Non-metal Material Is Organic Nitrogen-containing Compound Patents (Class 526/141)
  • Patent number: 6004677
    Abstract: There is provided a process for producing polydienes, such as polybutadiene and polyisoprene, in a gas phase fluidized bed reactor using a pre-activated nickel catalyst which is highly active for cost effective production of these dienes in gas phase.
    Type: Grant
    Filed: August 8, 1997
    Date of Patent: December 21, 1999
    Assignee: Union Carbide Chemicals & Plastics Technology Corporation
    Inventors: Kevin Joseph Cann, Maria Angelica Apecetche, Minghui Zhang
  • Patent number: 5986026
    Abstract: Syndiotactic 1,2-polybutadiene is a thermoplastic resin which has double bonds attached in an alternating fashion to its polymeric backbone. Films, fibers and molded articles can be made utilizing syndiotactic 1,2-polybutadiene. It can also be blended into rubbers and cocured therewith. In such applications, sometimes it is beneficial for the syndiotactic 1,2-polybutadiene to have more than one melting point. This invention discloses a process for preparing syndiotactic 1,2-polybutadiene having at least two different melting points which comprises: polymerizing 1,3-butadiene monomer in an aqueous medium in the presence of (1) a catalyst composition which is made by reacting (a) at least one cobalt compound selected from the group consisting of (i) .beta.-diketone complexes of cobalt, (ii) .beta.-keto acid ester complexes of cobalt, (iii) cobalt salts of organic carboxylic acids having 6 to 15 carbon atoms and (iv) complexes of halogenated cobalt compounds of the formula CoX.sub.
    Type: Grant
    Filed: May 5, 1997
    Date of Patent: November 16, 1999
    Assignee: The Goodyear Tire & Rubber Company
    Inventors: Tang Hong Wong, James Heber Cline
  • Patent number: 5948720
    Abstract: A catalyst for use in the production of flexible polyolefins using a pro-catalyst of (a) a magnesium halide, (b) an aluminum halide, (c) a tetravalent titanium halide, (d) an electron donor comprising at least one of 2,6-lutidine, 6-chloro-2-picoline, or 2,6-dichloropyridine; and (e) a silane having the formula R.sub.1 R.sub.2 Si(OR.sub.3)(OR.sub.4), wherein R.sub.1 and R.sub.2 are each an H, C.sub.1-6 alkyl, C.sub.1-6 aryl, C.sub.5-12 cycloalkane, each of which may be unsubstituted, mono- or di-substituted, and R.sub.3 and R.sub.4 are H, C.sub.1-6 alkane, or a mono- or di-substituted C.sub.1-6 alkane, and a co-catalyst of an organometallic compound, as well as an optional external modifier that may be combined to form a catalyst. Methods for preparing the catalyst, for using the same to produce flexible polyolefin compositions having reduced stickiness and tacticity, and the flexible polyolefin compositions produced thereby are also part of the invention.
    Type: Grant
    Filed: January 7, 1997
    Date of Patent: September 7, 1999
    Assignee: Huntsman Polymers Corporation
    Inventors: Lixin Sun, George C. Allen, Michael P. Hughes
  • Patent number: 5919876
    Abstract: The synthesis of cis-1,4-polyisoprene by polymerizing isoprene with a catalyst system which is comprised of a titanium tetrahalide, a trialkylaluminum compound and diphenylether is plagued with the formation of gel. This invention is based upon the unexpected discovery that gel formation can be reduced by conducting such polymerizations in the presence of a diarylamine, such as para-styrenated diphenylamine. The subject invention more specifically discloses a process for synthesizing cis-1,4-polyisoprene having a low gel content which comprises polymerizing isoprene in an inert organic solvent with a preformed catalyst system which is made by reacting an organoaluminum compound with titanium tetrahalide, such as titanium tetrachloride, in the presence of at least one ether, wherein said polymerization is conducted at a temperature which is within the range of about 0.degree. C. to about 100.degree. C., and wherein said polymerization is conducted in the presence of a diarylamine.
    Type: Grant
    Filed: October 7, 1998
    Date of Patent: July 6, 1999
    Assignee: The Goodyear Tire & Rubber Company
    Inventor: Kenneth Floyd Castner
  • Patent number: 5914377
    Abstract: Diene rubbers are produced in the gas phase by first polymerizing the dienes or diene mixtures in the presence of a catalyst system, which is based on rare earth compounds, at temperatures of from 0 to 150.degree. C. and at pressures of from 1 mbar to 50 bar, so that a pourable diene rubber having a Mooney viscosity ML (1+4', 100.degree. C.) of 70 to 180 Mooney units is obtained, and subsequently subjecting the pourable diene rubber obtained to a chemical or thermal decomposition reaction until a Mooney viscosity of 10 to 70 Mooney units is obtained.
    Type: Grant
    Filed: March 4, 1997
    Date of Patent: June 22, 1999
    Assignee: Bayer AG
    Inventors: Gerd Sylvester, Hugo Vernaleken
  • Patent number: 5908904
    Abstract: Catalysts consisting ofA) an alcoholate of the rare earths, a carboxylate of the rare earths, a complex compound of the rare earths with diketones and/or an addition compound of the halides of the rare earths with an oxygen or nitrogen donor compound,B) an aluminium trialkyl, a dialkyl aluminium hydride and/or an alumoxane,C) another Lewis acid andD) an inert, particulate inorganic solid with a specific surface of greater than 10 m.sup.2 /g (BET) and a pore volume of 0.3 to 15 ml/gare eminently suitable for the polymerization of conjugated dienes, more particularly butadiene, in the gas phase.
