Non-metal Material Is Organic Sulfur-containing Compound Patents (Class 526/140)
  • Patent number: 4259466
    Abstract: A titanium trichloride-catalyzed process for stereospecific polymerization of alpha-olefins, particularly propylene, to produce polymers of relatively high bulk density comprises employing as the TiCl.sub.3 catalyst component, used with an aluminum alkyl cocatalyst, a 0.1 to 30 millimicron fraction of a TiCl.sub.3 composition produced by(a) reacting TiCl.sub.4 with a complexing agent in a molar ratio of from 1:0.3 to 1:2;(b) reacting an organo-aluminum compound with a complexing agent in a molar ratio of at most 1:0.25;(c) reducing the complexed TiCl.sub.4 with the complexed organo-aluminum compound over a period of less than one hour at a temperature within the range 60.degree. to 110.degree. C. to produce TiCl.sub.3 particles having an average particle size of from 50 to 500 .mu.m;(d) subjecting the TiCl.sub.3 particles to a treatment to reduce the average particle size thereof to less than 50 .mu.m, and(e) classifying the TiCl.sub.
    Type: Grant
    Filed: November 8, 1979
    Date of Patent: March 31, 1981
    Assignee: Shell Oil Company
    Inventors: Andras G. T. G. Kortbeek, Adrianus A. Van Der Nat
  • Patent number: 4258161
    Abstract: Propylene is polymerized in the presence of a catalytic system of the type which comprises a solid titanium trichloride-based complex serving as a catalyst, said complex having an atomic ratio of aluminum to titanium in the range of below 0.15:1 and containing a complexing agent, and an organic aluminium compound of the general formula, AlR.sub.n.sup.1 Cl.sub.3-n wherein R.sup.1 represents an n-propyl group or an n-hexyl group and n is a value of 1.95-2.10. The catalytic system may further comprise an electron-donor compound as a third catalytic component.
    Type: Grant
    Filed: January 22, 1979
    Date of Patent: March 24, 1981
    Assignee: Mitsubishi Chemical Industries Ltd.
    Inventors: Genjiro Kakogawa, Masayoshi Hasuo, Yoshinori Suga, Hisashi Kitada, Yumito Uehara
  • Patent number: 4252670
    Abstract: A component of a polymerization catalyst is prepared by reacting an organo-magnesium compound, or a complex with an organo-aluminium compound, with an halogenating agent such as silicon tetrachloride or hydrogen chloride, and then reacting the product with a Lewis Base compound, particularly an ester and finally with titanium tetrachloride. The product obtained is combined with an organo-aluminium compound preferably together with a Lewis Base and used to polymerize an olefine monomer. The catalyst has a high activity and is stereospecific.
    Type: Grant
    Filed: March 26, 1979
    Date of Patent: February 24, 1981
    Assignee: Imperial Chemical Industries Limited
    Inventors: Anthony D. Caunt, Paul D. Gavens
  • Patent number: 4251389
    Abstract: Titanium chloride catalysts having improved activity to polymerize propylene are prepared by treating TiCl.sub.4 with an aluminum alkyl and treating the resulting titanium chloride catalysts with carbon dioxide and a Lewis base such as di(n-butyl) ether at an elevated temperature.
    Type: Grant
    Filed: January 14, 1980
    Date of Patent: February 17, 1981
    Assignee: Gulf Oil Corporation
    Inventors: Ronald E. Gilbert, Rajindar K. Kochhar
  • Patent number: 4250283
    Abstract: A titanium trihalide component of an olefine polymerization catalyst is prepared by reacting together a titanium tetrahalide and an organo-aluminium compound, and treating the solid reaction product with a hydrocarbon solution of an alkyl aluminium dihalide. It is preferred that the solid reaction product is treated with a complexing agent, particularly an ether such as di-isoamyl ether before contacting with the alkyl aluminium dihalide. The titanium trihalide can then be used together with an organo-metallic compound to polymerize an olefine monomer, particularly propylene. The catalyst system may include further components in addition to the titanium trihalide and organo-metallic compound.
    Type: Grant
    Filed: February 12, 1975
    Date of Patent: February 10, 1981
    Assignee: Imperial Chemical Industries Limited
    Inventors: Anthony D. Caunt, James F. R. Jaggard
  • Patent number: 4248988
    Abstract: The process described herein comprises the polymerization of a conjugated diene, such as butadiene-1,2, isoprene, etc., in an anhydrous hydrocarbon solution and in intimate contact with a catalyst system comprising a cobalt or nickel component, a hydrocarbyl aluminum compound and a halogenated hydrocarbon, such as CCl.sub.4, CH.sub.2 Cl.sub.2, CBr.sub.4, CHCl.sub.3, CHBr.sub.3, etc., containing 1-10 carbon atoms and 1-6 halogen atoms per molecule, with at least one of said halogen atoms being attached to an aliphatic carbon atom. Analysis shows that the polymer product has cyclic structure and this is confirmed by the determination of residual unsaturation which is found generally to be less than 20 percent of the normal unsaturation of the polymeric diene. The products are useful in molding compositions.
