At Least One Group Ivb Metal Atom (ti, Zr, Hf) And At Least One Group Vb Meta L (v, Nb, Ta) Patents (Class 526/116)
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Patent number: 4397762Abstract: A supported Ziegler catalyst prepared by the following steps, carried out under anhydrous conditions:(A) reacting a hydroxyl groups-containing support material comprising magnesium silicate or silica and magnesia with one or more organo-metallic compounds having the general formula MR.sup.1.sub.a Q.sub.b-a wherein M is a metal which is aluminium, boron, lithium, zinc or magnesium, R.sup.1 is a hydrocarbyl group, Q is halogen or an oxyhydrocarbyl group, b is the valency of M and a is an integer from 1 to b,(B) removing unreacted organometallic compound, if any, from the produced solid material,(C) impregnating the solid material obtained from step B with one or more halogen-containing transition metal compounds wherein the transition metal(s) comprise titanium, vanadium or zirconium.Type: GrantFiled: January 27, 1982Date of Patent: August 9, 1983Assignee: BP Chemicals LimitedInventor: Alexander Johnstone
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Patent number: 4396533Abstract: A supported Ziegler catalyst prepared by the following steps:(A) heating together at a temperature in the range of 250.degree. to 1100.degree. C. a refractory oxide support material having surface hydroxyl groups and one or more halogen-free metal derivatives which are hydrides and/or organic derivatives of the metal.(B) reacting the product from (A) with one or more organometallic compounds having the feneral formula MR.sup.1.sub.a Q.sub.b-a wherein M is a metal atom, R.sup.1 is a hydrocarbon group, Q is a halogen or an oxyhydrocarbyl group, b is the valency of M and a is an integer from 1 to b and wherein the metal atom M is aluminium, boron, lithium, zinc or magnesium,(C) impregnating the solid product from step (B) with one or more halogen-containing transition metal compounds wherein the transition metal or metals comprise titanium and/or vanadium and/or zirconium.Type: GrantFiled: January 27, 1982Date of Patent: August 2, 1983Assignee: BP Chemicals LimitedInventor: Alexander Johnstone
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Patent number: 4390454Abstract: There are disclosed components of catalysts for polymerizing ethylene and mixtures of ethylene with alpha-olefins comprising the reaction product of (A) a magnesium compound, such as Mg-chloride, Mg-alcoholate or a Grignard compound, with (B) a titanium, vanadium or zirconium compound having at least two metal-oxygen bonds, such as a tetra-alcoholate, and with (C) a halogenated compound of metals of B, such as Ti tetrachloride.According to an aspect of the invention, the reaction product (A)+(B), before being reacted with (C), is treated with a silicum compound having a halogenating and/or reducing action.The catalysts according to the invention are suitable for obtaining ethylene polymers having a broad distribution of molecular weights.Type: GrantFiled: July 23, 1981Date of Patent: June 28, 1983Assignee: Montedison S.p.A.Inventors: Illaro Cuffiani, Paolo Galli, Umberto Zucchini
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Patent number: 4389518Abstract: A process for producing polyethylene having a superior form and a narrower molecular weight distribution with a higher polymer yield is provided. In this process, a combination of a solid product (II) with an organoaluminum compound is used as a polymerization catalyst. This solid product is prepared by first reacting a trivalent metal halide with a divalent metal compound to form a solid product (I), which is then reacted with a halogen-containing transition metal compound and a halogen-free transition metal compound in the presence of a polysiloxane.Type: GrantFiled: August 25, 1981Date of Patent: June 21, 1983Assignee: Chisso CorporationInventors: Masato Harada, Atsushi Suzuki, Sadahiko Yamada, Jun Masuda
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Patent number: 4388219Abstract: A catalyst for polymerizing ethylene, especially at high temperature and high pressure, comprising at least two halogen compounds of transition metals, one of which is a titanium trichloride syncrystallized with aluminum chloride. The catalyst has the formula(TiCl.sub.3, 1/3AlCl.sub.3)(MX.sub.3).sub.x (MgX.sub.2).sub.ywherein 0.3.ltoreq.x.ltoreq.3, 0.ltoreq.y.ltoreq.20, M is a transition metal of Groups V B and VI B of the Periodic System, and X is a halogen. The second transition metal is preferably vanadium, chromium, molybdenum, or tungsten. The catalyst is made by subjecting titanium trichloride syncrystallized with aluminum chloride, the trivalent halide of M, and, optionally, anhydrous magnesium halide to a milling step in which the milling energy is at least equal to three kWh per kg of solid material treated, which results in a binary solid solution structure Ti-M of which the dimension of crystallites is less than or equal to 100 Angstroms.Type: GrantFiled: December 19, 1980Date of Patent: June 14, 1983Assignee: Societe Chimique des Charbonnages - CdF CHIMIEInventor: Karel Bujadoux
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Patent number: 4387199Abstract: A compound of tetravalent vanadium of the general formula ##STR1## wherein M represents a metal of the fourth group of the Periodic Table of the Elements and R represents and alkyl, cycloalkyl or aryl moiety of 1 to 20 carbon atoms and a process for its preparation. Also disclosed is the use of such vanadium compound as a catalyst for homopolymerization, copolymerization or terpolymerization of various monomers including olefins and vinyl monomers.Type: GrantFiled: October 9, 1981Date of Patent: June 7, 1983Assignee: Dynamit Nobel AktiengesellschaftInventors: Walter Josten, Hans-Joachim Vahlensieck
