Nontransition Heavy Metal Compound Is Halogen-containing Patents (Class 526/122)
  • Patent number: 4518752
    Abstract: A process for the homopolymerization or copolymerization of olefins is disclosed, which is carried out in the presence of an improved catalyst comprising a solid catalyst component and an organometal compound, said solid catalyst component being obtained by the reaction of: (a) a magnesium halide, (b) a compound represented by the formula: Me(OR).sub.n X.sub.z-n where Me is any of the Group I-VIII elements of the Periodic Table, excluding Al, Si, Ti and V, R is a hydrocarbon residual group having 1-24 carbon atoms, X is a halogen atom, z represents the valence of Me and n is 0<n.ltoreq.z, and (c) a compound represented by the formula: Si(OR').sub.m X.sub.4-m where R' is a hydrocarbon residual group having 1-20 carbon atoms, X is a halogen atom, and m is 0.ltoreq.m.ltoreq.4, and (d) a titanium compound and/or a vanadium compound. The resulting polymers are characterized by a large bulk density, a narrow range of molecular weight distribution, and small amounts of hexane extraction.
    Type: Grant
    Filed: November 15, 1983
    Date of Patent: May 21, 1985
    Assignee: Nippon Oil Co., Ltd.
    Inventors: Nobuyuki Kuroda, Toru Nakamura, Yutaka Shikatani, Kazuo Matsuura
  • Patent number: 4507449
    Abstract: A process for producing a novel highly active vanadium catalyst comprising a particulate solid produced by reacting a vanadium compound, a phosphorus compound, and a metal halide compound and its use in the polymerization of olefins.
    Type: Grant
    Filed: August 16, 1983
    Date of Patent: March 26, 1985
    Inventor: Joel L. Martin
  • Patent number: 4499247
    Abstract: A superior high-rigidity and high-melt-viscoelasticity polypropylene for sheets to be post-processed and for blow molding is provided which polypropylene is produced by subjecting propylene to a multi-stage polymerization into polymer portions of two sections in the presence of a specified Ziegler Natta catalyst, the relationship between the intrinsic viscosities of the polymer portions of the respective sections being regulated within a specified range and also the amount ratio of the polymer portions of the respective sections being regulated.
    Type: Grant
    Filed: June 7, 1983
    Date of Patent: February 12, 1985
    Assignee: Chisso Corporation
    Inventors: Hiromasa Chiba, Kenjiro Obama, Shunji Kawazoe, Takahiro Oka, Akihiro Satoh
  • Patent number: 4495338
    Abstract: Catalysts useful in the polymerization of olefins, more particularly of ethylene and mixtures thereof with alpha-olefins and/or diolefins, are disclosed. The new catalysts are obtained by mixing a halide of titanium or vanadium in which the metal has a valency lower than 4, with a support comprising an anhydrous magnesium or zinc halide in an active form under particular conditions, and then activating the resulting product with a hydride or organometallic compound of a metal belonging to Groups I to III, inclusive, of the Mendelyeev Periodic System.
    Type: Grant
    Filed: September 24, 1980
    Date of Patent: January 22, 1985
    Assignee: Montecatini Edison S.p.A.
    Inventors: Adolfo Mayr, Ermanno Susa, Ettore Giachetti
  • Patent number: 4483971
    Abstract: A process for producing terpolymers of propylene (as a main monomer), ethylene and another .alpha.-olefin having superior and well-balanced physical properties, almost without forming soluble polymer is provided.This process is characterized by preliminarily activating a catalyst consisting of a titanium trichloride composition and a specified organoaluminum halide, with a small amount of an .alpha.-olefin of 2 to 12 carbon atoms, a trialkylaluminum and an aromatic ester, and copolymerizing specified amounts of propylene, ethylene and an .alpha.-olefin of 4 to 12 carbon atoms in the presence of the preliminarily activated catalyst obtained above.