    Type: Grant
    Filed: October 18, 1979
    Date of Patent: February 3, 1981
    Assignee: The Firestone Tire & Rubber Company
    Inventor: Adel F. Halasa
  • Patent number: 4247418
    Abstract: The catalyst system disclosed herein comprises a combination or a chelate of a hydrocarbyl lithium compound with a bicyclic amine compound bridged together through nitrogen in each cyclic ring by means of 1-4, preferably 2-4 carbon atoms and each cyclic ring having at least one nitrogen and at least one other heteroatom in its cyclic structure selected from the class consisting of NR, O, S and PR. This catalyst system is particularly useful in the polymerization of vinyl compounds such as ethylene, propylene, styrene, butadiene, etc. The process for the polymerization of conjugated dienes produces polymers of excellent properties. For example, with butadiene-1,3 and other appropriate conditions, polybutadiene with high percentages of syndiotactic crystalline structure may be produced.
    Type: Grant
    Filed: October 18, 1979
    Date of Patent: January 27, 1981
    Assignee: The Firestone Tire & Rubber Company
    Inventors: Adel F. Halasa, James E. Hall
  • Patent number: 4246384
    Abstract: Magnesium metal is contacted with an organic halide in the absence of an ether or other complexing diluent to produce a magnesium reducing agent for converting titanium tetrahalide to titanium trihalide. In a first embodiment, the magnesium metal, organic halide, and titanium tetrahalide are introduced into a mill and milled. In a second embodiment, the organic halide is metered dropwise onto the magnesium metal in the absence of any extraneous diluent, and the resulting magnesium reducing agent is thereafter added to a titanium tetrahalide and milled. In a third embodiment, an organic halide containing the titanium tetrahalide is metered dropwise onto magnesium metal in the absence of any extraneous diluent. In each instance the resulting titanium trihalide catalyst component is contacted with an organoaluminum compound activator and used for the polymerization of olefins, preferably the polymerization of propylene.
    Type: Grant
    Filed: November 8, 1978
    Date of Patent: January 20, 1981
    Assignee: Phillips Petroleum Company
    Inventor: Charles M. Selman
  • Patent number: 4243782
    Abstract: A reaction product of a transition metal compound, for example titanium tetrachloride, and an organo-compound of a non-transition metal, for example an aluminium dialkyl halide, is treated with a sulphur containing organic compound, in an amount of up to 2.00, preferably up to 1.50 molar relative to the transition metal compound. The mixture is heated to a temperature in the range from 60.degree. C. up to 160.degree. C. Before treating with the sulphur compound, the reaction product can be heated to a temperature of up to 160.degree. C. The Lewis Base compound is a sulphone, a sulphonamide or a fused-ring heterocyclic compound such as phenoxathiin. The product obtained can be used as a component of an olefine polymerization catalyst.
    Type: Grant
    Filed: June 16, 1976
    Date of Patent: January 6, 1981
    Assignee: Imperial Chemical Industries Limited
    Inventors: Ashley D. Bye, Alan B. Newton
  • Patent number: 4235984
    Abstract: .alpha.-Olefin polymers of high stereoregularity are prepared by polymerizing the .alpha.-olefin with a catalyst prepared by mixing components (A), (B) and (C):(A) a solid titanium component prepared from an organo-magnesium compound, a silicon halide compound and/or an aluminum halide compound, an electron donor and TiCl.sub.4,(B) an organoaluminum activator, and(C) an electron donor.
    Type: Grant
    Filed: February 12, 1979
    Date of Patent: November 25, 1980
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Akinobu Shiga, Yoshiharu Fukui, Katsumi Hanji, Toshio Sasaki, Masahisa Okawa, Hideaki Matsuura, Yasuharu Yamada
  • Patent number: 4235747
    Abstract: Polymerization performance of organoaluminum reduced, electron donor complexed, brown solid, beta titanium trichloride catalyst component is improved in terms of polymer particle size by contacting said brown solid with at least one aluminum alkyl and at least one alpha-olefin in amounts and under conditions such that a low yield, polyalphaolefin structure is formed around the brown solid.
    Type: Grant
    Filed: April 19, 1979
    Date of Patent: November 25, 1980
    Assignee: Standard Oil Company (Indiana)
    Inventor: Linus K. Leung
  • Patent number: 4228253
    Abstract: A process for making crystalline polymers or copolymers of alpha-olefins containing 3 to 8 carbon atoms, such as polypropylene, by polymerization with a catalyst consisting of a combination of titanium chloride and an organic aluminum compound, in the presence of a stereospecificity additive.This stereospecificity additive is a cyclic polyether of the crown ether type, which may contain sulphur atoms and/or nitro radicals; this additive may be used together with an activator.The process produces polymers or copolymers with a high isotacticity index, while keeping catalyst activity sufficiently high.
    Type: Grant
    Filed: June 13, 1979
    Date of Patent: October 14, 1980
    Assignee: Ato Chimie
    Inventor: Gilbert Marie
  • Patent number: 4228262
    Abstract: A solid compound of a transition metal is ground in the presence of aluminum chloride; titanium tetrachloride and at least one specified organic sulphur-containing compound are added, the whole mixture is ground and the ground product is then washed with an aromatic liquid. The transition metal compound is typically titanium trichloride. The organic sulphur-containing compound can be a sulphone, a sulphonamide or a condensed ring system containing at least one heterocyclic sulphur atom. The organic sulphur-containing compound can be diphenylsulphone. The solid compound of the transition metal may be one which also includes aluminum chloride. The quantities of materials added to the transition metal compound are, for each mole of the transition metal compound, 0.10 up to 2.50 moles of the organic sulphur-containing compound, 0.01 up to 0.50 mole of titanium tetrachloride and 0.01 up to 2.50 moles of aluminum chloride.