    Type: Grant
    Filed: April 17, 1997
    Date of Patent: June 1, 1999
    Assignee: Bayer AG
    Inventors: Gerd Sylvester, Hugo Vernaleken
  • Patent number: 5883203
    Abstract: In gas phase polymerizations and copolymerizations of ethylene, reagents or cofeeds control the molecular weight, expressed as MI (wherein MI is measured according to ASTM D-1238 Condition E), of the resin product. Use of isopentane and electron donating compounds decrease MI; whereas, electron withdrawing compounds increase MI.
    Type: Grant
    Filed: October 10, 1997
    Date of Patent: March 16, 1999
    Assignee: Mobil Oil Coporation
    Inventors: Subrahmanyam Cheruvu, Frederick Y. Lo, Shih-May Christine Ong
  • Patent number: 5859156
    Abstract: By utilizing the vapor phase polymerization techniques of the present invention, numerous distinct and highly beneficial advantages are realized. For instance, cis-1,4-polyisoprene rubber and high cis-1,4-polybutadiene rubber having a consistent and controllable molecular weight can be easily and practically prepared without utilizing a solvent. The subject invention more specifically discloses a method for vapor phase polymerizing isoprene into cis-1,4-polyisoprene in a process comprising the steps of:(1) charging into a reaction zone said isoprene and a preformed catalyst system which is made by reacting an organoaluminum compound with titanium tetrachloride, preferably in the presence of at least one ether; wherein the isoprene is maintained in the vapor phase in said reaction zone by a suitable combination of temperature and pressure;(2) allowing said isoprene to polymerize into cis-1,4-polyisoprene in said reaction zone at a temperature within the range of about 0.degree. C. to about 100.degree. C.
    Type: Grant
    Filed: December 15, 1997
    Date of Patent: January 12, 1999
    Assignee: The Goodyear Tire & Rubber Company
    Inventors: Nissim Calderon, Joel Muse, Jr., Howard Allen Colvin, Kenneth Floyd Castner
  • Patent number: 5852145
    Abstract: Certain olefins such as ethylene, .alpha.-olefins and cyclopentene can be polymerized by using catalyst system containing a nickel or palladium .alpha.-diimine complex, a metal containing hydrocarbylation compound, and a selected Lewis acid, or a catalyst system containing certain nickel ?II! or palladium ?II! compounds, an .alpha.-diimine, a metal containing hydrocarbylation compound, and optionally a selected Lewis acid. The process advantageously produces polyolefins useful for molding resins, films, elastomers and other uses.
    Type: Grant
    Filed: July 21, 1997
    Date of Patent: December 22, 1998
    Assignee: E. I. du Pont de Nemours and Company
    Inventors: Stephan James McLain, Jerald Feldman
  • Patent number: 5824754
    Abstract: Cocatalytic composition resulting from bringing an organoaluminium halide (A) into contact with an electron-donating organic compound (ED) selected from esters, amides and ketones, the organoaluminium halide (A) possessing an atomic ratio halogen (X)/aluminium (Al) of greater than 1 and less than 1.3, the halide (A) and the compound (ED) being employed in a mole ratio halide (A)/compound (ED) of greater than 20. Catalytic systems which are usable for the polymerization of alpha-olefins, comprising such a cocatalytic composition and a solid based on titanium trichloride complexed with an electron-donating compound.
    Type: Grant
    Filed: February 23, 1996
    Date of Patent: October 20, 1998
    Assignee: Solvay Polyolefins Europe - Belgium (Societe Anonyme)
    Inventors: Paul Fiasse, Herve Collette
  • Patent number: 5780379
    Abstract: Process for the polymerization of alpha-olefins, which is carried out in the presence of a catalyst system comprising:(1) a solid based on completed titanium trichloride;(2) an organometallic compound of metals of groups IA, IIA, IIB and IIIB of the Periodic Table, and(3) an electron-donor organic compound, the solid (1) based on complexed titanium trichloride having been preactivated by being brought into contact with a preactivator comprising the product of reaction of a trialkylaluminum or alkylaluminum chloride compound (a) and of a compound (b) chosen from hydroxyaromatic compounds whose hydroxyl group is sterically hindered, then isolating the predetermined solid (1) from the medium in which it was found.This process enables propylene to be polymerized with an improved stereospecificity without any significant decrease in catalyst activity.
    Type: Grant
    Filed: May 13, 1997
    Date of Patent: July 14, 1998
    Assignee: Solvay Polyolefins Europe-Belgium (Societe Anonyme)
    Inventor: Paul Fiasse
  • Patent number: 5777056
    Abstract: A polyolefinic resin which is a homopolymer of an olefin or a copolymer of olefins, has (i) intrinsic viscosity ?.eta.! measured in decaline at the temperature of 135.degree. C. in the range of 0.5 to 10 deciliter/g and (ii) content of insoluble fraction in boiling n-heptane (W) in the range of 10 to 99 weight % and shows (iii) relation between relaxation time of rubber component measured by pulse NMR at the temperature of 30.degree. C. ?T.sub.2H.sup.R (30):.mu.s!, relaxation time of rubber component measured by pulse NMR at the temperature of 80.degree. C. ?T.sub.2H.sup.R (80):.mu.s! and the content of insoluble fraction in boiling n-heptane (W) satisfying the following equations:T.sub.2H.sup.R (80).ltoreq.670-2.2.times.WT.sub.2H.sup.R (80)/T.sub.2H.sup.R (30).ltoreq.8.8+0.086.times.
    Type: Grant
    Filed: November 25, 1996
    Date of Patent: July 7, 1998
    Assignee: Idemitsu Petrochemical Co., Ltd.