    Type: Grant
    Filed: February 25, 1983
    Date of Patent: November 20, 1984
    Assignee: Chisso Corporation
    Inventors: Akihiro Sato, Takeshi Suzuki, Kazutsune Kikuta, Hiromasa Chiba, Toshihiro Uwai, Kenji Matsuda, Tohru Hanari
  • Patent number: 4476289
    Abstract: Catalysts useful in the polymerization of olefins, more particularly of ethylene and mixtures thereof with higher alpha-olefins and/or diolefins, are disclosed. The new catalysts are obtained by mixing a hydride or organometallic compound of a metal belonging to Groups I to III of the Mendelyeev Periodic System with the product obtained by contacting a titanium tetrahalide with a support comprising an anhydrous magnesium or zinc halide in an active form, under particular conditions.
    Type: Grant
    Filed: June 2, 1981
    Date of Patent: October 9, 1984
    Assignee: Montecatini Edison S.p.A.
    Inventors: Adolfo Mayr, Ermanno Susa, Ettore Giachetti
  • Patent number: 4460757
    Abstract: A process for producing highly crystalline .alpha.-olefin polymers of good particle form with high yield is provided, which comprises polymerizing .alpha.-olefin in the presence of a preactivated catalyst obtained by reacting a reaction product (I) of organoaluminum compound (A.sub.1) with electron donor (B.sub.1), with TiCl.sub.4 to obtain a solid product (II); further reacting (II) with electron donor (B.sub.2) and electron acceptor to obtain a solid product (III); during or/and after the reaction step for obtaining (II) or/and during or/and after the reaction step for obtaining (III), subjecting (II) or (III), to polymerization treatment with .alpha.-olefin; and combining the resulting final solid product with organo-aluminum compound (A.sub.2) and a reaction product (G) of organo-aluminum compound (A.sub.3) with electron donor (B.sub.3) to obtain a preactivated catalyst; and preferably, in this combination, further subjecting a part or the total of the catalyst to polymerization treatment with .alpha.
    Type: Grant
    Filed: July 29, 1982
    Date of Patent: July 17, 1984
    Assignee: Chisso Corporation
    Inventors: Akihiro Sato, Masami Tachibana, Toshihiro Uwai, Kenji Matsuda, Yoshiharu Higuchi
  • Patent number: 4451626
    Abstract: Alpha olefins are polymerized in the presence of catalyst compositions which are the catalytic reaction products of (A) the reaction product or complex resulting from the mixing of (1) a mixture of a transition metal compound such as a tetraalkoxy titanium compound, a non-metallic oxygen-containing compound such as an alcohol and (2) a reducing alkylating agent such as a dialkyl magnesium compound and (B) a magnesium halide.
    Type: Grant
    Filed: March 30, 1983
    Date of Patent: May 29, 1984
    Assignee: The Dow Chemical Company
    Inventors: Randall S. Shipley, Donald F. Birkelbach
  • Patent number: 4446289
    Abstract: A novel process is disclosed for polymerizing and copolymerizing alpha olefins (ethylene included) also in the presence of conjugated diolephins, and more particularly for copolymerizing ethylene with 1,3-butadiene, based on the use of a plural-component catalyst system, one of said components being a novel complex which contains titanium and magnesium. The process gives, in yields higher than 200,000 grams of polymer per g of elemental Ti, ethylene-butadiene copolymers having a distribution of monomeric units characterized by a particular novel .sup.13 C-NMR spectrum, a high apparent specific gravity and such a grit size as to impart flowability to the dry product, and a distribution in the presence of sulphur and accelerators such as to acquire a gel content (fraction insoluble in boiling xylenes) over 50%.
    Type: Grant
    Filed: July 15, 1982
    Date of Patent: May 1, 1984
    Assignee: Agip Petroli S.p.A.
    Inventors: Antonio Carbonaro, Cesare Ferrero, Margherita Corbellini
  • Patent number: 4429087
    Abstract: A transition metal compound such as titanium tetrahydrocarbyloxides and a metal hydrocarbyloxide compound such as magnesium hydrocarbyloxides are chemically combined to form a first catalyst component which is treated with a second catalyst component comprising an organometallic compound precipitating agent to produce an active olefin polymerization catalyst. High polymer yields are realized per gram of catalyst when the catalyst thus produced is treated with a halide ion exchanging source and used with an organometallic cocatalyst.