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Patent number: 4387198Abstract: A process for producing .alpha.-olefin polymers characterized by employing an organomagnesium compound in the preparation of a preactivated catalyst therefor is provided. The resulting polymers have particularly a higher rigidity in addition to various superior properties. The process comprises reacting a trivalent metal halide with a divalent metal compound to obtain a solid product (I); reacting this product with an organomagnesium compound, an electron donor (ED) and an electron acceptor (EA), once to 10 times, and at that time, using TiCl.sub.4 at least once as the (EA) to obtain a solid product (II); combining this product with an organoaluminum compound (OAl) and an (ED), and at that time, subjecting a combination of (II) and (OAl) or that of (II), (OAl) and (ED) to polymerization treatment with an .alpha.-olefin, and in the case of the former combination, further adding (ED), to obtain a preactivated catalyst; and polymerizing .alpha.-olefin(s) in the presence of this catalyst.Type: GrantFiled: March 12, 1980Date of Patent: June 7, 1983Assignee: Chisso CorporationInventors: Akihiro Sato, Masami Tachibana, Kazutsune Kikuta, Yoshiharu Higuchi, Masazumi Miyajima
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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: 4383939Abstract: A supported Ziegler catalyst component prepared by (A) reacting a refractory oxide support material having surface --OH groups, for example silica, with halogen-containing transition metal compound, eg titanium tetrachloride, (B) reacting the product with an organometallic compound, for example triethyl aluminium and (C) reacting with transition metal compound in which vanadium is present, for example vanadyl chloride. The catalyst component is conventionally activated with organometallic compound and can be used to polymerize 1-olefins, for example ethylene.Type: GrantFiled: January 27, 1982Date of Patent: May 17, 1983Assignee: BP Chemicals LimitedInventor: Alexander Johnstone
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Patent number: 4384087Abstract: A transition metal compound and a metal halide compound selected from metal dihalide compounds and metal hydroxyhalide compounds are chemically combined to form a composition of matter. The composition of matter is suitable for use with an organometallic compound to produce an active olefin polymerization catalyst. Exceptionally high polymer yields are realized per gram of catalyst when the catalyst is treated with a halide ion exchanging source and used with an organometallic cocatalyst.Type: GrantFiled: August 20, 1981Date of Patent: May 17, 1983Assignee: Phillips Petroleum CompanyInventor: Charles E. Capshew
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Patent number: 4384088Abstract: According to this invention, there is provided a process for preparing polyolefins wherein olefins are polymerized or copolymerized using as catalyst a solid component and an organometallic compound, characterized in that said solid component is a substance obtained by the copulverization of:(1) a reaction product resulting from a heat reaction of magnesium oxide and aluminum trichloride,(2) a titanium compound and/or a vanadium compound, and(3) if desired, an organic halide.Type: GrantFiled: June 7, 1978Date of Patent: May 17, 1983Assignee: Nippon Oil Company, LimitedInventors: Mitsuo Matsuno, Etsuo Kawamata, Nobuyuki Kuroda, Kazuo Matsuura, Mitsuji Miyoshi
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Patent number: 4379074Abstract: This application relates to a process for the homopolymerization (or copolymerization) of unsaturated compounds, particularly ethylene and higher alpha olefines, to give homopolymers (or copolymers) having a wide molecular weight distribution.The polymerization yields are very high, even at relatively low pressures (10 bars), i.e. such as not to require scrubbing in order to remove the catalytic residue from the polymer.These results are obtained by using, in union with an organometallic aluminium compound, a catalyst in the form of a new titanium trihalide-based chemical composition satisfying the following formula:TiX.sub.3.mM'Y.sub.n.qM"Y'.sub.p.cAlY".sub.3-s R.sub.Type: GrantFiled: December 5, 1980Date of Patent: April 5, 1983Assignees: Anic S.p.A., Snamprogetti, S.p.A.Inventors: Agostino Balducci, Margherita Corbellini, Mirko Osellame
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Patent number: 4378455Abstract: The present disclosure relates to a process for alternating copolymerization of propylene and butadiene in the absence of a polymerization solvent. The disclosure contains information relative to commercial production of the said copolymer and detailed teachings relative to the preparation of catalyst for use in the said process.Type: GrantFiled: February 19, 1980Date of Patent: March 29, 1983Assignee: Maruzen Petrochemical Co., Ltd.Inventors: Akihiro Kawasaki, Tsuyoshi Matsumoto, Masanobu Taniguchi, Isao Maruyama, Masaaki Matsui, Masao Kaneko, Akihiko Imai