    Inventors: Masayuki Tsuruoka, Akira Tanaka, Masaru Nakagawa
  • Patent number: 5756608
    Abstract: A process for polymerizing C.sub.2 -C.sub.10 -alk-1-enes in the presence of a metallocene complex of the formula I ##STR1## where the substituent groups have the meanings described in the specification.
    Type: Grant
    Filed: July 12, 1996
    Date of Patent: May 26, 1998
    Assignee: BASF Aktiengesellschaft
    Inventors: Franz Langhauser, David Fischer, Jurgen Kerth, Gunther Schweier, Hans-Herbert Brintzinger, Elke Barsties, Werner Roell
  • Patent number: 5756606
    Abstract: Syndiotactic 1,2-polybutadiene is a thermoplastic resin which has double bonds attached in an alternating fashion to its polymeric backbone. Films, fibers and molded articles can be made utilizing syndiotactic 1,2-polybutadiene. It can also be blended into rubbers and cocured therewith. It is generally preferred to synthesize syndiotactic 1,2-polybutadiene in an aqueous medium by suspension or emulsion polymerization. In such aqueous polymerization techniques reactor fouling and particle size control problems are frequently encountered. This invention is based upon the unexpected finding that reactor fouling can be greatly reduced or eliminated and that particle size can be regulated by conducting such aqueous polymerizations in the presence of a controlled amount of dissolved oxygen which is within the range of about 0.01 ppm to about 4 ppm.
    Type: Grant
    Filed: May 22, 1997
    Date of Patent: May 26, 1998
    Assignee: The Goodyear Tire & Rubber Company
    Inventor: Tang Hong Wong
  • Patent number: 5726263
    Abstract: Macromonomers formed by chain transfer catalysis polymerization methods may be decolorized by selective extraction and/or adsorption. The dimers and trimers formed during the polymerization reaction are also removed from the macromonomer mixture so that the remaining mixture has a very low optical density and a desirable degree of polymerization.
    Type: Grant
    Filed: January 30, 1997
    Date of Patent: March 10, 1998
    Assignee: E. I. du Pont de Nemours and Company
    Inventor: Alexei Alexeyevich Gridnev
  • Patent number: 5703181
    Abstract: Disclosed are a catalyst for olefin polymerization comprising (A) a compound of a transition metal in Group IVB of the periodic table which contains a ligand having a cyclopentadienyl skeleton, (B) an organoaluminum compound and any one of (C1) a Br.o slashed.nsted acid; (C2) a material obtained by contacting (c-1) a magnesium compound with (c-2) an electron donor; and (C3) a material obtained by contacting (c-1) a magnesium compound, (c-2) an electron donor and (c-3) an organometallic compound with each other. Also disclosed are processes for polymerizing an olefin in the presence of the above-mentioned catalysts for olefin polymerization. Such catalysts and processes for olefin polymerization as described above are excellent in olefin polymerization activity and economical efficiency.
    Type: Grant
    Filed: January 16, 1996
    Date of Patent: December 30, 1997
    Assignee: Mitsui Petrochemical Industries, Ltd.
    Inventors: Takashi Tashiro, Takashi Ueda
  • Patent number: 5688883
    Abstract: The invention provides a polymerizable composition formed by mixing a liquid and a powder composition. The liquid composition includes a peroxide, which decomposes by at most fifty percent by weight of the peroxide within 10 hours at a temperature of at least 75.degree. C., and a polymerizable monomer. The powder composition comprising a proton donor, and a metal containing compound. The polymerizable composition has from 0.2 to 5 percent by weight of the peroxide, from 5 to 99 percent by weight of the polymerizable monomer, and from 0.1 to 3 percent by weight of the proton donor, and from 0.02 to 3 percent by weight of the metal containing compound. The polymerizable composition has an initial setting time and a storage setting time after storage of the first (liquid) composition for at least 12 months at a temperature of at least 23.degree. C. The initial setting time is within 2 minutes of the storage setting time.
    Type: Grant
    Filed: March 14, 1995
    Date of Patent: November 18, 1997
    Assignee: Dentsply GmbH
    Inventors: Joachim E. Klee, Uwe Walz
  • Patent number: 5677400
    Abstract: In a process for producing syndiotactic-1,2-polybutadiene by suspension polymerization wherein a mixture composed of 1,3-butadiene, a cobalt compound, and an organometallic compound or metal hydride containing a metal of group I, II or III of the periodic table is contacted with an initiator selected from the group consisting of carbon disulfide, phenyl isothiocyanate and xanthogenic compounds in an aqueous medium, the improvement comprising, after the preparation of the mixture, adding thereto an anti gelling agent selected from the group consisting of alcohols, aldehydes, ketones, carboxylic acid esters, nitriles, sulfoxides, amides and phosphoric acid esters, whereby the formation of a rubber-like gelation product in the mixture is inhibited.
    Type: Grant
    Filed: May 1, 1996
    Date of Patent: October 14, 1997
    Assignee: UBE Industries, Ltd.
    Inventors: Nobuhiro Tsujimoto, Yoshisuke Baba, Osamu Kimura, Shuichi Sakaue
  • Patent number: 5652304
    Abstract: By utilizing the vapor phase polymerization techniques of the present invention, numerous distinct and highly beneficial advantages are realized. For instance, cis-1,4-polyisoprene rubber and high cis-1,4-polybutadiene rubber having a consistent and controllable molecular weight can be easily and practically prepared without utilizing a solvent. The subject invention more specifically discloses a method for vapor phase polymerizing isoprene into cis-1,4-polyisoprene in a process comprising the steps of:(1) charging into a reaction zone said isoprene and a preformed catalyst system which is made by reacting an organoaluminum compound with titanium tetrachloride, preferably in the presence of at least one ether; wherein the isoprene is maintained in the vapor phase in said reaction zone by a suitable combination of temperature and pressure;(2) allowing said isoprene to polymerize into cis-1,4-polyisoprene at a temperature within the range of about 35.degree. C. to about 70.degree. C.
