulting from mixing in an inert hydrocarbon diluent a mixture of (A) an organomagnesium material, (B) an organic hydroxyl-containing material, (C) a reducing halide source and (D) the reaction product or complex formed from the admixture of a transition metal compound and an organozinc compound.Type: GrantFiled: October 21, 1982Date of Patent: June 26, 1984Inventor: Ricardo Fuentes, Jr.
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Patent number: 4429089Abstract: A novel catalytic system is disclosed which is especially adapted for the polymerization and the copolymerization of aliphatic conjugated diolefines, the system comprising an organic compound of aluminum, a Lewis acid containing at least one halogen, and an organic compound of a lanthanide metal. The catalyst system has outstanding and hitherto unparalleled activity. The method of preparation of the catalytic system is also described in detail.Type: GrantFiled: July 15, 1981Date of Patent: January 31, 1984Assignee: Anic, S.p.A.Inventors: Ugo Pedretti, Gabriele Lugli, Sergio Poggio, Alessandro Mazzei
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Patent number: 4426316Abstract: A catalyst for polymerizing olefins is the product resulting from heating in an inert hydrocarbon diluent a mixture of (A) an organomagnesium material, (B) an organic hydroxyl-containing material, (C) a reducing halide source and (D) a transition metal compound.Type: GrantFiled: September 10, 1982Date of Patent: January 17, 1984Assignee: The Dow Chemical CompanyInventor: Donald E. Gessell
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Patent number: 4418184Abstract: Improved process for preparing an ethylene polymer wax which comprises polymerizing ethylene or copolymerizing ethylene with up to 10 mole % of an alpha-olefin having 3 to 20 carbon atoms in the presence of (A) a highly active titanium catalyst component activated by a magnesium compound and (B) an organoaluminum catalyst component composed of (B-1) an organoaluminum compound free from halogen bonded directly to the aluminum atom and (B-2) a halogen compound of an element selected from the group consisting of elements other than titanium of Groups III and IV of the Mendelejeff's periodic table, the atomic ratio of halogen to aluminum in the organoaluminum catalyst component (B) being from about 1:6 to about 9:10, provided that when said halogen compound is a halogen compound of carbon, this atomic ratio is from about 1:6 to about 10:1, and said polymerization or copolymerization being carried out under such conditions that the concentration of ethylene polymer wax in the polymerization or copolymerization sysType: GrantFiled: March 22, 1982Date of Patent: November 29, 1983Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Takashi Ueda, Norio Kashiwa
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Patent number: 4415712Abstract: Alpha-olefins are polymerized in the presence of a catalyst which is the catalytic reaction product of(A) the reaction product or complex formed by mixing at a temperature for a time sufficient to provide a color change(a) a transition metal compound having at least one hydrocarbyloxy group attached to said transition metal and(b) a boron compound;(B) a magnesium halide resulting from the reaction of(a) an organomagnesium component and(b) a halide source; and(C) an organoaluminum compound, if required.Type: GrantFiled: March 1, 1982Date of Patent: November 15, 1983Assignee: The Dow Chemical CompanyInventors: Randall S. Shipley, Larry E. Freyer
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Reaction products of transition metal compounds and boron compounds and catalysts prepared therefrom
Patent number: 4412939Abstract: Compositions consisting of the reaction product or complex resulting from the mixing of a transition metal compound such as a tetraalkoxy titanium compound and a boron compound such as a trialkyl boron compound are useful in the preparation of catalysts for polymerizing .alpha.-olefins exhibiting ultra-high efficiencies at high polymerization temperatures.Type: GrantFiled: March 1, 1982Date of Patent: November 1, 1983Assignee: The Dow Chemical CompanyInventors: Randall S. Shipley, Larry E. Freyer -
Patent number: 4409126Abstract: Compositions consisting of the reaction product or complex resulting from the mixing of a transition metal compound such as a tetraalkoxy titanium compound and an organo compound of magnesium, aluminum, boron or lithium such as a dialkyl magnesium compound are useful in the preparation of catalysts for polymerizing .alpha.-olefins at ultra-high efficiencies at high polymerization temperatures.Type: GrantFiled: October 22, 1981Date of Patent: October 11, 1983Assignee: The Dow Chemical CompanyInventors: Randall S. Shipley, Donald F. Birkelbach
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Patent number: 4387200Abstract: A process for polymerizing olefins employing as a catalyst therefor, the reaction product of (A) the reaction product of (1) the reaction product of (a) an alkyl magnesium compound such as dibutylmagnesium, with (b) an oxygen-containing and/or nitrogen-containing compound such as n-propyl alcohol, or isopropylamine, with (2) a halide source such as titanium tetrachloride or silicon tetrachloride; and (B) a transition metal compound such as titanium tetrachloride and (C) a reducing agent such as triisobutylaluminum. The polymers which are produced in the presence of this catalyst and a cocatalyst such as triethylaluminum have a low catalyst support to transition metal ratio and therefore, the catalyst efficiency based on quantity of polymer per quantity of total catalyst is very high resulting in a polymer having good color and very little, if any, corrosion.Type: GrantFiled: March 22, 1982Date of Patent: June 7, 1983Assignee: The Dow Chemical CompanyInventors: Donald E. Gessell, Ronald L. Gibbs, Ricardo Fuentes, Jr.