    Type: Grant
    Filed: April 13, 1979
    Date of Patent: October 14, 1980
    Assignee: Imperial Chemical Industries Limited
    Inventors: Anthony D. Caunt, Ian G. Williams
  • Patent number: 4228252
    Abstract: A process for making crystalline polymers or copolymers of alpha-olefins containing 3 to 8 carbon atoms, such as polypropylene, by polymerization with a catalyst consisting of a combination of titanium chloride and an organic aluminum compound, in the presence of a stereospecificity additive.This stereospecificity additive has the formula:R.sub.1 --O--(C.sub.p H.sub.2p)--S--R.sub.2,where:R.sub.1 and R.sub.2 are alkyl radicals containing 1 to 4 carbon atoms or are linked together to form a divalent --(C.sub.m H.sub.2m)--radical, andp and m are integers each with a value of 1 to 6;this additive may be used in the presence of an activator.
    Type: Grant
    Filed: June 13, 1979
    Date of Patent: October 14, 1980
    Assignee: Ato Chimie
    Inventor: Gilbert Marie
  • Patent number: 4224181
    Abstract: A new improved Ziegler type catalyst system for alpha-olefin type polymerization includes R'.sub.3 Y or R'.sub.2 YX and mixtures thereof, at least one Group IVB -VIII transition metal halide and an alkyl metal compound selected from R'.sub.2 YNR.sub.2 and R'XYNR.sub.2, wherein Y is Al, Ga or In and at least one Lewis base. The improved catalyst system provides increased polymerization activity without significantly affecting the crystallinity of the polymer.
    Type: Grant
    Filed: March 7, 1979
    Date of Patent: September 23, 1980
    Assignee: Exxon Research & Engineering Co.
    Inventor: Arthur W. Langer, Jr.
  • Patent number: 4224182
    Abstract: A new catalyst system for alphaolefin type polymerizations, includes at least one hindered alkyl metal amide compound having the formula R'.sub.2 YNR.sub.2 in combination with a Group IVB-VIII transition metal compound on a support and at least one Lewis base wherein R is selected from the group consisting of C.sub.4 to C.sub.20 bulky alkyl, cycloalkyl, aralkyl, aryl and substituted aryl groups or R.sub.2 N is a hindered cyclic amide group; R' is selected from the group consisting of C.sub.1 to C.sub.20 primary alkyl, secondary alkyl, tertiary alkyl, neopentyl alkyl, branched alkyl, cycloalkyl or aralkyl groups, and Y is selected from the group consisting of aluminum, gallium or indium. The catalyst system provides polymers having increased isotactic stereoregularity as well as lower catalyst residue.
    Type: Grant
    Filed: March 7, 1979
    Date of Patent: September 23, 1980
    Assignee: Exxon Research & Engineering Co.
    Inventors: Arthur W. Langer, Jr., John J. Steger, Terry J. Burkhardt
  • Patent number: 4215014
    Abstract: A new improved catalyst system for alpha-olefin type polymerizations includes a metal alkyl cocatalyst having the formula T.sub.n MR'.sub.3-n in combination with a Group IVB-VIII transition metal compound on a support and a Lewis base wherein n is equal to one or two, T is equal to R.sub.3 DCH.sub.2, and wherein D is selected from the group consisting of Si, Ge or Sn, R is methyl or ethyl, and R' is selected from the group consisting of C.sub.1 to C.sub.8 primary alkyl or aralkyl groups including unhindered branched groups and M is selected from the group consisting of aluminum, gallium, or indium. The improved catalyst system provides both increased polymerization activity and polymers having a high degree of isotactic stereoregularity as well as lower catalyst residue.
    Type: Grant
    Filed: June 18, 1979
    Date of Patent: July 29, 1980
    Assignee: Exxon Research & Engineering Co.
    Inventor: Arthur W. Langer, Jr.
  • Patent number: 4213878
    Abstract: A transition metal composition has the formula:TiCl.sub.3 (AlR.sub.x X.sub.3-x).sub.n E.sub.a L.sub.bwhere E is an ether or thioether; L is an organic sulphur-containing compound; and a and b are each greater than 0.001 and not more than 0.50. The composition has a low surface area, typically less than 50 m.sup.2 /g. The composition can be prepared by reacting titanium tetrachloride with an organo-aluminium compound, optionally heating the reaction product, contacting the reaction product at an elevated temperature with at least E, and preferably L and washing the product. In the composition, E is conveniently di-n-butyl ether or di-isoamyl ether and L can be phenoxathiin or diphenyl sulphone. The composition can be used as a component of a catalyst for the polymerization of olefine monomers such as propylene.
    Type: Grant
    Filed: August 25, 1978
    Date of Patent: July 22, 1980
    Assignee: Imperial Chemical Industries Limited
    Inventor: Ashley D. Bye
  • Patent number: 4211670
    Abstract: An improved titanium trichloride catalyst component is prepared by treating a crude titanium trichloride composition with two different electron donor compounds via successive treatment with first one of the donor compounds and then with the other. The treated composition provides greater stereospecificity in the polymerization and copolymerization of propylene.