    Type: Grant
    Filed: June 28, 1996
    Date of Patent: July 29, 1997
    Assignee: The Goodyear Tire & Rubber Company
    Inventors: Nissim Calderon, Kenneth Floyd Castner, Howard Allen Colvin, Joel Muse, Jr.
  • Patent number: 5621047
    Abstract: This invention relates to a process for preparation of non-crosslinked linear monofunctional and telechelic difunctional unsaturated polymers wherein the functional groups are acrylate or methacrylate groups. The average functionality number of the monofunctional unsaturated polymers is at least 0.7, as determined by nuclear magnetic resonance spectroscopy (NMR). The average functionality number of the telechelic difunctional polymers is at least 1.7, as determined by NMR. Alkyl acrylates or alkyl methacrylates are reacted with cyclic olefinic non-conjugated compounds or unsaturated hydrocarbon polymers to prepare monofunctional and difunctional polymers. The process is substantially free of side reactions comprising double bond migration and cyclization.
    Type: Grant
    Filed: October 13, 1995
    Date of Patent: April 15, 1997
    Assignee: Amoco Corporation
    Inventors: Philip O. Nubel, Howard B. Yokelson, Steven A. Cohen, William G. Bouslog
  • Patent number: 5599882
    Abstract: The present invention discloses a polycyclic norbornene-based ring-opening polymer which comprises(A) 90-5% by mol of a repeating unit represented by the following formula [I] or the alkyl-substituted derivative thereof, and(B) 10-95% by mol of at least one repeating unit selected from a repeating unit represented by the following formula [II], the alkyl-substituted derivative thereof, a repeating unit represented by the following formula [III], the alkyl-substituted derivative thereof, or the alkylidene-substituted derivative thereof, and which has an intrinsic viscosity [.eta.] of 0.01-20 dl/g as determined in toluene at 25.degree. C., the hydrogenation products thereof, and a process for production thereof ##STR1## wherein ------ denotes a single bond or a double bond.
    Type: Grant
    Filed: February 13, 1990
    Date of Patent: February 4, 1997
    Assignee: Nippon Zeon Co., Ltd.
    Inventors: Yoshikatsu Nishi, Masayoshi Ohshima, Teiji Kohara, Toshiyasu Matsui, Tadao Natsuume
  • Patent number: 5589548
    Abstract: This invention relates to difunctional telechelic linear non-crosslinked polyolefins without pendant chain branched groups. The polyolefin compounds of this invention are useful for preparing high molecular weight polyesters, polyamides, polyureas and polyurethanes of high density without branching of the polymer chains, and with low permeability to gases and solvents.
    Type: Grant
    Filed: June 2, 1995
    Date of Patent: December 31, 1996
    Assignee: Amoco Corporation
    Inventors: Philip O. Nubel, Howard B. Yokelson
  • Patent number: 5527751
    Abstract: A polymerization catalyst comprising a reaction product of an organic rare earth metal compound of the formula (I),Cp.sub.a Lx.sub.b M.sub.c D.sub.d (I)(wherein in the formula (I), Cp is a substituted or unsubstituted cyclopentadienyl group, indenyl group, fluorenyl group or their derivatives, or a multidentate coordination compound residue obtained by bonding these groups by way of hydrocarbon or silicon,L is a metal selected from the group consisting of elements having an atomic number of 39 and 57-71,X is a halogen atom,M is an alkaline metal or alkaline earth metal,D is an electron donor,a is 1-2,b is 1-2,c is 0-1, andd is 0-3) with a Grignard reagent of the formula (II),RMgX (II)wherein in the formula (II), R is a hydrocarbon group, and X is a halogen atom); a method for producing a polyolefin or an olefin block copolymer by using the above-mentioned catalyst; and an olefin block copolymer produced by the above-mentioned method.
    Type: Grant
    Filed: June 27, 1994
    Date of Patent: June 18, 1996
    Assignee: Maruzen Petrochemical Co., Ltd.
    Inventors: Kunihiro Inamatsu, Tsuyoshi Matsumoto, Kazuo Soga
  • Patent number: 5519101
    Abstract: A polymerization process for preparation of oligomers and polymers having at least one internal carbon-to-carbon double bond and containing functional groups comprising terminal carbon-to-carbon double bonds is disclosed. The polymerization process is substantially free of side reactions comprising double bond migration. The oligomers and polymers are prepared from acyclic polyenes of from 2 to about 30 carbon atoms. The catalyst system comprises a metathesis catalyst (A) comprising a transition metal compound, an activator (B) selected from the group consisting of organic tin compounds and organic aluminum halides and (C) an organic Lewis base. Yields are at least 60% of theoretical based on acyclic polyene reactant.
    Type: Grant
    Filed: May 27, 1993
    Date of Patent: May 21, 1996
    Assignee: Amoco Corporation
    Inventors: Philip O. Nubel, Vahid Bagheri
  • Patent number: 5512635
    Abstract: This invention relates to a process for preparation of non-crosslinked linear monofunctional and telechelic difunctional unsaturated polymers wherein the functional groups are reactive terminal groups other than vinyl groups. The average functionality number of the monofunctional unsaturated polymers is at least 0.7, as determined by nuclear magnetic resonance spectroscopy (NMR). The average functionality number of the telechelic difunctional polymers is at least 1.7, as determined by NMR. Monofunctional olefins and difunctional olefins are reacted with cyclic olefins or unsaturated polymers to prepare difunctional polymers. The process is substantially free of side reactions comprising double bond migration and cyclization.