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Patent number: 4371679Abstract: This invention provides a process for preparing polyolefins by polymerizing or copolymerizing olefins using as the catalyst a titanium compound-containing solid component and an organometal compound, said solid component comprising a substance obtained by copulverizing (1) magnesium halide and/or manganese halide, (2) an organic halide compound, (3) a chain or cyclic silicone compound with a recurring structural unit represented by the general formula ##STR1## wherein R' and R" respectively represent a hydrogen, alkyl, aryl, alkoxy or hydroxyl group and (4) tetravalent and/or trivalent titanium compound(s).Type: GrantFiled: January 28, 1981Date of Patent: February 1, 1983Assignee: Nippon Oil Company, Ltd.Inventors: Nobuyuki Kuroda, Akira Sano, Toru Nakamura, Kazuo Matsuura, Mituji Miyoshi
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Patent number: 4368305Abstract: A process for producing polyolefins and particularly polyethylene which are high in molecular weight or which are wide in molecular weight distribution and thus suitable for extrusion or blow molding purposes, the process comprising polymerizing olefins such as ethylene by the use of a catalytic system which is comprised of a solid catalytic component obtained by mixing or interacting oxygen-containing organometal compounds or halides of (a) vanadium and (b) hafnium or a solid catalytic component obtained by mixing or interacting oxygen-containing organometal compounds or halides of (A) vanadium, (B) hafnium and (C) titanium, and (D) an organoaluminum compound, and of an organoaluminum compound.Type: GrantFiled: August 1, 1980Date of Patent: January 11, 1983Assignee: Mitsubishi Chemical Industries, Ltd.Inventors: Toru Tanaka, Eiji Tanaka
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Patent number: 4368306Abstract: Poly-.alpha.-olefins, particularly polyethylene, having a broad molecular weight distribution, can be prepared discontinuously or continuously in the gaseous phase or in hydrocarbons as dispersants, at a pressure of from 2 to 40 bar and at a temperature of from 60.degree. C. to 100.degree. C., optionally with the use of hydrogen as a molecular weight regulator in the presence of a catalyst solid which is manufactured in two reaction steps, from a primary solid containing magnesium and chlorine which has been reacted, in a reaction stage A, with peroxy compound(s) and with halogen-containing metal compounds of elements of IV and/or V sub-group(s) of the Mendeleev Periodic Table and, in reaction stage B, with halogen-containing metal compounds of elements of IV and/or V subgroup(s) of the Mendeleev Periodic Table, and/or metal organyl compounds of metals of the II and/or III main group(s) of the Mendeleev Periodic Table.Type: GrantFiled: May 1, 1981Date of Patent: January 11, 1983Assignee: Wacker-Chemie GmbHInventor: Dieter Kurz
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Patent number: 4368304Abstract: A process for producing .alpha.-olefin polymers is provided, which comprises: reacting an organoaluminum compound with an electron donor in a specified ratio in a solvent at a specified temperature to obtain a solid product (I); reacting solid product (I) with TiCl.sub.4 at a specified temperature in a specified ratio of Al/Ti and then removing a liquid portion from the resulting material followed by washing to obtain a solid product (II) having no free TiCl.sub.4 ; reacting solid product (II) with an electron donor and an electron acceptor in a specified ratio at a specified temperature to obtain a solid product (III); and polymerizing .alpha.-olefin(s) in the presence of a catalyst comprising a combination of solid product (III) with an organoaluminum compound. This process provides a catalyst having a high storing and thermal stability and a polymer having a uniform particle size.Type: GrantFiled: February 4, 1981Date of Patent: January 11, 1983Assignee: Chisso CorporationInventors: Akihiro Sato, Toshihiro Uwai, Tohru Hanari, Kazutsune Kikuta, Masazumi Miyajima
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Patent number: 4366298Abstract: Poly-.alpha.-olefins, particularly polyethylene, having a broad molecular-weight distribution, can be prepared in the presence of a catalyst solid which is manufactured in two reaction steps, from a primary solid containing magnesium and chlorine which has been reacted, in a reaction stage A, with secondary and/or tertiary alcohols and with halogen-containing metal compounds of elements of IV and/or V sub-group(s) of the Mendeleev Periodic Table, and, in a reaction stage B, with halogen-containing metal compounds of elements of IV and/or V sub-group(s) of the Mendeleev Periodic Table and metal organyl compounds of metals of the II and/or III main group(s) of the Mendeleev Periodic Table. The sequence of the reaction stages A and B is not critical for the success of the process according to the invention.Type: GrantFiled: June 19, 1980Date of Patent: December 28, 1982Assignee: Wacker-Chemie GmbHInventor: Dieter Kurz
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Patent number: 4363901Abstract: A process for producing high-quality .alpha.-olefin polymers with a higher yield in a long lasting stabilized manner even in the case of gas phase polymerization is provided. In the production process of .alpha.-olefin polymers which comprises reacting a trivalent metal halide with a divalent metal compound to obtain a solid product (I); reacting this product with at least one electron donor (ED) and at least one electron acceptor (EA), once to 10 times, and at that time, using TiCl.sub.4 at least once as the (EA) to obtain a solid product (II); combining this product with an organoaluminum compound (OAl) and an (ED) (these three being referred to as catalyst components), the improvement which comprises subjecting a part or the whole of the catalyst components to polymerization treatment with a small amount of an .alpha.-olefin, at least in the coexistence of the solid product (II) and (OAl), in the combination of the catalyst components to obtain a preactivated catalyst, and subjecting .alpha.Type: GrantFiled: February 12, 1981Date of Patent: December 14, 1982Assignee: Chisso CorporationInventors: Kazutsune Kikuta, Masami Tachibana, Akihiro Sato