    Type: Grant
    Filed: January 25, 1979
    Date of Patent: July 8, 1980
    Assignee: Hercules Incorporated
    Inventor: Edwin J. Vandenberg
  • Patent number: 4210735
    Abstract: Process for the polymerization of .alpha.-olefins in the presence of an activator selected from among the organic compounds of metals of groups Ia, IIa, IIb and IIIa of the Periodic Table and a solid catalytic element prepared by(a) reducing TiCl.sub.4 by means of a reducing metal selected from among the metals of groups Ia, IIa, IIb, IIIa of the Periodic Table so as to prepare a double chloride of titanium and the reducing metal(b) treating the double chloride thus prepared by means of a complexant(c) reacting the double chloride thus treated with TiCl.sub.4(d) separating the solid catalytic element thus prepared.
    Type: Grant
    Filed: October 12, 1972
    Date of Patent: July 1, 1980
    Assignee: Solvay & Cie.
    Inventors: Jean-Pierre Hermans, Paul Henrioulle
  • Patent number: 4210738
    Abstract: Solid catalytic complexes are useful for stereospecific polymerization of .alpha.-olefins to solid crystalline polymers. The complexes are formed by reducing TiCl.sub.4 with an alkylaluminum, treating thus-obtained reduced solid with a complexing agent and contacting the resultant with TiCl.sub.4. They have a specific surface greater than 75 m.sup.2 /g.
    Type: Grant
    Filed: March 21, 1972
    Date of Patent: July 1, 1980
    Assignee: Solvay & Cie.
    Inventors: Jean P. Hermans, Paul Henrioulle
  • Patent number: 4210729
    Abstract: Storage stability of Ziegler-type catalysts for .alpha.-olefin polymerization and having a specific surface greater than 75 m.sup.2 /g is improved by treating the catalysts with a preactivator which is an organic compound of a metal of one of Groups Ia, IIa, IIb and IIIa of the Periodic Table.CROSS-REFERENCE TO RELATED APPLICATIONThe invention described herein is directly related to that described in copending Application Ser. No. 236,407, filed Mar. 21st, 1972. The entire text of that application is incorporated herein by reference.BACKGROUND OF THE INVENTIONZiegler-type microporous catalytic complexes having a specific surface area greater than 75 m.sup.2 /g and useful for the polymerization of .alpha.-olefins are prepared by (a) reducing TiCl.sub.4 by means of an aluminum alkyl; (a') optionally isolating the reduced solid, based on TiCl.sub.
    Type: Grant
    Filed: August 27, 1973
    Date of Patent: July 1, 1980
    Assignee: Solvay & Cie.
    Inventors: Jean-Pierre Hermans, Paul Henrioulle
  • Patent number: 4203867
    Abstract: A transition metal composition has the formula:TiCl.sub.3 (AlR.sub.x X.sub.3-x).sub.n E.sub.a L.sub.bwhere E is an ether or thioether; L is a defined ester, an amine or a ketone; and a and b are each greater than 0.001 and not more than 0.50. The composition has a low surface area, typically less than 50 m.sup.2 /g. The composition can be prepared by reacting titanium tetrachloride with an organo-aluminium compound, optionally heating the reaction product, contacting the reaction product at an elevated temperature with at least one of E and L and washing the product subsequent to the treatment with E. In the composition, E is conveniently di-n-butyl ether or di-isoamyl ether and L can be tetramethylethylenediamine; ethyl benzoate; benzophenone; glycerol monostearate; glycerol triacetate; glycerol tripalmitate; glycerol trimethacrylate; pentaerythritol tetra-acrylate or ethyl phenyl acetate. The composition can be used as a component of a catalyst for the polymerization of olefine monomers such as propylene.
    Type: Grant
    Filed: August 25, 1978
    Date of Patent: May 20, 1980
    Assignee: Imperial Chemical Industries Limited
    Inventor: Ashley D. Bye
  • Patent number: 4201850
    Abstract: Elastomeric copolymers of butadiene and piperylene containing at least 50 mole percent butadiene and having a random distribution of monomer units enchained in a stereo-regulated manner are characterized by, (1) vinyl unsaturation pendant to the main polymer chain which is equal to or less than 10 percent of the total unsaturation present in the polymer; (2) enchainment of at least 95 percent of the piperylene as the 1,2-trans and 1,4-trans-stereoisomers; and (3) selective enchainment of between 50 and 95 percent of the butadiene as the 1,4-trans-stereoisomer. The copolymers, which are prepared from a mixture of the monomers with the aid of an iodine-containing hydrocarbon-soluble catalyst system comprising TiX.sub.n --xMI.sub.n --yI.sub.2 --zAlR.sub.3 --QLB, can be compounded with other elastomers and with process oils, resins, plasticizers and reinforcing agents such as carbon black, silica, talc and the like.
    Type: Grant
    Filed: August 7, 1978
    Date of Patent: May 6, 1980
    Assignee: Exxon Research & Engineering Co.
    Inventors: Erik G. M. Tornqvist, Albert M. Gessler
  • Patent number: 4193893
    Abstract: A transition metal product, for example a titanium trichloride material, is obtained by milling a solid transition metal compound with a carboxylic acid or an ester thereof, for example methylmethacrylate and contacting with an organo-Lewis Base such as an amine, an organo-phosphorus compound or a sulphone derivative. The organo-Lewis Base may be milled with the transition metal compound or may be added to the transition metal compound as a solution in an inert liquid. The product can be used as a component of an olefine polymerization catalyst.