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Patent number: 4385161Abstract: A catalyst component is a transition metal composition which is obtained by reacting together an inert particulate material, an organic magnesium compound, a halogen-containing compound such as carbon tetrachloride silicon tetrachloride or boron trichloride and a specified transition metal compound such as VOCl.sub.3, bis(n-butoxy) titanium dichloride or zirconium tetrabenzyl. The catalyst component obtained can be used, together with an organic metal compound, to give an olefin polymerization catalyst. The catalyst can be used to effect the polymerization of olefin monomers, for example, the copolymerization of ethylene with an alpha-olefin monomer such as butene-1 in a fluidized bed reactor.Type: GrantFiled: January 6, 1981Date of Patent: May 24, 1983Assignee: Imperial Chemical Industries LimitedInventors: Anthony D. Caunt, Paul D. Gavens, John McMeeking
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Patent number: 4383097Abstract: There is disclosed a process for the regulation of the molecular weight of high cis polybutadiene prepared by polymerizing butadiene under solution polymerization conditions employing as the catalyst system a mixture of (a) organoaluminum compounds; (b) organonickel compounds; and (c) fluorine containing compounds; said polymerization being conducted in the presence of nonconjugated diolefins of the formula of the structure ##STR1## wherein R.sub.1 may be; --CH.sub.2 --; --C.sub.2 H.sub.4 --; --C.sub.3 H.sub.6 --; ##STR2## and R.sub.2 may be H, --CH.sub.3, --C.sub.2 H.sub.5 or --C.sub.3 H.sub.7 and R.sub.2 is trans to R.sub.1.Type: GrantFiled: August 21, 1981Date of Patent: May 10, 1983Assignee: The Goodyear Tire & Rubber CompanyInventors: Kenneth F. Castner, Paul H. Sandstrom
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Patent number: 4339351Abstract: A process for producing olefin polymers, which comprises polymerizing or copolymerizing olefins in the presence of a catalyst comprising a solid catalyst component and an organoaluminum compound, said solid catalyst component being a titanium compound and/or a vanadium compound supported on a solid product obtained by the reaction between a Grignard compound and a boron compound represented by the general formula B(OR.sup.1).sub.a R.sup.2.sub.b R.sup.3.sub.c, wherein a, b and c are numbers defined by the formulas 0<a.ltoreq.3, 0.ltoreq.b<3, 0.ltoreq.c<3 and a+b+c=3, R.sup.1 represents a hydrocarbon radical having 1 to 20 carbon atoms, and R.sup.2 and R.sup.3, which may be the same or different, represent each a hydrogen atom, a hydrocarbon radical having 1 to 20 carbon atoms, or a halogen atom.Type: GrantFiled: December 4, 1980Date of Patent: July 13, 1982Assignee: Sumitomo Chemical Company, LimitedInventors: Kentaro Mashita, Katsumi Hanji
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Patent number: 4335229Abstract: A process for polymerizing an .alpha.-olefin comprising contacting the olefin in liquid phase at a temperature of about 120.degree. to about 320.degree. C. with a catalyst comprising a component (A) and an organometal component (B), the component (A) being produced by reacting a hydrocarbon-soluble organomagnesium component (i) of the formula,M.sub..alpha. MgR.sub.p.sup.1 R.sub.q.sup.2 X.sub.r.sup.1 X.sub.s.sup.2 D.sub.twherein.alpha., p, q, r and s each independently is 0 or a number greater than 0,t is a number greater than 0,p+q+r+s=m.alpha.+2,O.ltoreq.(r+s)/(.alpha.+1)<2,m is the valance of M,M is a metal of the 1st to 3rd groups of the Periodic Table,R.sup.1 and R.sup.2 each independently is a hydrocarbon group having 1 to 20 carbon atoms,X.sup.1 and X.sup.Type: GrantFiled: August 13, 1980Date of Patent: June 15, 1982Assignee: Asahi Kasei Kogyo Kabushiki KaishaInventors: Hisaya Sakurai, Yoshihiko Katayama, Tadashi Ikegami, Masayasu Furusato