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Patent number: 4363902Abstract: Poly-.alpha.-olefins, particularly polyethylene, having a broad molecular-weight distribution, can be prepared in the presence of a catalyst solid which is manufactured in two reaction steps, from a primary solid containing magnesium and chlorine which has been reacted, in a reaction stage A, with alkoxy compounds of elements of Groups I to VI of the Mendeleev Periodic Table which contains at least one secondary or tertiary alkoxy group, and with halogen-containing metal compounds of elements of IV and/or V sub-group(s) of the Mendeleev Periodic Table and, in reaction stage B, with halogen-containing metal compounds of elements of IV and/or V sub-group(s) of the Mendeleev Periodic Table, and/or metal organyl compounds of metals of the II and/or III main group(s) of the Mendeleev Periodic Table. The sequence of the reaction stages A and B is not critical for the success of the process according to the invention.Type: GrantFiled: December 10, 1980Date of Patent: December 14, 1982Assignee: Wacker-Chemie GmbHInventor: Dieter Kurz
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Patent number: 4356295Abstract: A process for polymerizing an olefin which comprises causing the olefin to contact a catalyst comprising a combination of a component A which is a solid composition A obtained by causing:(a) a solid which contains a halogen-containing compound of a metal selected from the group consisting of magnesium, manganese, zinc and calcium,(b) a titanium compound,(c) a metal halide type Lewis acid which may be used as Friedel-Crafts catalyst, and(d) an organic compound selected from the group consisting of halohydrocarbons, halogen-containing organic acid esters and alcohols,to contact each other and a component B which is an organoaluminum compound.Type: GrantFiled: May 30, 1979Date of Patent: October 26, 1982Assignee: Mitsubishi Petrochemical Company LimitedInventors: Masaki Fujii, Shiro Goto
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Patent number: 4352915Abstract: In a slurry polymerization for producing an ethylene homopolymer or ethylene-.alpha.-olefin copolymer in multiple stages, in which the gas phase hydrogen concentration in each stage is different, using a catalyst system comprising a transition metal compound component and an organoaluminum compound component, the improvement which comprises conducting the polymerization by the use of a solid catalyst component comprising a titanium compound and/or vanadium compound supported on a specified magnesium compound, as the transition metal compound component, in a molar ratio of gas phase hydrogen to ethylene of 0.5 to 15 in the first stage thereby obtaining 30 to 95% by weight, of the total polymer, and in the second stage in a molar ratio of gas phase hydrogen to ethylene, not exceeding 0.2. By this process, it is possible to produce polyethylene having high melt flow and good homogeneity to give molded articles having fewer fish-eyes and less unevenness.Type: GrantFiled: May 23, 1980Date of Patent: October 5, 1982Assignee: Sumitomo Chemical Company, LimitedInventors: Kentaro Mashita, Katsumi Hanji
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Patent number: 4333851Abstract: A supported Ziegler catalyst prepared by reacting, under substantially anhydrous conditions, a refractory oxide support material having acidic surface hydroxyl groups, e.g. silica, and an organo metallic compound, e.g. a trialkyl aluminium compound, separating any unreacted organo metallic compound and impregnating the solid product with a halogen-containing titanium compound and a halogen-containing vanadium compound. The catalyst, preferably together with a conventional Ziegler catalyst activator, e.g. an aliminium alkyl, is employed to polymerize 1-olefins, for example ethylene.Type: GrantFiled: July 7, 1980Date of Patent: June 8, 1982Assignees: BP Chemicals Limited, The University of NottinghamInventors: John G. Speakman, Nicholas P. Wilkinson
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Patent number: 4330647Abstract: A process for polymerizing an .alpha.-olefin comprising contacting the olefin in liquid phase at a temperature of about 120.degree. to 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.t.alpha., p, q, r, s and t each independently is O or a number greater than 0,p+q+r+s=m.alpha.+2O.ltoreq.(r+s)/(.alpha.+1)<2,m is the valence of M, M is a metal of the 1st to 3rd groups of the Periodic Table,R.sup.1 is a hydrocarbon group having 1 to 20 carbon atoms, R.sup.2 is a secondary or tertiary alkyl group having 3 to 20 carbon atoms,X.sup.1 and X.sup.2 each independently is a hydrogen atom or an organic electronegative group containing O, N or S,D is an electron donor,with a compound (ii) of the formula,R.sub.a.sup.3 C Y.sub.4-awhereinR.sup.Type: GrantFiled: August 13, 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: 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: 4326988Abstract: A transition metal compound and a metal halide compound are chemically combined to form a composition of matter. The composition of matter is mixed with a precipitating agent to form an active olefin polymerization catalyst. The catalyst can be further treated with a halide ion exchanging source to form an active olefin polymerization catalyst. Prepolymer is deposited on the catalyst(s) in an amount effective to reduce polymer fines when the catalyst(s) are used in polymerization processes.Type: GrantFiled: August 12, 1980Date of Patent: April 27, 1982Assignee: Phillips Petroleum CompanyInventors: Melvin B. Welch, Richard E. Dietz, Charles E. Capshew