    Type: Grant
    Filed: December 2, 1977
    Date of Patent: March 18, 1980
    Assignee: Imperial Chemical Industries Limited
    Inventors: Anthony D. Caunt, Peter I. Vincent, Alan B. Newton
  • Patent number: 4192774
    Abstract: A process for the preparation of an active TiCl.sub.3 catalyst which comprises:(a) reacting TiCl.sub.4 with a complexing agent in a molar ratio of from 1:0.3 to 1:2;(b) reacting an organo-aluminum compound with a complexing agent in a molar ratio of at most 1:0.25;(c) reducing the complexed TiCl.sub.4 with the complexed organo-aluminum compound over a period of less than one hour at a temperature within the range 60.degree. to 110.degree. C. to produce TiCl.sub.3 particles having an average particle size of from 50 to 500 .mu.m;(d) subjecting the TiCl.sub.3 particles to a treatment to reduce the average particle size thereof to less than 50 .mu.m, and(e) classifying the TiCl.sub.3 particles to separate a fraction having an average particle size of from 0.1 to 30 .mu.m.
    Type: Grant
    Filed: January 18, 1979
    Date of Patent: March 11, 1980
    Assignee: Shell Oil Company
    Inventors: Andras G. T. G. Kortbeek, Adrianus A. van der Nat
  • Patent number: 4187385
    Abstract: 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: Grant
    Filed: May 16, 1977
    Date of Patent: February 5, 1980
    Assignee: Mitsui Toatsu Chemical, Inc.
    Inventors: Tetsuya Iwao, Heizo Sasaki, Akira Ito, Masahiro Kono
  • Patent number: 4183824
    Abstract: A method for preparing a solid catalyst comprising reacting a titanium trichloride composition with a mixture of(1) an ether compound and carbon atom and represented by the general formula (IV): ##STR1## wherein R.sup.5, R.sup.6 and R.sup.7, which may be the same or different, each has up to 18 carbon atoms and represents an aliphatic hydrocarbon group, which may be straight chain, branched chain or cyclic, or an aromatic hydrocarbon group, with at least one of R.sup.5, R.sup.6 and R.sup.7 being an aromatic hydrocarbon group, with at least one of R.sup.5, R.sup.6 and R.sup.7 being an aromatic hydrocarbon group, the amount of the hydrocarbon compound being about 0.01 to about 10 moles per mole of titanium trichloride in the titanium trichloride composition; and/or(2) (b) an organic sulfur compound represented by the general formulas (VI) and (VIII):R.sup.9 --S--S--R.sup.10 (V)HS--(CH.sub.2).sub.d --SH (VI)wherein each of R.sup.9 and R.sup.
    Type: Grant
    Filed: March 10, 1978
    Date of Patent: January 15, 1980
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Akinobu Shiga, Yoshiharu Fukui, Kazuhiro Matsumura, Toshio Sasaki, Masahisa Okawa
  • Patent number: 4182811
    Abstract: A catalyst for the (co)polymerization of ethylene, .alpha.-olefines, conjugated and non-conjugated dienes, a method of preparation, and a mode of using same. The catalyst contains from 0.1 to 50 wt.% of a compound of a transition metal of the IV-VIII Groups chemically combined and distributed over the surface and within the volume of a rubber-like polymeric carrier containing from 1 to 50 wt.% of electron-donor and/or electron-acceptor groups and is in the form of a gel which is swellable, but insoluble in the reaction medium.A co-catalyst comprising an organic compound of a metal of Groups I-III is employed chemically combined and/or non-combined with the catalyst.The catalyst is prepared by mixing the metal compound with said carrier swollen or dissolved in a solvent, and by extracting the resulting compound with a solvent.(Co)polymerization is effected in a solvent such as a hydrocarbon or a hologenated hydrocarbon derivative at a temperature not exceeding 200.degree. C.
    Type: Grant
    Filed: February 27, 1978
    Date of Patent: January 8, 1980
    Inventors: Jury N. Bocharov, Viktor A. Kabanov, Marina A. Martynova, Valery G. Popov, Vladimir I. Smetanjuk, Viktor V. Fedorov
  • Patent number: 4168244
    Abstract: Method of polymerizing conjugated diolefinic monomers containing from 4 to about 12 carbon atoms to high molecular weight polymers by bringing said monomers into contact with a catalyst system consisting of (1) an iron-containing compound, (2) an organometallic reducing agent from Groups I and III of the Periodic Table, and (3) a nitrogen-containing ligand.
    Type: Grant
    Filed: June 2, 1978
    Date of Patent: September 18, 1979
    Assignee: The Goodyear Tire & Rubber Company
    Inventor: Morford C. Throckmorton
  • Patent number: 4161461
    Abstract: A solid compound of a transition metal is ground in the presence of aluminium chloride; titanium tetrachloride and at least one specified organic sulphur-containing compound are added, the whole mixture is ground and the ground product is then washed with an aromatic liquid. The transition metal compound is typically titanium trichloride. The organic sulphur-containing compound can be a sulphone, a sulphonamide or a condensed ring system containing at least one heterocyclic sulphur atom. The organic sulphur-containing compound can be diphenylsulphone. The solid compound of the transition metal may be one which also includes aluminium chloride. The quantities of materials added to the transition metal compound are, for each mole of the transition metal compound, 0.10 up to 2.50 moles of the organic sulphur-containing compound, 0.01 up to 0.50 mole of titanium tetrachloride and 0.01 up to 2.50 moles of aluminium chloride.