    Type: Grant
    Filed: March 11, 1982
    Date of Patent: January 31, 1984
    Assignee: Phillips Petroleum Company
    Inventor: Charles E. Capshew
  • Patent number: 4429089
    Abstract: 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: Grant
    Filed: July 15, 1981
    Date of Patent: January 31, 1984
    Assignee: Anic, S.p.A.
    Inventors: Ugo Pedretti, Gabriele Lugli, Sergio Poggio, Alessandro Mazzei
  • Patent number: 4419501
    Abstract: A process for the preparation of an olefin polymerization catalyst component which comprises contacting a solid composition obtained by combining a magnesium halide, an electron donor and a tetravalent titanium compound, this composition being substantially free from aluminum compounds, with a liquid medium comprising a halide of B, Al, Ga, In, Tl, Sn or Sb, these elements being present in their highest valency state or a halide of tetravalent Te, and removing from the catalyst component substantially all metal halide originating from the liquid medium as by washing the catalyst component with a hydrocarbon or halohydrocarbon liquid.
    Type: Grant
    Filed: February 4, 1982
    Date of Patent: December 6, 1983
    Assignee: Shell Oil Company
    Inventors: Brian L. Goodall, Jacob C. Van Der Sar
  • Patent number: 4418184
    Abstract: 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 sys
    Type: Grant
    Filed: March 22, 1982
    Date of Patent: November 29, 1983
    Assignee: Mitsui Petrochemical Industries, Ltd.
    Inventors: Takashi Ueda, Norio Kashiwa
  • Patent number: 4415712
    Abstract: 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: Grant
    Filed: March 1, 1982
    Date of Patent: November 15, 1983
    Assignee: The Dow Chemical Company
    Inventors: Randall S. Shipley, Larry E. Freyer
  • Patent number: 4410671
    Abstract: 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: Grant
    Filed: February 22, 1982
    Date of Patent: October 18, 1983
    Assignee: Phillips Petroleum Company
    Inventors: Melvin B. Welch, Richard E. Dietz, Charles E. Capshew
  • Patent number: 4405769
    Abstract: 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.
    Type: Grant
    Filed: February 22, 1982
    Date of Patent: September 20, 1983
    Inventors: Charles E. Capshew, James N. Short, M. Bruce Welch, Richard E. Dietz
  • Patent number: 4403081
    Abstract: A method for producing .alpha.-olefin polymers is provided. This method provides products having superior properties such as higher bulk density and uniform particle form which is close to sphere, with such an extremely higher catalyst efficiency that ash-removal step can be omitted without fear of coloring.
    Type: Grant
    Filed: February 21, 1979
    Date of Patent: September 6, 1983
    Assignee: Chisso Corporation
    Inventors: Masato Harada, Akihiro Sato, Sadahiko Yamada, Kazutsune Kikuta, Atsushi Suzuki, Hiroshi Shimizu, Jun Masuda, Tadamitsu Hamasaki, Atsuyuki Kachi
  • Patent number: 4396748
    Abstract: Alpha olefins are polymerized in the presence of catalyst compositions which are the catalytic reaction products of (A) the reaction product or complex resulting from the mixing of (1) a mixture of a transition metal compound such as a tetraalkoxy titanium compound and an alcohol and (2) an essentially non-reducing alkylating agent such as a dialkyl zinc compound and (B) a magnesium halide.
    Type: Grant
    Filed: October 22, 1981
    Date of Patent: August 2, 1983
    Assignee: The Dow Chemical Company
    Inventor: Randall S. Shipley
  • Patent number: 4394291
    Abstract: A method for making novel catalysts for the polymerization of olefins, said catalysts being prepared by reacting a metal dihalide with certain transition metal compounds and reacting that product with certain organoaluminum compounds wherein in one embodiment that product is contacted with a halide exchanging source selected from halides of Groups IVA and VA of the Periodic Table and wherein in another embodiment a third component, such as an electron donor, is included in the reaction between the metal dihalide and the transition metal compound.