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Patent number: 4325837Abstract: A transition metal compound and a metal halide compound are chemically combined to form a composition of matter. The composition of matter is rapidly mixed with a precipitating agent to form an active olefin polymerization catalyst under an olefin atmosphere and prepolymer is formed on said catalyst to yield a catalyst capable of producing low fines content polymer.Type: GrantFiled: August 12, 1980Date of Patent: April 20, 1982Assignee: Phillips Petroleum CompanyInventors: Charles E. Capshew, James N. Short, M. Bruce Welch, Richard E. Dietz
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Patent number: 4325835Abstract: A component for an olefin polymerization catalyst which is the product of treating a particulate support material with (a) an organo-magnesium compound, (b) an aluminium compound e.g. ethyl aluminium dichloride, (c) an organometallic compound of general formula R.sub.m MX.sub.p wherein M is a metal of Groups IA, IIA, IIB, IIIB, VA or VIA of the Periodic Table, R is a hydrocarbyl or substituted hydrocarbyl group, X is a singly charged anionic ligand or a monodentate neutral ligand, m is an integer up to the highest valency of the metal M and p is 0 or an integer up to 2 less than the valency of the metal M, e.g. zirconium tetrabenzyl, and (d) at least one transition metal compound of Groups IVA, VA or VIA, e.g. titanium tetrachloride. The catalyst component can be used to effect copolymerization of ethylene with an alpha-olefin monomer such as butene-1 in a fluidized bed reactor.Type: GrantFiled: July 1, 1980Date of Patent: April 20, 1982Assignee: Imperial Chemical Industries LimitedInventors: Angus J. Hartshorn, Eric Jones
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Patent number: 4324691Abstract: A component for an olefin polymerisation catalyst which component is the product of treating a particulate support material with (a) an organomagnesium compound, (b) a transition metal compound of Groups IVA, VA or VIA, e.g. bis-butoxy titanium dichloride, (c) a pacifying agent, e.g. HCl and (d) optionally an aluminium compound, e.g. ethyl aluminium dichloride, an organometallic compound, e.g. zirconium tetrabenzyl, a halogenating agent e.g. silicon tetrachloride, or a Lewis Base compound, e.g. ethyl benzoate.Type: GrantFiled: July 1, 1980Date of Patent: April 13, 1982Assignee: Imperial Chemical Industries LimitedInventors: Angus J. Hartshorn, Eric Jones
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Patent number: 4324875Abstract: A method for producing .alpha.-olefin polymers or copolymers by the use of an improved catalyst consisting of a combination of an organoaluminum compound with a specified solid product (III) which is produced by reacting a trivalent metal halide with a divalent metal hydroxide, oxide, carbonate, or a composite compound containing the foregoing compound(s) or a hydrate of a compound containing a divalent metal; reacting the resultant solid product (I) with a transition metal compound in the presence of an electron donor to produce a solid product (II); and further reacting said solid product (II) with a halogen-containing transition metal compound and a halogen-free transition metal compound.Type: GrantFiled: May 21, 1980Date of Patent: April 13, 1982Assignee: Chisso CorporationInventors: Masato Harada, Sadahiko Yamada, Atsushi Suzuki, Jun Masuda
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Patent number: 4321345Abstract: A method for producing .alpha.-olefin polymers which enables to control molecular weight distribution in a narrower range, with a higher yield and a higher crystallinity of products, is proposed. A catalyst used in said method is also proposed. The solid component of said catalyst is obtained by reacting a trivalent metal halide with a hydroxide, an oxide, a carbonate of a divalent metal, a double compound containing any of these compounds or a hydrate of a compound containing a divalent metal to produce a solid product (I); reacting one or more electron donors and one or more electron acceptors separately or simultaneously each in from one step 10 steps but by using TiCl.sub.4 as an acceptor at least in one step, with said solid product (I) to obtain a solid product (II); and then combining an organoaluminum compound and an electron donor with said solid product (II).Type: GrantFiled: March 15, 1979Date of Patent: March 23, 1982Assignee: Chisso CorporationInventors: Akihiro Sato, Masami Tachibana, Kazutsune Kikuta