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Patent number: 4330646Abstract: A process for polymerizing an .alpha.-olefin comprising contacting the olefin in liquid phase at a temperature of about 120.degree. to about 320.degree. C. with a catalyst comprising a component (A) and an organometal component (B), the component (A) being produced by reacting a hydrocarbon-soluble organomagnesium component (i) of the formulaM.sub..alpha. Mg.sub..beta. R.sub.p.sup.1 R.sub.q.sup.2 X.sub.r.sup.1 X.sub.s.sup.2wherein.alpha., p, q, r and s each independently is 0 or a number greater than 0,.beta. is 1 or a number greater than 1,p+q+r+s=m.alpha.+2.beta.,0.ltoreq.(r+s)/(.alpha.+.beta.)<2,m is the valence of M,M is a metal of the 1st to 3rd groups of the Periodic Table,R.sup.1 and R.sup.2 each independently is a hydrocarbon group having 1 to 20 carbon atoms,X.sup.1 and X.sup.Type: GrantFiled: July 21, 1980Date of Patent: May 18, 1982Assignee: Asahi Kasei Kogyo Kabushiki KaishaInventors: Hisaya Sakurai, Yoshihiko Katayama, Tadashi Ikegami, Masayasu Furusato
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Patent number: 4308369Abstract: Olefins are polymerized in the presence of a catalyst prepared by reacting tetravalent titanium compounds such as a titanium tetraalkoxide, an anhydrous zinc compound such as diethyl zinc, an organomagnesium component such as a hydrocarbon soluble complex of dialkyl magnesium and an alkyl aluminum and a halide source such as a hydrogen halide or an alkyl aluminum halide and an aluminum compound if the halide source or organomagnesium component does not contain sufficient quantities of aluminum. 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 and these catalysts produce polymers having broader molecular weight distributions than do corresponding catalysts without the anhydrous zinc compound.Type: GrantFiled: June 2, 1980Date of Patent: December 29, 1981Assignee: The Dow Chemical CompanyInventors: Randall S. Shipley, Donald F. Birkelbach, Kirby Lowery, Jr.
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Patent number: 4250284Abstract: Polymerization and copolymerization is carried out in the presence of an improved transition metal based catalyst. The catalyst is obtained by activating with an organometallic compound, the solid product which results from the reaction of a halogen containing transition metal compound with an alkoxy metal compound of the formula X.sub.m-n M(OR).sub.n wherein M is at least one metal selected from the elements of Groups Ia, IIa, IIb, IIIa and VIIb of the Periodic Table, X is a monovalent inorganic radical, R is a monovalent hydrocarbon radical, m is the valence of M and n is an integer such that 1 .ltoreq. n .ltoreq. m.Type: GrantFiled: February 24, 1975Date of Patent: February 10, 1981Assignee: Solvay & CieInventors: Andre Delbouille, Jean L. Derroitte
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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: 4158088Abstract: Polymerization of ethylene or .alpha.-olefins is carried out with use of a catalyst comprising a modified titanium component obtained by pulverizing the starting titanium component of Ziegler solid catalysts and subjecting the resultant to a modification treatment through contact with an inert organic solvent or a mixture thereof with a modifier, and an organoaluminum component.The pulverized product of the starting titanium component is pulverized together with an organoaluminum compound and a small amount of ethylene or .alpha.-olefins thereby controlling the particle size distribution.Type: GrantFiled: July 15, 1977Date of Patent: June 12, 1979Assignee: Mitsui Toatsu Chemicals, Inc.Inventors: Tetsuya Iwao, Masahiro Kono, Heizo Sasaki, Akira Ito
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Patent number: 4151337Abstract: Polyolefin is prepared by polymerizing an olefin by using a catalyst system combining an auxiliary catalytic component of an organoaluminum compound and a solid catalytic component obtained by reacting a mixture of a vanadium trichloride ether complex and a titanium trichloride ether complex with an aluminum halide and/or a boron halide.Type: GrantFiled: May 25, 1977Date of Patent: April 24, 1979Assignee: Mitsubishi Chemical Industries Ltd.Inventors: Natsuki Kanoh, Toru Tanaka, Nobuo Enokido
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Patent number: 4145497Abstract: Uranium-containing mixed catalysts containing uranium in the formal oxidation state +4 as uranium salts of carboxylic acids, a Lewis acid, and an organometallic aluminum compound are prepared and can be used for stereospecific polymerization of diolefins or mixtures of diolefins and monoolefins.Type: GrantFiled: May 31, 1977Date of Patent: March 20, 1979Assignee: Bayer AktiengesellschaftInventors: Gerd Sylvester, Josef Witte, Gunter Marwede