    Type: Grant
    Filed: March 4, 1981
    Date of Patent: July 19, 1983
    Assignee: Phillips Petroleum Company
    Inventor: Gil R. Hawley
  • Patent number: 4390671
    Abstract: A supported titanium catalyst component is produced by cogrinding an organo aluminum catalyst component with a supported titanium (IV) halide on a magnesium halide. The resulting supported titanium halide catalyst component, when employed with an organo aluminum catalyst component to form a catalyst system is highly useful for the stereoregular polymerization of .alpha.-olefins as well as the copolymerization of .alpha.-olefins.
    Type: Grant
    Filed: September 26, 1980
    Date of Patent: June 28, 1983
    Assignee: Toa Nenryo Kogyo Kabushiki Kaisha
    Inventors: Masafumi Imai, Hiroshi Ueno, Naomi Inaba, Makoto Yoda, Shozo Wada
  • Patent number: 4389518
    Abstract: 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: Grant
    Filed: August 25, 1981
    Date of Patent: June 21, 1983
    Assignee: Chisso Corporation
    Inventors: Masato Harada, Atsushi Suzuki, Sadahiko Yamada, Jun Masuda
  • Patent number: 4387200
    Abstract: 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: Grant
    Filed: March 22, 1982
    Date of Patent: June 7, 1983
    Assignee: The Dow Chemical Company
    Inventors: Donald E. Gessell, Ronald L. Gibbs, Ricardo Fuentes, Jr.
  • Patent number: 4387198
    Abstract: 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: Grant
    Filed: March 12, 1980
    Date of Patent: June 7, 1983
    Assignee: Chisso Corporation
    Inventors: Akihiro Sato, Masami Tachibana, Kazutsune Kikuta, Yoshiharu Higuchi, Masazumi Miyajima
  • Patent number: 4384983
    Abstract: Catalyst for production of polyolefins of improved morphology comprises (A) organometallic promoter and (B) reaction product of (1) at least one hydrocarbon-soluble aromatic nitro compound with (2) catalytic complex comprising an intimate association of at least one reduced Group IVB-VB metal halide, at least one divalent metal halide and at least one aluminum compound. Aromatic nitro compound is used in an amount effective to improve polymer morphology without substantial adverse effects on other catalytic properties.
    Type: Grant
    Filed: May 26, 1981
    Date of Patent: May 24, 1983
    Assignee: Standard Oil Company (Indiana)
    Inventor: Glen R. Hoff
  • Patent number: 4384087
    Abstract: 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: Grant
    Filed: August 20, 1981
    Date of Patent: May 17, 1983
    Assignee: Phillips Petroleum Company
    Inventor: Charles E. Capshew
  • Patent number: 4379074
    Abstract: 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: Grant
    Filed: December 5, 1980
    Date of Patent: April 5, 1983
    Assignees: Anic S.p.A., Snamprogetti, S.p.A.
    Inventors: Agostino Balducci, Margherita Corbellini, Mirko Osellame
  • Patent number: 4378455
    Abstract: 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: Grant
    Filed: February 19, 1980
    Date of Patent: March 29, 1983
    Assignee: Maruzen Petrochemical Co., Ltd.
    Inventors: Akihiro Kawasaki, Tsuyoshi Matsumoto, Masanobu Taniguchi, Isao Maruyama, Masaaki Matsui, Masao Kaneko, Akihiko Imai
  • Patent number: 4376064
    Abstract: Catalyst for production of polyolefins of improved morphology comprises (A) organometallic promoter and (B) product obtained by contacting (1) at least one oxygenated compound of phosphorus with (2) catalytic complex comprising an intimate association of at least one reduced Group IVB-VB metal halide, at least one divalent metal halide and at least one aluminum compound. Oxygenated phosphorus compound is used in an amount effective to improve polymer morphology without substantial adverse effects on other catalytic properties.