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Patent number: 4317897Abstract: A process for the preparation of an extensively amorphous homo- or copolymer of an .alpha.-olefin of 3-32 carbon atoms comprises polymerizing an .alpha.-olefin using a titanium-containing Ziegler-Natta catalyst, the catalyst comprising a mixture of(A) the reaction product of(a) a .mu.-oxoalkoxide of the formulaTi.sub.x O.sub.(x+y-1) M.sub.y.sup.m (OR.sup.1).sub.(2x+1) Z.sub.(m-1)ywhereinM is a metal of valence m,R.sup.1 is an alkyl residue of 1-10 carbon atoms,Z is C.sub.1-18 alkanoyloxy or C.sub.1-10 alkoxy,x is a whole or fractional number of 1-4,y is a whole or fractional number of 1-2 andm is 2,3 or 4;with(b) a halogen-containing organoaluminum compound of the formulaR.sub.n.sup.2 AlX.sub.3-nwhereinR.sup.2 is C.sub.1-16 alkyl,X is chlorine, bromine or iodine, andn is a whole or fractional number of 0.5-2.5, and(B) an aluminum trialkyl of up to 16 carbon atoms in each alkyl group.Type: GrantFiled: February 4, 1980Date of Patent: March 2, 1982Assignee: Chemische Werke Huels, A.G.Inventors: Christoph Herrmann, Roland Streck
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Patent number: 4311816Abstract: A solution polymerization process for the preparation of homopolymers of ethylene and copolymers of ethylene and higher .alpha.-olefins and a coordination catalyst for such a process are disclosed. In the process monomer is polymerized in the presence of the coordination catalyst which consists of a particular admixture of (a) a solution of an organoaluminum compound and an organomagnesium compound, with (b) a solution of a titanium compound and a vanadium compound. The catalyst exhibits relatively high activity in the polymerization of the monomers.Type: GrantFiled: May 5, 1980Date of Patent: January 19, 1982Assignee: E. I. Du Pont de Nemours and CompanyInventors: Alistair N. Mollison, Vaclay G. Zboril
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Patent number: 4309521Abstract: A process for producing .alpha.-olefin polymers is provided which comprises:reacting an organoaluminum compound (A.sub.1) with an electron donor (B.sub.1) to obtain a reaction product (I);reacting (I) with TiCl.sub.4 to obtain a solid product (II);reacting (II) with an electron donor (B.sub.2) and an electron acceptor to obtain a solid product (III);combining (III) with an organoaluminum compound (A.sub.2) and a reaction product (G) of an organoaluminum (A.sub.3) with an electron donor (B.sub.3) ((III), (A.sub.2) and (G) being referred to as catalyst components), and in this combination, subjecting a part or the whole of the catalyst components to polymerization treatment with an .alpha.-olefin at least in the presence of (III) and said (A.sub.2) to obtain a preliminarily activated catalyst;andpolymerizing an .alpha.-olefin in the presence of the catalyst.Type: GrantFiled: May 14, 1980Date of Patent: January 5, 1982Assignee: Chisso CorporationInventors: Akihiro Sato, Kazutsune Kikuta, Kenji Matsuda, Toshihiro Uwai, Tohru Hanari
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Patent number: 4304891Abstract: A process for producing .alpha.-olefins is provided which comprises:milling (A) a trivalent metal halide together with (B) a divalent metal compound, in a specified ratio of (A) to (B), and reacting them to obtain a solid product (I);reacting with this product (I), (C) an electron donor and (D) an electron acceptor, (C) and (D) being respectively reacted once or more up to ten times, and TiCl.sub.4 being employed as the electron acceptor at least once, to obtain a solid product (II);combining with this product (II), (E) a trialkylaluminum and (G) a reaction product of an electron donor with an electron acceptor, and in this combination, subjecting a part or the whole of the catalyst components (product (II), (E) and (G)) to polymerization treatment by reacting (F) an .alpha.-olefin at least in the presence of the product (II) and trialkylaluminum, to obtain a preliminarily activated catalyst; andpolymerizing an .alpha.-olefin in the presence of this catalyst.Type: GrantFiled: April 28, 1980Date of Patent: December 8, 1981Assignee: Chisso CorporationInventors: Akihiro Sato, Masami Tachibana, Kazutsune Kikuta, Yoshiharu Higuchi
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Patent number: 4298717Abstract: A process for polymerizing ethylene under high pressure and temperature in at least one reactor having at least one reaction zone. A catalyst system is used that comprises (a) an activator selected from trialkylaluminums, hologenodialkylaluminums, and alkylsiloxalanes, (b) a halogen compound of a transition metal of groups IV to VI A, and (c) a complexing agent that is injected into the reactor in such a manner that its concentration in the reactor may be adjusted independently from the concentration of (b). The complexing agent may be selected from silicone oils and from compounds having the formula X(OR).sub.n, wherein X is hydrogen or a metal, n is the valence of X, and R is an alkyl radical of up to 20 carbon atoms.Type: GrantFiled: August 1, 1978Date of Patent: November 3, 1981Assignee: Societe Chimique des Charbonnages-CdF ChimieInventor: Jean-Pierre Machon
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Patent number: 4297462Abstract: For the polymerization of ethylene, as such or with one or more alpha-olefines, a novel catalyst composition is suggested, which has a high yield of polymer per weight unit of catalyst. Such compositions are prepared from a titanium compound in which the valency of Ti is 3 or more, said compound being reacted with the vapors of one or more metals of the group consisting of Al, Cr, Mn, V, Ti, Zr, Mo, Zn and Ca in the presence of a halogen donor which is preferably an organic halide, certain inorganic halides being capable of being used provided that the halide metal has at least two degrees of valency. The composition is used in association with an aluminium hydrocarbyl halide. Yields as high as 30,000 grams of polymer per gram of elemental Ti can be obtained.Type: GrantFiled: September 25, 1979Date of Patent: October 27, 1981Assignees: Snamprogetti S.p.A, Anic S.p.AInventors: Margherita Corbellini, Alberto Greco, Mirko Osellame