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Patent number: 4127710Abstract: A 1,3-cyclodiene comonomer and a linear conjugated diene comonomer are copolymerized employing a catalyst formed from a mixture comprising a triorganoaluminum compound, a nickel (II) compound and a Friedel-Crafts type cocatalyst. Also, a catalyst and a method for the production thereof which is useful in the copolymerization is provided.Type: GrantFiled: October 2, 1974Date of Patent: November 28, 1978Assignee: Phillips Petroleum CompanyInventor: Henry L. Hsieh
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Patent number: 4096322Abstract: A process for producing cis-1,4-polybutadiene by contacting butadiene with a catalyst consisting of (1) at least one organoaluminum compound, (2) at least one organonickel compound selected from the class consisting of nickel salts of carboxylic acids, organic complex compounds of nickel and nickel tetracarbonyl, (3) boron trifluoride gas or a boron trifluoride etherate complex, and (4) at least one alkyl substituted hydroxy containing aromatic compound wherein the alkyl groups leave the hydroxy groups unhindered for chemical activity in that no alkyl groups are present simultaneously on both positions ortho to the hydroxy groups.Type: GrantFiled: December 23, 1974Date of Patent: June 20, 1978Assignee: The Goodyear Tire & Rubber CompanyInventor: Morford C. Throckmorton
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Patent number: 4063010Abstract: Novel amorphous copolymers of mono-olefins or of mono-olefins and non-conjugated dienes with unsaturated derivatives of imides are disclosed. These copolymers containing from 99.9 to 80% by weight of non-polar units derived from at least two mono-olefins containing 2 to 18 carbon atoms, particularly ethylene and propene or ethylene and butene-1, and possibly one or more non-conjugated dienes, and from 0.1 to 20% units derived from an imide having the formula ##STR1## wherein Z is an alkenyl radical containing 2 to 16 carbon atoms, andA designates a saturated or unsaturated divalent hydrocarbon radical which contains 2 to 12 carbon atoms and which may possibly carry amino, halogeno or carboxyl groups.Some of said copolymers may be used as polymer additives in lubricating compounds to improve their viscosity index and to disperse the slurry which they may contain.Type: GrantFiled: December 3, 1975Date of Patent: December 13, 1977Assignee: Societe Nationale Elf Aquitaine (SNEA)Inventors: Gilbert Marie, Andre Lang, Gilbert Chapelet
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Patent number: 4020255Abstract: There is disclosed a method of preparing high cis-1,4-polybutadiene which comprises continuously polymerizing butadiene in mixture with an inert aliphatic or cycloaliphatic solvent employing as a catalyst a mixture comprising (A) at least one trialkyl aluminum wherein the alkyl group contains from 2 to 8 carbon atoms, (B) at least one nickel salt of carboxylic acids and (C) at least one boron trifluoride complex of ethers in which each of the individual catalyst components are continuously injected into the polymerization vessel containing the mixture of butadiene and inert solvent.Type: GrantFiled: May 7, 1975Date of Patent: April 26, 1977Assignee: The Goodyear Tire & Rubber CompanyInventors: Donald P. Schoneman, Robert W. Stachowiak
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Patent number: 3985677Abstract: A method of polymerizing butadiene and/or butadiene in mixture with other diolefins to form polymers with a high cis-1,4 addition wherein the improvement relates to improved catalysts for producing the high cis-1,4-polybutadiene.Type: GrantFiled: June 24, 1974Date of Patent: October 12, 1976Assignee: The Goodyear Tire & Rubber CompanyInventors: Morford C. Throckmorton, Paul H. Sandstrom
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Patent number: 3985941Abstract: A method of polymerization of butadiene to form polymers with a high (greater than 90 percent) content of cis-1,4 configuration wherein a mixed fluoride bearing catalyst system is utilized to control the polymerization rate and the molecular weight.Type: GrantFiled: May 12, 1975Date of Patent: October 12, 1976Assignee: The Goodyear Tire & Rubber CompanyInventors: Robert M. Pierson, Leonard J. Kuzma