    Type: Grant
    Filed: May 26, 1981
    Date of Patent: March 8, 1983
    Assignee: Standard Oil Co. (Indiana)
    Inventors: Glen R. Hoff, Peter Fotis
  • Patent number: 4368304
    Abstract: 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: Grant
    Filed: February 4, 1981
    Date of Patent: January 11, 1983
    Assignee: Chisso Corporation
    Inventors: Akihiro Sato, Toshihiro Uwai, Tohru Hanari, Kazutsune Kikuta, Masazumi Miyajima
  • Patent number: 4367321
    Abstract: A process for the preparation of homopolymers and copolymers of .alpha.-monoolefins by polymerizing the monomer or monomers with a Ziegler catalyst system comprising (1) a titanium-containing catalyst component and (2) a relevant conventional organo-aluminum compound, (1.1) the catalyst component (1) having been prepared by (1.1.1) milling a titanium compound (I) of the formula TiCl.sub.3.z(AlCl.sub.3) or Cl.sub.m Ti(OB).sub.4-m, where z is from 0 to 0.5, m is from 0 to 3 and B is alkyl, together with (1.1.2) a magnesium alcoholate (II) and, if desired, (1.1.3) a metal chloride (III) of the formula AlCl.sub.3, ZnCl.sub.2 or MnCl.sub.2, to form a milled product (IV), in which polymerization process a catalyst component (1) is employed, in the preparation of which (1.2) the milled product (IV) obtained according to (1.1) is brought together, in an additional step (1.2.1), with (1.2.2) an alkanol (V) and (1.2.3) a liquid alkane (VI), to form a suspension (VII), and thereafter (1.
    Type: Grant
    Filed: March 31, 1981
    Date of Patent: January 4, 1983
    Assignee: BASF Aktiengesellschaft
    Inventors: Robert Bachl, Peter Klaerner, Guenther Schweier, Ehler Ehlers
  • Patent number: 4366297
    Abstract: In a process for producing a rubber olefin copolymer which comprises random copolymerization of at least two olefins in the presence of a catalyst composed of (A) a titanium compound and (B) an organometallic compound of a metal of Groups I to III of the periodic table, the improvement wherein the titanium compound (A) is a liquid product obtained by treating a titanium tetrahalide of the general formula TiX.sub.4 in which X represents Cl, Br or I in a hydrocarbon, a halogenated hydrocarbon or a mixture of both in the presence of an ether with at least one member selected from the group consisting of (1) an organoaluminum compound, (2) an organomagnesium compound and (3) a combination of hydrogen and at least one metal or metal compound selected from the group consisting of metals of Group IB, IIB, IVB and VIII of the periodic table, compounds of metals of Group VIII of the periodic table, cuprous chloride, titanium hydride and zirconium hydride.
    Type: Grant
    Filed: October 23, 1980
    Date of Patent: December 28, 1982
    Assignee: Japan EP Rubber Co., Ltd.
    Inventors: Kenya Makino, Hideo Sakurai, Masaru Watanabe, Toshiyuki Nishimura
  • Patent number: 4363901
    Abstract: 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: Grant
    Filed: February 12, 1981
    Date of Patent: December 14, 1982
    Assignee: Chisso Corporation
    Inventors: Kazutsune Kikuta, Masami Tachibana, Akihiro Sato
  • Patent number: 4363902
    Abstract: 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: Grant
    Filed: December 10, 1980
    Date of Patent: December 14, 1982
    Assignee: Wacker-Chemie GmbH
    Inventor: Dieter Kurz
  • Patent number: 4359563
    Abstract: Copolymers of acetylene are prepared by catalytic polymerization of mixtures of acetylene and heteroalkynes with Ziegler catalysts. The polymers may be used as pigments or as colored coatings on metal, glass or plastic.