    Type: Grant
    Filed: December 15, 1993
    Date of Patent: April 30, 1996
    Assignee: Amoco Corporation
    Inventors: Philip O. Nubel, Howard B. Yokelson, Steven A. Cohen, Raymond T. Behrends, William G. Bouslog, James P. Nelson
  • Patent number: 5502125
    Abstract: An olefin copolymer is prepared by copolymerizing ethylene, an .alpha.-olefin and, optionally a diene having non-conjugated double bonds by solution polymerization in the presence of:(a) an organoaluminum compound,(b) a vanadium compound in the oxidation state from +3 to +5, and(c) an activator in a molar ratio of from 0.5 to 100 relative to vanadium of said vanadium compound, and an activator of a 2-halomalonic ester substituted by an aromatic group and having the formula ##STR1## wherein X=F, Cl, Br or I, Ar is an aromatic radical which is unsubstituted, monosubstituted or polysubstituted by alkyl or alkoxy groups and which is bound to the central carbon atom either directly or by an intervening carbonyl group; and R.sub.1 and R.sub.2 are hydrocarbon radicals having from 1 to 20 carbon atoms.
    Type: Grant
    Filed: March 10, 1995
    Date of Patent: March 26, 1996
    Assignee: Huels Aktiengesellschaft
    Inventors: Radu Bordeianu, Christoph Theis
  • Patent number: 5492983
    Abstract: This catalyst consists of the reaction product, with at least one organomagnesium compound and/or organolithium compound R.sup.1 Li (R.sup.1 =alkyl) or ArLi (Ar=phenyl or benzyl), of the reaction product of (Cp).sub.2 MX.sub.2 Li(OR.sub.2).sub.2 (M=lanthanide, Sc, Y; (Cp)=optionally substituted cyclopentadienyl; and R=alkyl), with at least one bidentate ligand, such as .beta.-diketone or .beta.-keto imine CZ.sub.3 COCHZCDCZ.sub.3, Z selected from halogen, alkyl and H, D=O, NH or NR.sup.3 (R.sup.3 =alkyl or aryl); and phosphorus ylid R.sup.2.sub.3 P.dbd.CA--CO--R.sup.2, R.sup.2 chosen from alkyl and aryl; A=alkyl or H. It advantageously takes the form of a solution at least partially containing an aromatic hydrocarbon. The process for the polymerization of ethylene may be carried out at 20.degree.-250.degree. C. at a pressure which may range up to approximately 200 bars, in solution or in suspension in an at least C.sub.
    Type: Grant
    Filed: June 7, 1994
    Date of Patent: February 20, 1996
    Assignee: ECP Enichem Polymeres France
    Inventors: Xavier Olonde, Karel Bujadoux, Andre Mortreux, Francis Petit, deceased
  • Patent number: 5468707
    Abstract: The invention relates to the use of cyclic organometallic compounds as components in coordination catalyst systems, to corresponding coordination catalyst systems and also to processes for the preparation of polymers by coordination polymerization and of unsaturated hydrocarbons by catalyzed metathesis of alkenes and alkynes using such coordination catalyst systems.
    Type: Grant
    Filed: July 29, 1994
    Date of Patent: November 21, 1995
    Assignee: Merck Patent Gesellschaft mit Beschrankter Haftung
    Inventors: Ludwig Pohl, Fike Poetsch, Herbert Schumann, Karin Weiss, Karl-Heinz Thiele, Hans-Ludwig Hirsch
  • Patent number: 5468822
    Abstract: A 1,2-polybutadiene composition having an excellent reinforcing effect for rubber and synthetic resin materials including at least two polybutadiene components different in melting point from each other and each having, as a main structure, a 1,2-polybutadiene structure, produced by polymerizing a 1,3-butadiene-containing monomer in a water-containing polymerization system in the presence of a catalyst comprising a transition metal compound, an organic compound of one of the Group I to III metals, and one of carbon disulfide, phenyl isothiocyanate, and xanthic acid compounds, while adding a melting point-regulating agent comprising at least one of ketones, aldehydes, alcohols, esters, nitriles, sulfoxides, amides, and phosphoric acid esters in one or two or more separate adding operations or a continuous adding operation.
    Type: Grant
    Filed: February 8, 1994
    Date of Patent: November 21, 1995
    Assignee: UBE Industries, Ltd.
    Inventors: Nohiro Tsujimoto, Kenichi Hongyo, Yoshisuke Baba, Michinori Suzuki, Kazuhiro Akikawa
  • Patent number: 5455318
    Abstract: Method of metathetical polymerization and copolymerization of cycloalkenes of norbornene type in the presence of catalytic system which is comprised ofa) a catalytic precursor prepared by reaction of a tungsten compound containing at least one atom of chlorine, bromine and/or iodine with sterically hindered amines, whereby concentration of the tungsten is 0.01 to 50 milimols per mol of monomer and molar ratio of tungsten/amine is 0.01 to 1:5,b) cocatalyst selected from the group of organic compounds of aluminium, tin, lead, silicon, lithium, magnesium, boron, zinc or germanium, whereby molar ratio tungsten/cocatalyst is 1:1 to 1:20 and possibly,c) moderator of the polymerization reaction selected from the group of ethers, esters, ketons or nitriles in mole ratio cocatalyst/moderator 1:1 to 1:10.