    Type: Grant
    Filed: November 7, 1977
    Date of Patent: July 17, 1979
    Assignee: Imperial Chemical Industries Limited
    Inventors: Anthony D. Caunt, Ian G. Williams
  • Patent number: 4158088
    Abstract: 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: Grant
    Filed: July 15, 1977
    Date of Patent: June 12, 1979
    Assignee: Mitsui Toatsu Chemicals, Inc.
    Inventors: Tetsuya Iwao, Masahiro Kono, Heizo Sasaki, Akira Ito
  • Patent number: 4151112
    Abstract: A titanium trichloride catalyst complex is produced by reducing titanium tetrachloride with an organo-metal compound and then activating the resulting reduced solids by treatment with a chlorinated hydrocarbon and titanium tetrachloride in the presence of a Lewis base complexing agent. The employment of the chlorinated hydrocarbon and titanium tetrachloride in the presence of the Lewis base complexing agent unexpectedly produces a synergistic effect whereby activating conditions, e.g., temperature, time and TiCl.sub.4 concentration can be employed resulting in a titanium trichloride complex having superior alpha-olefin polymerization properties as compared to titanium trichloride catalyst complexes obtained by treatment under the same conditions in the absence of either titanium tetrachloride or chlorinated hydrocarbon. Moreover, unexpectedly high yields of activated catalyst can be recovered without loss of activity.
    Type: Grant
    Filed: June 30, 1977
    Date of Patent: April 24, 1979
    Assignee: Exxon Research & Engineering Co.
    Inventor: Harry J. Wristers
  • Patent number: 4148756
    Abstract: A new improved catalyst system for polymeric polymerizations, includes at least one metal alkyl compound having the formula R.sub.n MR'.sub.3-n in combination with a Group IVB-VIII transition metal compound on a support and at least one Lewis base wherein R is selected from the group consisting of C.sub.3 to C.sub.20 secondary or tertiary alkyl, cycloalkyl, alkenyl or aralkyl groups, or ##STR1## wherein R" is a methyl or ethyl group and R"' is a C.sub.1 to C.sub.10 alkyl group; R' is selected from the group consisting of C.sub.1 to C.sub.20 primary alkyl, alkenyl or aralkyl groups, or a hydride, M is selected from the group consisting of aluminum, gallium, or indium; and n = 1-3. The improved catalyst system provides polymers having increased isotactic stereoregularity as well as lower catalyst residue.
    Type: Grant
    Filed: March 29, 1978
    Date of Patent: April 10, 1979
    Assignee: Exxon Research & Engineering Co.
    Inventor: Arthur W. Langer, Jr.
  • Patent number: 4147664
    Abstract: A catalyst for polymerization, copolymerization and oligomerization of olefins and diolefins is described, which is a compound having the general formula MX.sub.n wherein M is a metal belonging to IVA -- VIA groups of the Periodic System or a cobalt, X is a halogen, hydrogen, cyclopentadienyl, alkoxy-, aryloxy-, or amido group, and n is an integer denoting the valency of M; a compound having the general formula M'R.sub.p Z.sub.k-p wherein M' is a metal of I--III groups of the Periodic System, R is a hydrocarbon radical, Z is a halogen, hydrogen, alkoxy-, aryloxy- or amido group, k is an integer denoting the valency of M', 1.ltoreq.p.ltoreq.k; or compound having the general formula MR.sub.m X.sub.n-m, wherein 2.ltoreq.m.ltoreq.n, said component being chemically bonded with the surface of a carbon-chain polymer carrier through the fragment ##STR1## WHEREIN R' = H, CH.sub.3, C.sub.2 H.sub.5, CH.sub.2 = CH.sub.2, C.sub.6 H.sub.5 ;R" = h, or CH.sub.3 ;R"' = h, or CH.sub.3 ;y = OH, NHR', SR; COCH.sub.3, CH.sub.
    Type: Grant
    Filed: May 12, 1977
    Date of Patent: April 3, 1979
    Inventors: Anatoly D. Pomogailo, Alla P. Lisitskaya, Viktor S. Oskin, Fridrikh S. Dyachkovsky, Ardalion N. Ponomarev, Nina S. Gorkova
  • Patent number: 4142991
    Abstract: A substantially agglomeration-free, finely divided catalyst component which is suitable for use as a cocatalyst with organoaluminum compounds in the polymerization of alpha olefins, which is formed by grinding a titanium trichloride material, an effective amount of an electron pair donor compound to enhance the performance of said catalyst component, and an effective amount for agglomeration control of an agglomeration control agent. The agglomeration control agent is effective in either reducing the attractive forces between the finely divided particles in the catalyst component or by preventing the close approach of these particles which would result in agglomeration.
    Type: Grant
    Filed: November 8, 1976
    Date of Patent: March 6, 1979
    Assignee: Stauffer Chemical Company
    Inventors: Gregory G. Arzoumanidis, Richard F. Gold, Christian G. Michel
  • Patent number: 4136057
    Abstract: A transition metal compound containing at least one .eta..sup.6 -arene is contacted with a solid material of the formula MX.sub.2 nL where X is a halogen atom, n is such that 0<n.ltoreq.6 and L is an organic Lewis Base compound. The transition metal compound can be a compound such as TiCl.sub.2.2AlCl.sub.3 -arene. The solid material is preferably of high surface area and this may be inherent in the solid material or can be achieved by a grinding procedure. The solid material may be MgCl.sub.2 2.0 C.sub.2 H.sub.5 OH; MgCl.sub.2 2.0 CH.sub.3 COOH or MgCl.sub.2 1.0 CH.sub.3 COOC.sub.2 H.sub.5. The solid material can be treated with a halogen-containing compound either before, during or after the contacting with the transition metal compound. The product of the contacting is useful either as catalyst for the polymerization of unsaturated hydrocarbon monomers or as a component of such a catalyst.