    Type: Grant
    Filed: May 19, 1981
    Date of Patent: November 16, 1982
    Assignee: BASF Aktiengesellschaft
    Inventors: Herbert Naarmann, Klaus Penzien, Heinz G. Viehe
  • Patent number: 4356295
    Abstract: 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: Grant
    Filed: May 30, 1979
    Date of Patent: October 26, 1982
    Assignee: Mitsubishi Petrochemical Company Limited
    Inventors: Masaki Fujii, Shiro Goto
  • Patent number: 4354010
    Abstract: A solid transition metal compound is ground with an organo-sulphur compound which is a defined aromatic sulphone, sulphonamide or sulphide such as diphenylsulphone, N,N-diethyl-4-phenoxy benzenesulphonamide or phenoxathiin. A Lewis Acid such as titanium tetrachloride can be present during the grinding operation. Alternatively there may be present, during the grinding, an oxidizing agent capable of generating tetravalent titanium in the presence of titanium trichloride, for example carbon tetrachloride or gaseous oxygen. The grinding can be effected in a ball-mill or a vibrating mill. The materials may be added during the grinding and the temperature may be varied during the grinding. A liquid which is a solvent for the organo-sulphur compound or complexes thereof with aluminum chloride may be present during a part of the grinding.
    Type: Grant
    Filed: September 24, 1980
    Date of Patent: October 12, 1982
    Assignee: Imperial Chemical Industries Limited
    Inventor: Alan B. Newton
  • Patent number: 4343721
    Abstract: A process for the preparation of an olefin polymerization catalyst component which comprises contacting a solid composition obtained by combining a magnesium halide, an electron donor and a tetravalent titanium compound, this composition being substantially free from aluminum compounds, with a liquid medium comprising a halide of B, Al, Ga, In, Tl, Sn or Sb, these elements being present in their highest valency state or a halide of tetravalent Te, and removing from the catalyst component substantially all metal halide originating from the liquid medium as by washing the catalyst component with a hydrocarbon or halohydrocarbon liquid.
    Type: Grant
    Filed: November 18, 1980
    Date of Patent: August 10, 1982
    Assignee: Shell Oil Company
    Inventors: Brian L. Goodall, Jacob C. van der Sar
  • Patent number: 4335229
    Abstract: 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: Grant
    Filed: August 13, 1980
    Date of Patent: June 15, 1982
    Assignee: Asahi Kasei Kogyo Kabushiki Kaisha
    Inventors: Hisaya Sakurai, Yoshihiko Katayama, Tadashi Ikegami, Masayasu Furusato
  • Patent number: 4330646
    Abstract: 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: Grant
    Filed: July 21, 1980
    Date of Patent: May 18, 1982
    Assignee: Asahi Kasei Kogyo Kabushiki Kaisha
    Inventors: Hisaya Sakurai, Yoshihiko Katayama, Tadashi Ikegami, Masayasu Furusato
  • Patent number: 4326988
    Abstract: 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: Grant
    Filed: August 12, 1980
    Date of Patent: April 27, 1982
    Assignee: Phillips Petroleum Company
    Inventors: Melvin B. Welch, Richard E. Dietz, Charles E. Capshew
  • Patent number: 4325837
    Abstract: 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: Grant
    Filed: August 12, 1980
    Date of Patent: April 20, 1982
    Assignee: Phillips Petroleum Company
    Inventors: Charles E. Capshew, James N. Short, M. Bruce Welch, Richard E. Dietz
  • Patent number: 4324875
    Abstract: 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: Grant
    Filed: May 21, 1980
    Date of Patent: April 13, 1982
    Assignee: Chisso Corporation
    Inventors: Masato Harada, Sadahiko Yamada, Atsushi Suzuki, Jun Masuda
  • Patent number: 4324692
    Abstract: A process for preparing a supported Ziegler catalyst component by reacting together an alcohol and a halogen-containing transition metal compound in the presence of a zinc halide, and impregnating a support material having surface hydroxyl groups with the reaction mixture. The alcohol can be aliphatic or aromatic, for example, isopropanol. The transition metal compound can be, for example, a halide, halo-alkoxide or oxyhalide of titanium, vanadium, zirconium or chromium. The zinc halide is preferably zinc chloride. The supported catalyst component can be activated using conventional Ziegler catalyst activators and used to polymerize 1-olefins.