    Type: Grant
    Filed: October 15, 1993
    Date of Patent: October 3, 1995
    Assignee: Chemopetrol, s.p. Litvinov, Vyzkumny ustav makromolekularni chemie
    Inventors: Jiri Stohandl, Pavel Vozka, Irena Varekova, Miroslav Karafiat, Jiri Ondr j, Jiri Mejzlik, Hynek Balcar, Kamil Stepanek, Gerhardt Heller, Jaromir Lederer
  • Patent number: 5451645
    Abstract: Novel chromium-containing compounds are prepared by forming a mixture of a chromium salt, a metal amide, and an ether. These novel chromium-containing, or chromium pyrrolide, compounds, with a metal alkyl and an unsaturated hydrocarbon, can be used as a cocatalyst system in the presence of an olefin polymerization catalyst system to produce a comonomer in-situ. The resultant polymer, although produced from predominately one monomer, has characteristics of a copolymer.
    Type: Grant
    Filed: August 20, 1993
    Date of Patent: September 19, 1995
    Assignee: Phillips Petroleum Company
    Inventors: William K. Reagen, Ted M. Pettijohn, Jeffrey W. Freeman, Elizabeth A. Benham
  • Patent number: 5451646
    Abstract: Cis-1,4-polybutadiene can be synthesized by polymerizing 1,3-butadiene monomer with a three component nickel catalyst system containing (a) an organonickel compound, (b) an organoaluminum compound, and (c) a fluorine containing compound. However, the molecular weight of the cis-1,4-polybutadiene prepared is typically too high to be utilized as a non-oil extended rubber. This invention is based upon the discovery that para-styrenated diphenylamine acts to reduce the molecular weight and to improve the processability of cis-1,4-polybutadiene prepared with such nickel based catalyst systems. The use of para-styrenated diphenylamine as a modifier in such polymerizations does not change the microstructure of the cis-1,4-polybutadiene produced.
    Type: Grant
    Filed: December 5, 1994
    Date of Patent: September 19, 1995
    Assignee: The Goodyear Tire & Rubber Company
    Inventor: Kenneth F. Castner
  • Patent number: 5434230
    Abstract: Compositions containing a radical-polymerizable olefinically unsaturated compound and a hydrazone of an aromatic aldehyde or ketone are provided. Also provided are methods for the production of such compositions and methods for the use of such compositions as an adhesive and sealing compound or its use for the coating and production of plastic moldings. The compositions polymerize radically at room temperature upon exposure to ambient air.
    Type: Grant
    Filed: January 11, 1994
    Date of Patent: July 18, 1995
    Assignee: Henkel Kommanditgesellschaft auf Aktien
    Inventors: Thomas Huver, Petra P. Kremeyer, Wolfgang Klauck, Christian Nicolaisen, Lothar Kammer
  • Patent number: 5424379
    Abstract: A catalyst for production of 1,4-polybutadiene which comprisesas the catalyst component (A) a transition metal compound represented by the formula M(R).sub.l (OR').sub.m X.sub.n-(l+m), wherein M denotes a transition metal atom, R and R' each denote a hydrocarbon group of 1-20 carbon atoms, X denotes a halogen atom, and l, m and n denote numerals satisfying the equations l.gtoreq.0, m.gtoreq.0 and n-(l+m).gtoreq.0, n corresponding to the valence of the transition metal,as the catalyst component (B) an organoaluminum compound represented by the formula AlR.sup.1.sub.a X'.sub.3-a, wherein R.sup.1 denotes a hydrocarbon group of 1-20 carbon atoms, X denotes a halogen atom, and a denotes a numeral satisfying the equation 1.gtoreq.a.gtoreq.3, or an aluminoxane obtained by the reaction of said organoaluminum compound with water, andas the catalyst component (C) an organic compound having at least two hydroxyl groups.
    Type: Grant
    Filed: May 16, 1994
    Date of Patent: June 13, 1995
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Masahiro Kakugo, Tatsuya Miyatake, Koozi Mizunuma, Yoshio Yagi, Kazuhiro Watanabe
  • Patent number: 5416053
    Abstract: A process for the production of polyethylenes or EPRs comprising contacting a mixture comprising ethylene, one or more alpha-olefins, and, optionally, a diene, under polymerization conditions, with a catalyst system comprising:(A) a catalyst precursor comprising:(i) a vanadium compound, which is the reaction product of(a) VX.sub.3 wherein each X is independently chlorine, bromine, or iodine; and(b) an electron donor, which is a liquid, organic Lewis base in which VX.sub.3 is soluble;(ii) a modifier having the formula BX.sub.3 or AlR.sub.(3-a) X.sub.a wherein each R is independently alkyl having 1 to 14 carbon atoms; each X is as defined above; and a is 0, 1, or 2; and(iii) a support for said vanadium compound and modifier,said catalyst precursor being in an independent or prepolymerized state,(B) a cocatalyst consisting of a compound having the formula AlR.sub.(3-a) X.sub.
    Type: Grant
    Filed: June 28, 1993
    Date of Patent: May 16, 1995
    Assignee: Union Carbide Chemicals & Plastics Technology Corporation
    Inventors: Xinlai Bai, Kevin J. Cann
  • Patent number: 5412131
    Abstract: Novel tertiary amine-aluminoxane halide derivatives are disclosed along with olefin polymerization catalyst and polymerization processes using such derivatives in combination with metallocenes.
    Type: Grant
    Filed: July 9, 1993
    Date of Patent: May 2, 1995
    Assignee: Albemarle Corporation
    Inventor: Samuel A. Sangokoya
  • Patent number: 5409875
    Abstract: A polymer supported catalyst comprises Ziegler-Natta catalysts immobilized on a magnesium-modified polymer support. The catalyst support is prepared by (1) dissolving a carboxyl group-containing polymer in a solvent and precipitating the polymer in a polar non-solvent, (2) wet-grinding the precipitated polymer, and (3) mixing the ground polymer with an organomagnesium compound or a complex of an organomagnesium compound and an organoaluminum compound to give a magnesium-modified polymer support. Optionally, the resulting magnesium-modified support is treated with a halogen-containing silicon compound. The catalysts may be loaded onto the support by reacting the magnesium-modified support with a transition metal compound to form a catalyst constituent, and then combining the catalyst constituent with an appropriate organo-metallic compound.