    Type: Grant
    Filed: August 8, 1977
    Date of Patent: January 23, 1979
    Assignee: Imperial Chemical Industries Limited
    Inventors: John P. Candlin, John A. A. A. G. Segal
  • Patent number: 4136243
    Abstract: An olefine polymerisation catalyst comprises a titanium trichloride component of high surface area, an organo-metallic component, a Lewis Base component and optionally a polyene. The TiCl.sub.3 component which may have a high porosity is conveniently obtained by the reaction of TiCl.sub.4 and an organo-aluminium compound, treating the reaction product with a complexing agent and then contacting this product with TiCl.sub.4. The organo-metallic component is preferably aluminium triethyl, the Lewis Base component hexamethylphosphoric triamide and the polyene is cycloheptatriene. This system has high polymerisation activity combined with good stereospecificity. Polypropylene can be obtained in high yield thereby giving low catalyst residues and the polymer has a high stiffness modulus.
    Type: Grant
    Filed: December 4, 1974
    Date of Patent: January 23, 1979
    Assignee: Imperial Chemical Industries Limited
    Inventors: George D. Appleyard, Anthony D. Caunt, Michael S. Fortuin, Thomas G. Heggs
  • Patent number: 4134855
    Abstract: A transition metal compound containing at least one .eta..sup.6 -arene is contacted with a compound of the formula MX.sub.n Y.sub.2-n mL; or Z.sub.3 Al[MgZ.sub.2 ].sub.y AlZ.sub.3 where L, M, X, Y, Z, m, n, and y are defined. The transition metal compound can be a compound such as TiCl.sub.2.2AlCl.sub.3 -arene. The compound of the defined formula may be a solid compound which may be insoluble in hydrocarbon liquids when it may be of high surface area which may be inherent in the solid or can be achieved by a grinding procedure. The compound of the defined formula may be Mg(OC.sub.2 H.sub.5).sub.2 ; Mg(CH.sub.3).sub.2 ; Mg(CH.sub.2 C.sub.6 H.sub.5).sub.2 ; (C.sub.2 H.sub.5).sub.3 Al[Mg(C.sub.2 H.sub.5).sub.2 ]-Al(C.sub.2 H.sub.5).sub.3 or (iC.sub.3 H.sub.7 O).sub.3 Al(Mg(OiC.sub.3 H.sub.7).sub.2 ]Al(OiC.sub.3 H.sub.7).sub.3. During or after the contacting with the transition metal compound, treatment with a halogen-containing compound may be effected.
    Type: Grant
    Filed: August 8, 1977
    Date of Patent: January 16, 1979
    Assignee: Imperial Chemical Industries Limited
    Inventors: John P. Candlin, John A. A. A. G. Segal
  • Patent number: 4115319
    Abstract: New catalyst components comprising compounds containing titanium, magnesium and halogens, and catalysts for polymerizing olefins obtained by mixing said components with organometallic Al compounds are disclosed.
    Type: Grant
    Filed: September 17, 1976
    Date of Patent: September 19, 1978
    Assignee: Montedison S.p.A.
    Inventors: Umberto Scata, Luciano Luciani, Pier Camillo Barbe
  • Patent number: 4086185
    Abstract: A method for activating a catalyst for propylene polymerization before polymerization is proposed. According to this method, a catalyst which has stability at the time of use and reduces the ratio of amorphous polymer at the time of polymerization is obtained. Said method comprises causing a catalyst dispersion prepared by mixing a specified .delta.-type titanium trichloride composition and an alkylaluminum trichloride in an inert solvent and maintained at a temperature of 10.degree. to 50.degree. C, to absorb a small amount of propylene in an amount of 0.5 to 5 times by weight that of said .delta.-type titanium trichloride.
    Type: Grant
    Filed: March 11, 1976
    Date of Patent: April 25, 1978
    Assignee: Chisso Corporation
    Inventors: Isoo Shirai, Takeshi Suzuki, Tsutomu Takahashi
  • Patent number: 4068052
    Abstract: A method for preventing polymer buildup in the polymerization reactor during the suspension polymerization of vinyl chloride monomer to form polyvinyl chloride polymer and copolymers, the method comprising coating reactor surfaces in contact with the reaction medium with a material selected from the group consisting of alumina, dithiooxamide, and mixtures of these prior to carrying out this polymerization.
    Type: Grant
    Filed: June 23, 1976
    Date of Patent: January 10, 1978
    Assignee: Continental Oil Company
    Inventors: Dean Raymond Weimer, Albert M. Durr, Jr.
  • Patent number: 4065609
    Abstract: Polymerization of a mono-.alpha.-olefine monomer is effected by contacting the gaseous monomer with a solid phase comprising polymer and catalyst at a pressure and temperature which are such that the temperature is in the range from tp + 0.1.degree. C up to tp + 5.0.degree. C, where tp is the temperature at which the monomer condenses at a pressure which is equal to the monomer partial pressure within the polymerization vessel.