    Type: Grant
    Filed: October 8, 1980
    Date of Patent: April 13, 1982
    Assignee: BP Chemicals Limited
    Inventor: Alexander Johnstone
  • Patent number: 4323665
    Abstract: .alpha.-Olfins, particularly higher olefins, are polymerized in the presence of a catalyst prepared by reacting (A) tetravalent tianium compounds such as titanium tetraalkoxide, (B) an organoaluminum compound, (C) an organomagnesium component such as a hydrocarbon soluble complex of dialkyl magnesium and an organoaluminum compound such as triethyl aluminum and, (D) as a halide source, a tetravalent tin compound such as tin tetrachloride. Polymers prepared by this process provide higher efficiencies than polymers prepared from a process utilizing catalysts employing HCl as the halide source.
    Type: Grant
    Filed: April 14, 1980
    Date of Patent: April 6, 1982
    Assignee: The Dow Chemical Co.
    Inventors: Kirby Lowery, Jr., Donald F. Birkelbach, Randall S. Shipley
  • Patent number: 4321345
    Abstract: 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: Grant
    Filed: March 15, 1979
    Date of Patent: March 23, 1982
    Assignee: Chisso Corporation
    Inventors: Akihiro Sato, Masami Tachibana, Kazutsune Kikuta
  • Patent number: 4314911
    Abstract: New, highly active catalysts for the polymerization of ethylene and mixtures of ethylene with higher alpha-olefins and/or diolefins, are disclosed. The catalysts are prepared by mixing (a) hydrides or organometallic compounds of metals belonging to Groups I, II or III of the Mendelyeev Periodic Table with (b) the products obtained by contacting titanium compounds with activated anhydrous halides of magnesium or manganese, diluted with anhydrous compounds of metals belonging to Groups III or IV of said Periodic Table, and which are different from either (a) or the titanium compound of (b).
    Type: Grant
    Filed: August 23, 1979
    Date of Patent: February 9, 1982
    Assignee: Montecatini Edison S.p.A.
    Inventors: Umberto Giannini, Paolo Longi, Domenico Deluca, Angelo Pricca
  • Patent number: 4315088
    Abstract: This invention relates to a process for producing an .alpha.-olefin polymer having a high stereoregularity in a high yield by polymerizing .alpha.-olefin in the presence of a catalyst composed of solid catalyst component (I) prepared by contacting (A) magnesium halide, (B) aromatic carboxylic acid ester, (C) halogen compound of titanium, and (D) siloxyaluminum compound with each other, and (II) an organometallic compound of a metal of Group I to III in the Periodic Table.
    Type: Grant
    Filed: December 11, 1979
    Date of Patent: February 9, 1982
    Assignee: Mitsubishi Petrochemical Co., Ltd.
    Inventors: Sadao Kitagawa, Isao Okada, Teruo Saito
  • Patent number: 4309521
    Abstract: 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: Grant
    Filed: May 14, 1980
    Date of Patent: January 5, 1982
    Assignee: Chisso Corporation
    Inventors: Akihiro Sato, Kazutsune Kikuta, Kenji Matsuda, Toshihiro Uwai, Tohru Hanari
  • Patent number: 4308369
    Abstract: 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: Grant
    Filed: June 2, 1980
    Date of Patent: December 29, 1981
    Assignee: The Dow Chemical Company
    Inventors: Randall S. Shipley, Donald F. Birkelbach, Kirby Lowery, Jr.
  • Patent number: 4304891
    Abstract: 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: Grant
    Filed: April 28, 1980
    Date of Patent: December 8, 1981
    Assignee: Chisso Corporation
    Inventors: Akihiro Sato, Masami Tachibana, Kazutsune Kikuta, Yoshiharu Higuchi