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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: 4287328Abstract: A method for producing .alpha.-olefin polymers is provided. According to this method, particularly the catalyst stability is improved, resulting in polymers having a higher crystallinity, a narrower range of molecular weight, improved shape of polymer particles with a higher yield per a solid product component and per a transition metal component of the catalyst. Said catalyst is obtained by reacting a trivalent metal halide with a hydroxide, an oxide, a carbonate of a divalent metal, a double compound containing any of these compounds or a hydrate of a compound containing a divalent metal to form a solid product (I); reacting said solid product with one or more electron donors and one or more electron acceptors separately or simultaneously each in one to 10 steps but using TiCl.sub.Type: GrantFiled: March 21, 1979Date of Patent: September 1, 1981Assignee: Chisso CorporationInventors: Kazutsune Kikuta, Masami Tachibana, Akihiro Sato
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Patent number: 4267293Abstract: A catalyst for producing ethylene polymers in which a first component composed of titanium, vanadium, halogen, and OR groups, wherein R is selected from among alkyl, cycloalkyl, aryl, acyl, and combinations thereof, is combined with an organometallic compound. A method for producing a catalyst system in which an organoaluminum compound component is contacted with a component composition produced by reacting a mixture of titanium and vanadium compounds with an organometallic compound to form a product mixture which is then contacted with titanium tetrachloride. A method for producing polymers of ethylene by contacting ethylene with a catalyst system produced as above under conditions suitable for polymerization.Type: GrantFiled: December 21, 1979Date of Patent: May 12, 1981Assignee: Phillips Petroleum CompanyInventor: Darryl R. Fahey
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Patent number: 4260723Abstract: A method for producing .alpha.-olefin polymers or copolymers by the use of an improved catalyst having a specific solid product combined with an organoaluminum compound is provided.The specific solid product (III) is prepared byreacting a trivalent metal halide with a specified divalent metal compound to obtain a solid product (I);reacting this product (I) with a transition metal compound of 4a group or 5a group of the Periodic Table in the presence of a polysiloxane to obtain a solid product (II); andfurther reacting this product (II) with at least two transition metal compounds of 4a group or 5a group, consisting of at least one member selected from the group (A) consisting of halogen-containing transition metal compounds of 4a group or 5a group, and at least one member selected from the group (B) consisting of halogen-free transition metal compounds of 4a group or 5a group to obtain the solid product (III).By employing this improved solid product (III) as a catalyst component, it is possible to produce .Type: GrantFiled: June 25, 1979Date of Patent: April 7, 1981Assignee: Chisso CorporationInventors: Masato Harada, Yoshikatsu Ishigaki, Sadahiko Yamada, Atsushi Suzuki, Jun Masuda, Tadamitsu Hamazaki, Toshiaki Yoshida, Kiyoto Fukuda
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Patent number: 4258159Abstract: A process for low temperature polymerization and copolymerization of alpha-olefins comprising conducting the polymerization in the presence of a catalytic system comprising an organic compound of a metal of Group IA, IIA, IIB, IIIA and IVA of the Periodic Table and a solid catalytic complex which is prepared by reacting a compound of a metal of Groups IVB, VB and VIB of the Periodic Table with a porous aluminum oxide on which a magnesium compound is deposited.Type: GrantFiled: December 4, 1975Date of Patent: March 24, 1981Assignee: Solvay & CieInventor: Charles Bienfait
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Patent number: 4246383Abstract: Solid supported catalysts which can be employed for the polymerization of .alpha.-olefins are prepared by (A) reacting in the presence of a diluent such as n-hexane a mixture of (1) the reaction product of (a) an organo magnesium compound such as dibutyl magnesium and (b) at least one of water, carbon dioxide or an organic, oxygen-containing compound such as n-propyl alcohol; and (2) a transition metal halide such as titanium tetrachloride and (B) recovering the solid precipitate such as by decanting and (C) washing the solid with a solvent such as n-hexane. The resultant solid supported catalyst contains sufficient transition metal which when activated with a suitable activating agent serves as a polymerization catalyst for .alpha.-olefins. The polymers prepared employing these catalysts have a relatively narrow molecular weight distribution and low residual amounts of transition metal and halides.Type: GrantFiled: June 25, 1979Date of Patent: January 20, 1981Assignee: The Dow Chemical CompanyInventor: Donald E. Gessell