    Type: Grant
    Filed: March 8, 1993
    Date of Patent: April 25, 1995
    Assignee: Queen's University
    Inventors: Cheng C. Hsu, Lixin Sun
  • Patent number: 5410002
    Abstract: The present invention relates to a process for the production of homopolymers of ethylene and copolymers of ethylene with olefins CH.sub.2 .dbd.CHR, wherein R is an alkyl or aryl radical having a number of carbon atoms of from 1 to 10, and having a density greater than 0.86 g/cm.sup.3, comprising at least one (co)polymerization step in the gas phase, in the presence of an active catalyst obtained from a titanium compound supported on a magnesium halide in active form and an Al-alkyl compound. The process is characterized in that a small amount compared with the polymer is fed to the gas-phase reactor of a polyfunctional compound having at least two groups, the same or different, capable of reacting with the alkyl aluminum compound and capable of selectively inhibiting the reactivity of the polymer particle fines compared with the average granulometric size of the polymer present in the bed of a gas-phase polymerization reactor.
    Type: Grant
    Filed: January 29, 1993
    Date of Patent: April 25, 1995
    Assignees: Spherilene S.r.l., Himont Incorporated
    Inventors: Gabriele Govoni, Giovanni Patroncini
  • Patent number: 5405924
    Abstract: An olefin metathesis catalyst system and process for the metathesis polymerization of cyclic olefins, such as dicyclopentadiene, are disclosed. The catalyst system comprises the reaction product of:(a) an imido transition metal halide complex of formula: ##STR1## wherein Ar is C.sub.6-20 aryl, preferably phenyl; M is a transition metal selected from the second and third rows of Groups 5, 6, 7 and 8 of the Periodic Table (IUPAC 1989 convention) and including for example niobium, tantalum, molybdenum, tungsten, rhenium, ruthenium or osmium, preferably tungsten or molybdenum; R is independently halide, C.sub.1-20 alkyl, C.sub.1-12 alkoxy, C.sub.1-12 haloalkyl, C.sub.6-20 aryl, C.sub.6-20 aryloxy, cyano or combinations thereof; L is independently a complexing ligand selected from carbonyl, C.sub.1-12 alkoxy, C.sub.1-12 haloalkoxy, C.sub.1-12 alkyl ethers, including mono-, di- and higher ethers, C.sub.12 alkylnitriles, C.sub.5-20 pyridines, C.sub.
    Type: Grant
    Filed: June 22, 1994
    Date of Patent: April 11, 1995
    Assignee: Shell Oil Company
    Inventor: Donald R. Kelsey
  • Patent number: 5403904
    Abstract: A process is disclosed for preparation of telechelic difunctional unsaturated oligomers and polymers having at least one internal carbon-to-carbon double bond wherein the functional groups are terminal reactive groups. The reactants are acyclic polyenes with terminal carbon-to-carbon double bonds and olefins with at least one functional group. The polymerization process is substantially free of side reactions comprising double bond migration and cyclization. The telechelic difunctional unsaturated oligomers and polymers have a functionality of about 2 and are suitable for preparation of block copolymers, ion exchange resins, adhesives, and flocculants and for further functionalization.
    Type: Grant
    Filed: May 27, 1993
    Date of Patent: April 4, 1995
    Assignee: Amoco Corporation
    Inventors: Philip O. Nubel, Robert B. Morland, Howard B. Yokelson
  • Patent number: 5399539
    Abstract: Supported olefin polymerization catalyst systems can be produced using waste chromium compounds. Olefin polymers can be prepared using a catalyst system composition comprising a waste chromium compound and an alkyl aluminum compound, both supported on an inorganic oxide support, wherein at least a portion of the waste chromium compound is in a hexavalent state.
    Type: Grant
    Filed: June 24, 1994
    Date of Patent: March 21, 1995
    Assignee: Phillips Petroleum Company
    Inventors: William K. Reagen, Ted M. Pettijohn
  • Patent number: 5376612
    Abstract: Novel chromium-containing compounds, such as, for example, chromium pyrrolides, are prepared by forming a mixture of a chromium salt, a metal amide, and an electron pair donor solvent, such as, for example, an ether. These novel chromium-containing, or chromium pyrrolide, compounds can be used either unsupported or supported on an inorganic oxide support, with a metal alkyl and an unsaturated hydrocarbon, to trimerize, oligomerize, and/or polymerize olefins.
    Type: Grant
    Filed: August 20, 1993
    Date of Patent: December 27, 1994
    Assignee: Phillips Petroleum Company
    Inventors: William K. Reagen, Ted M. Pettijohn, Jeffrey W. Freeman
  • Patent number: 5360879
    Abstract: Supported olefin polymerization catalyst systems can be produced using waste chromium compounds. Olefin polymers can be prepared using a catalyst system composition comprising a waste chromium compound and an alkyl aluminum compound, both supported on an inorganic oxide support, wherein at least a portion of the waste chromium compound is in a hexavalent state.