    Type: Grant
    Filed: April 1, 1976
    Date of Patent: December 27, 1977
    Assignee: Imperial Chemical Industries Limited
    Inventor: Bruce Albert Edward Willmore
  • Patent number: 4063010
    Abstract: 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: Grant
    Filed: December 3, 1975
    Date of Patent: December 13, 1977
    Assignee: Societe Nationale Elf Aquitaine (SNEA)
    Inventors: Gilbert Marie, Andre Lang, Gilbert Chapelet
  • Patent number: 4057680
    Abstract: In the method of polymerizing .alpha.-olefins by contacting an .alpha.-olefin under polymerization conditions with a stereospecific catalyst comprising a titanium trichloride component and an organoaluminium compound, the improvement wherein said titanium trichloride component is ground during or after contact with a treating agent, said treating agent being selected from at least one ofA. an alkylene oxide, andB. a lactone.
    Type: Grant
    Filed: August 10, 1976
    Date of Patent: November 8, 1977
    Assignee: Showa Denko Kabushiki Kaisha
    Inventors: Isamu Yamazaki, Yoichi Toyama, Kiwami Hirota, Hisashi Takeuchi
  • Patent number: 4053697
    Abstract: A process for producing a homopolymer of propylene or a copolymer of propylene which comprises polymerizing propylene or a mixture of propylene and another unsaturated hydrocarbon monomer such as ethylene in liquid propylene, in the presence of a catalyst system consisting essentially of (a) an activated titanium compound obtained by reducing titanium tetrachloride with an organic aluminum compound and activating the resulting titanium compound and (b) an organic aluminum compound to produce a polymer slurry, introducing the polymer slurry into an upper part of a counter-current washing zone, such as a washing tower, and counter-currently contacting the polymer slurry with liquid propylene which is introduced into a lower part of the washing zone, whereby the polymer and catalyst residues dissolved in the polymer slurry are removed.
    Type: Grant
    Filed: January 16, 1975
    Date of Patent: October 11, 1977
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Mamoru Asada, Akinobu Shiga, Kiyoshi Matsuyama
  • Patent number: 4052545
    Abstract: Conjugated dienes and alpha-olefins, such as butadiene and propylene, are copolymerized by a new catalyst system which gives copolymers containing a high proportion of the alpha-olefin with accompanying desired properties. This catalyst system comprises: (1) A titanium or vanadium halide, preferably chloride, (2) an aluminum hydrocarbon compound which also has Cl, Br or H attached to the Al atom and preferably the hydrocarbon group or groups are alkyl groups which have 1-8 carbon atoms in each of said alkyl groups and (3) CS.sub.2. The copolymers produced by this process have molecular weights in the range of 100,000-5,000,000; referably 250,000-500,000, and other desirable properties.
    Type: Grant
    Filed: February 11, 1976
    Date of Patent: October 4, 1977
    Assignee: The Firestone Tire & Rubber Company
    Inventors: Adel Farhan Halasa, Richard Gutierrez
  • Patent number: 4051308
    Abstract: 1,3-Butadiene is polymerized in the liquid phase in the presence of a catalyst composition comprising:A. A complex of a cobalt salt;B. AlR.sub.3 wherein R is hydrocarbon, andC. CS.sub.2.The complex comprises one of a cobalt salt, preferably CoCl.sub.2, with an organic compound containing nitrogen and oxygen or sulfur, preferably with no more than 2 carbon atoms separating the nitrogen and oxygen or sulfur, and the organometal reducing agent AlR.sub.3, wherein R is a hydrocarbon radical, preferably of no more than 10 carbon atoms. The polybutadiene has a microstructure of at least 80% and generally more than 90% 1,2, is also syndiotactic in character, has a melting point of 190.degree.-227.degree. C, and may be obtained in approximately quantitative yields.
    Type: Grant
    Filed: November 6, 1975
    Date of Patent: September 27, 1977
    Assignee: The Firestone Tire & Rubber Company
    Inventor: Adel Farhan Halasa
  • Patent number: 4048418
    Abstract: Method of polymerizing conjugated diolefinic monomers containing from 4 to about 12 carbon atoms to high molecular weight polymers by bringing said monomers into contact with a catalyst system consisting of (1) an iron-containing compound, (2) an organometallic reducing agent from Groups I and III of the Periodic Table, and (3) a nitrogen-containing ligand.
    Type: Grant
    Filed: November 22, 1974
    Date of Patent: September 13, 1977
    Assignee: The Goodyear Tire & Rubber Company
    Inventor: Morford C. Throckmorton
  • Patent number: T966013
    Abstract: a process is provided in which a solid compound of a transition metal of Groups IVA to VIA is ground with at least one polymeric material containing sulphone groups and containing at least two repeat units of the formula:--Ar--SO.sub.2 --in which Ar is a bivalent aromatic radical and may vary from unit to unit in the polymer chain. The Ar radical preferably contains two aromatic rings linked together, as in: ##STR1## where X is an O or S atom, a direct link or the residue obtained by removing H from each --OH group present in an aromatic diol. If Ar varies the material is a copolymer. The polymeric material can be a polyethersulphone.The transition metal can be zirconium, vanadium or titanium. Preferably the transition metal compound is a halide such as titanium trichloride.
    Type: Grant
    Filed: December 3, 1976
    Date of Patent: January 3, 1978
    Assignee: Imperial Chemical Industries Limited
    Inventors: Alan Branford Newton, John Edward Priddle