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Patent number: 4245071Abstract: This invention relates to an improved process for the polymerization and copolymerization of olefins, to the novel catalytic component and catalytic system used for such polymerization and to a process for preparing such catalytic system, in which the polymerization of the olefins is carried out in the presence of a catalytic system comprising an organometallic compound of a metal of Group I, II, or III or the Periodic Table and a solid catalytic component obtained by reacting together metallic magnesium, a hydroxylated organic compound, an organic oxygenated compound of a metal of Group IVb, Vb, or VIb of the Periodic Table, an aluminum halide, and a halogen-containing compound of a metal of Group IVb, Vb or VIb of the Periodic Table.Type: GrantFiled: November 14, 1977Date of Patent: January 13, 1981Assignee: Solvay & Cie.Inventors: Yozo Kondo, Toshikazu Kasai, Yoshiaki Kano
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Patent number: 4239873Abstract: An alpha-olefin such as ethylene is polymerized in the presence of a catalyst system consisting of (1) an alkyl-halide, alkyl-derivative or hydride of a metal belonging to one of the first three groups of the periodic system and (2) the combination product of a transition metal chloride and titanium trichloride, supported on a previously chlorinated material such as chlorinated .gamma.-alumina having a high superficial area.Type: GrantFiled: December 23, 1977Date of Patent: December 16, 1980Assignee: SnamprogettiInventors: Sebastiano Cesca, Alberto Greco, Guglielmo Bertolini, Mario Bruzzone
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Patent number: 4233182Abstract: High activity alpha-olefin polymerization catalysts comprising an organometallic promoter and a component prepared from at least one compound of a Group IVB, VB, or VIB metal, at least one support material which is a divalent metal salt of a phosphorus acid ester having at least one phosphorous acid ester group bonded to metal through oxygen or sulfur, and at least one alkylaluminum halide.Type: GrantFiled: December 26, 1978Date of Patent: November 11, 1980Assignee: Standard Oil Company (Indiana)Inventors: Glen R. Hoff, Peter Fotis
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Patent number: 4226965Abstract: Polymerization or copolymerization of the starting monomers is carried out in a hydrocarbon medium in the presence of a catalyst containing an alkylaluminium chloride compound, a trialkylvanadate and an alkoxyderivative of titanium, or zirconium, or hafnium. The method of the present invention makes it possible to considerably increase the polymerization rate and degree of conversion in the preparation of polymers and copolymers of higher .alpha.-olefines. The resulting polymers of higher .alpha.-olefines have a stereoregular structure with a high degree of crystallinity which is manifested in an increased melting point of the resulting polymer.Type: GrantFiled: September 28, 1978Date of Patent: October 7, 1980Inventors: Vasily A. Grigoriev, Zinaida V. Arkhipova, Gurgen A. Balaev, Nikolai G. Bakajutov, Vera I. Vysotskaya, Arkady V. Polyakov, Vitaly M. Zapletnyak
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Patent number: 4217245Abstract: A novel catalyst system for the polymerization or copolymerization of olefines, more particularly to ethylene is disclosed. For preparing the novel catalyst system, a titanium compound (Ti IV) is previously attached to a solid supporting member, whereafter the so anchored Ti is reacted with vapors of a metal, in the presence of a halogenated compound or not. Very high polymer yields are obtained and examples are given.Type: GrantFiled: June 2, 1978Date of Patent: August 12, 1980Assignee: Snamprogetti, S.p.A.Inventors: Margherita Corbellini, Alessandro Gamba, Carlo Busetto
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Patent number: 4203866Abstract: For the polymerization of ethylene, as such or with one or more alpha-olefins, a novel catalyst composition is described, which gives a high yield of polymer per weight unit of catalyst. Such compositions are prepared from a titanium compound in which the valency of Ti is 3 or more, said compound being reacted with the vapors of one or more metals of the group consisting of Al, Cr, Mn, V, Ti, Zr, Mo, Zn and Ca in the presence of a halogen donor which is preferably an organic halide, certain inorganic halides being capable of being used provided that the halide metal has at least two degrees of valency. The composition is used in association with an aluminium hydrocarbyl halide. Yields as high as 30,000 grams of polymer per gram of elemental Ti can be obtained.Type: GrantFiled: June 16, 1978Date of Patent: May 20, 1980Assignee: Snamprogetti, S.p.A.Inventors: Margherita Corbellini, Alberto Greco, Mirko Osellame
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Patent number: 4199475Abstract: A catalyst for producing polymers of ethylene in which a first composition prepared by reacting an inorganic support containing surface hydroxyl groups with titanium or vanadium compounds which also comprise halogen and/or OR groups wherein R is hydrocarbyl is further reacted to form a second composition by subsequent contact with a compound of titanium or vanadium as defined above chosen from compounds of the metal not reacted to form the first composition, producing a third composition by reaction of the second composition with an organoaluminum compound with the third composition being reacted with titanium tetrahalide to form the catalyst composite. A method for producing polymers of ethylene by contacting ethylene monomer in the presence of the catalyst composite described above and an organoaluminum compound under conditions suitable for polymerization.Type: GrantFiled: September 22, 1978Date of Patent: April 22, 1980Assignee: Phillips Petroleum CompanyInventors: M. Bruce Welch, Darryl R. Fahey