    Type: Grant
    Filed: March 24, 1994
    Date of Patent: November 1, 1994
    Assignee: Phillips Petroleum Company
    Inventors: William K. Reagen, Ted M. Pettijohn
  • Patent number: 5356997
    Abstract: Strain crystallizable 3,4-polyisoprene having a 3,4-microstructure content which is within the range of about 65% to about 85%, a cis-1,4-microstructure content which is within the range of about 15% to about 35%, and essentially no trans-1,4-microstructure or 1,2-microstructure can be synthesized in organic solvents to quantitative yields after short polymerization times by utilizing the catalyst systems of this invention. This invention specifically discloses a process for the synthesis of 3,4-polyisoprene which comprises polymerizing isoprene monomer in an organic solvent at a temperatIre which is within the range of about -10.degree. C. to about 100.degree. C.
    Type: Grant
    Filed: October 30, 1992
    Date of Patent: October 18, 1994
    Assignee: The Goodyear Tire & Rubber Company
    Inventors: Johnny D. Massie, II, Wen-Liang Hsu, Adel F. Halasa, Paul H. Sandstrom
  • Patent number: 5349033
    Abstract: It is possible to obtain globular polymers in the polymerization of alpha-olefins by means of a highly active, spherical Ziegler catalyst. The polymers have a high bulk density and can be processed very easily.
    Type: Grant
    Filed: September 7, 1993
    Date of Patent: September 20, 1994
    Assignee: Hoechst Aktiengesellschaft
    Inventor: Gerhard Thum
  • Patent number: 5349034
    Abstract: A catalyst for production of 1,4-polybutadiene which comprisesas the catalyst component (A) a transition metal compound represented by the formula M(R)l(OR')m X.sub.n-(l+m), wherein M denotes a transition metal atom, R and R' each denote a hydrocarbon group of 1-20 carbon atoms, X denotes a halogen atom, and l, m and n denote numerals satisfying the equations l.gtoreq.0, m.gtoreq.0 and n-(l+m).gtoreq.0, n corresponding to the valence of the transition metal,as the catalyst component (B) an organoaluminum compound represented by the formula AlR.sup.1.sub.a X'.sub.3-a, wherein R.sup.1 denotes a hydrocarbon group of 1-20 carbon atoms, X denotes a halogen atom, and a denotes a numeral satisfying the equation 1.ltoreq.a.ltoreq.3, or an aluminoxane obtained by the reaction of said organoaluminum compound with water, andas the catalyst component (C) an organic compound having at least two hydroxyl groups.
    Type: Grant
    Filed: July 22, 1993
    Date of Patent: September 20, 1994
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Masahiro Kakugo, Tatsuya Miyatake, Koozi Mizunuma, Yoshio Yagi, Kazuhiro Watanabe
  • Patent number: 5348925
    Abstract: A solid component of catalyst, active in the polymerization of propylene and other .alpha.-olefins in stereoregular polymers, is obtained:(i) by treating a non-activated silica support in particles with a tin tetrahalide, to at least partially block the hydroxylic groups of the silica and to obtain a blocked silica;(ii) by impregnating the blocked silica with magnesium dialkyl or magnesium alkyl halide to make the magnesium compound react with the tin compound and with possible residual hydroxylic groups of the silica and to obtain a support;(iii) by halogenating the support by contact with a halogenating agent selected from the halides of tin, antimonium or silicon to obtain a halogenated support;(iv) by titanating the halogenated support with an excess of a titanium tetrahalide to obtain a titanated support;(v) by putting the titanated support in contact with a Lewis base, to obtain a solid component of catalyst.
    Type: Grant
    Filed: February 22, 1993
    Date of Patent: September 20, 1994
    Assignee: ECP Enichem Polimeri S.r.l.
    Inventors: Federico Milani, Luciano Luciani, Antonio Labianco
  • Patent number: 5346971
    Abstract: A process for producing polybutadiene essentially consisted of syndiotactic-1,2-polybutadiene in an aqueous medium includes a step off polymerizing diene essentially consisted of 1,3-butadiene in the presence of: (A) a catalyst composition including (a) a transition metal compound, and (b) an organometallic compound which includes a metal selected from the elements consisting off groups 1, 2, 12, and 13 of Periodic Table; (B) an initiator comprising at least one component selected from a group consisting of carbon disulfide, an isothiocyanate compound, and a xanthogenic compound; and (C) an inert organic liquid having a density of at least 1.10, thereby resultant particles of syndiotactic-1,2-polybutadiene have a diameter up to 2 min.
    Type: Grant
    Filed: May 11, 1993
    Date of Patent: September 13, 1994
    Assignee: UBE Industries, Ltd.
    Inventors: Kenichi Hongyo, Michinori Suzuki, Kazuhiro Akikawa
  • Patent number: 5340785
    Abstract: Supported olefin polymerization catalyst systems can be produced using waste chromium compounds. Olefin polymers can be prepared using a catalyst system composition comprising a waste chromium compound and an alkyl aluminum compound, both supported on an inorganic oxide support, wherein at least a portion of the waste chromium compound is in a hexavalent state.
    Type: Grant
    Filed: February 26, 1993
    Date of Patent: August 23, 1994
    Assignee: Phillips Petroleum Company
    Inventors: William K. Reagen, Ted M. Pettijohn
  • Patent number: 5332793
    Abstract: A process for the production of EPRs comprising contacting ethylene, propylene, and optionally, a diene, under polymerization conditions, with a catalyst system comprising:(A) a catalyst precursor comprising:(i) a vanadium compound, which is the reaction product of(a) VX.sub.3 wherein each X is independently chlorine, bromine, or iodine; and(b) an electron donor, which is a liquid, organic Lewis base in which VX.sub.3 is soluble;(ii) a modifier having the formula BX.sub.3 or AlR.sub.(3-a) X.sub.
    Type: Grant
    Filed: June 28, 1993
    Date of Patent: July 26, 1994
    Assignee: Union Carbide Chemicals & Plastics Technology Corporation
    Inventor: Kevin J. Cann