Group Iva (ge, Sn, Pb) Or Group Va (as, Sb, Bi) Metal Is Bonded To Hydrogen Or Carbon Atom Patents (Class 526/166)
  • Patent number: 8481659
    Abstract: The present invention relates to cure accelerators useful for anaerobic curable compositions, such as adhesives and sealants.
    Type: Grant
    Filed: October 7, 2011
    Date of Patent: July 9, 2013
    Assignees: Henkel Corporation, Henkel Ireland Ltd.
    Inventors: David P. Birkett, Martin Wyer, Andrew Messana, Philip Klemarczyk, Anthony F. Jacobine
  • Patent number: 7863394
    Abstract: A method of polymerizing poly(cyclic)olefin monomers encompassing (a) combining a monomer composition containing the poly(cyclic)olefin monomers, a non-olefinic chain transfer agent and an activator compound to form a mixture; (b) heating the mixture; and (c) adding a polymerization catalyst containing Ni and/or Pd. The non-olefinic chain transfer agent includes one or more compounds selected from H2, alkylsilanes, alkylalkoxysilanes, alkylgermanes, alkylalkoxygermanes, alkylstannanes, and alkylalkoxystannanes. The activator is characterized as having an active hydrogen with a pKa of at least 5. The resulting poly(cyclic)olefin polymers can be used in photoresist compositions.
    Type: Grant
    Filed: September 7, 2006
    Date of Patent: January 4, 2011
    Assignee: Promerus LLC
    Inventors: Larry F. Rhodes, Dennis A. Barnes, Andrew Bell, Brian K. Bennett, Chun Chang, John-Henry Lipian, Xiaoming Wu
  • Publication number: 20090221773
    Abstract: A method for forming a polymer on a substrate is disclosed. The method may include providing a substrate having a substrate surface, the substrate surface being at least partially hydrogen-terminated and reacting the substrate surface in a solution comprising at least one radical initiator and at least one monomer to form a polymer on the substrate surface. The monomer may comprise at least one of a monofunctional monomer and a polyfunctional monomer. A stationary phase for use in separation applications such as chromatography and solid-phase extraction is also disclosed. The stationary phase may include a plurality of diamond bodies and a polymeric compound covalently bonded to at least a surface portion of the plurality of diamond particles.
    Type: Application
    Filed: February 28, 2008
    Publication date: September 3, 2009
    Applicant: Brigham Young University
    Inventors: Matthew R. Linford, Li Yang
  • Patent number: 7446073
    Abstract: The present invention relates to a cyclic germanium bridged bulky ligand metallocene-type catalyst compound, a catalyst system thereof, and to its use in a process for polymerizing olefin(s) to produce enhanced processability polymers.
    Type: Grant
    Filed: October 19, 2004
    Date of Patent: November 4, 2008
    Assignee: ExxonMobil Chemical Patents Inc.
    Inventors: Donna J. Crowther, Phillip T. Matsunaga
  • Publication number: 20080207855
    Abstract: A robust, impurity tolerant method of making substantially linear polymers of acyclic aliphatic olefins using catalyst complexes comprising a single palladium metal center and a substituted tri-aryl ligand is disclosed.
    Type: Application
    Filed: February 20, 2008
    Publication date: August 28, 2008
    Inventors: David M. Conner, Brian Leslie Goodall, Lester Howard McIntosh
  • Patent number: 7323526
    Abstract: A supported catalyst composition having improved flow properties is disclosed comprising an alkylalumoxane, a metallocene-alkyl an inorganic oxide support having an average particle size of from 0.1 to 50 ?m and calcined at a temperature greater than 600° C., and optionally an antifoulant agent and. In one embodiment, the metallocene-alkyl is a Group 4, 5 or 6 metallocene-alkyl, and in another embodiment is a hafnocene-alkyl. Also disclosed is a method of polymerization using such a supported catalyst composition.
    Type: Grant
    Filed: July 29, 2005
    Date of Patent: January 29, 2008
    Assignee: Univation Technologies, LLC
    Inventors: Agapios K. Agapiou, Phuong Anh Cao, Sun-Chueh Kao
  • Patent number: 7202316
    Abstract: A modified particle obtained by a process containing contacting a Bi compound, a compound having an electron-withdrawing group and an active hydrogen and particle; and a catalyst component for addition polymerization containing the modified particle; a catalyst for addition polymerization prepared by a process containing contacting the modified particle (A) and a transition metal compound of Groups 3 to 11 or lantanide series (B); and a catalyst for addition polymerization prepared by a process containing contacting the modified particle (A) and a transition metal compound of Groups 3 to 11 or lantanide series (B) and an orbanoaluminum compound (C); and a process for producing an addition polymer with the catalyst.
    Type: Grant
    Filed: September 22, 2003
    Date of Patent: April 10, 2007
    Assignee: Sumitomo Chemical Company, Limited
    Inventor: Kazuo Takaoki
  • Patent number: 7037990
    Abstract: A method is provided for the polymerization of olefins substituted with a functional group using a transition metal catalyst that, by virtue of one or more stabilizing groups incorporated within the catalyst structure, “fixes” the stereoconfiguration of each olefinic monomer relative to the transition metal complex during each successive reaction in the polymerization process. The invention substantially reduces the likelihood of olefin rearrangement at the active site of the catalyst during polymerization. In one particular embodiment, the functional group is a polar, electron-donating group and the stabilizing group is a Lewis acid substituent; examples of polymers that can be prepared with such a system include poly(vinyl acetate), poly(vinyl alcohol), and poly(vinyl ethers). Novel complexes and catalyst systems useful in the polymerization method are also provided.
    Type: Grant
    Filed: January 3, 2003
    Date of Patent: May 2, 2006
    Assignee: Nippon Synthetic Chemical Company
    Inventors: Christopher D. Tagge, Robert B. Wilson, Jr., Hiroyuki Ono
  • Patent number: 6982306
    Abstract: This invention relates to the field of olefin polymerization catalyst compositions, and methods for the polymerization and copolymerization of olefins, including polymerization methods using a catalyst composition. One aspect of this invention is the formation and use of a catalyst composition comprising a stannoxy-substituted half-sandwich metallocene and an activator for olefin polymerization processes. For example, this invention encompasses the preparation of (?5-C5H5)Ti(OSnPh3)Cl2, its contact with an activator, for example, zinc-impregnated chlorided alumina, to form a catalyst composition, and the use of this catalyst composition for polymerizing olefins or acetylenes.
    Type: Grant
    Filed: November 26, 2003
    Date of Patent: January 3, 2006
    Assignee: Chevron Phillips Chemical Company, L.P.
    Inventors: Joel L. Martin, Michael D. Jensen, Max P. McDaniel
  • Patent number: 6936393
    Abstract: A catalyst for preparing a polyester for a toner, comprising an inorganic tin(II) compound; a polyester resin composition comprising a polyester and the catalyst; and a toner comprising the polyester resin composition. The catalyst for preparing a polyester is suitably used for a toner which is used for developing electrostatic latent images formed in electrophotography, electrostatic recording method, electrostatic printing method, and the like.
    Type: Grant
    Filed: December 4, 2002
    Date of Patent: August 30, 2005
    Assignee: Kao Corporation
    Inventors: Takashi Kubo, Katsutoshi Aoki, Eiji Shirai, Masayuki Maruta
  • Patent number: 6870016
    Abstract: Olefin polymerization processes using catalyst systems based on metallocenes and olefin, in particular, propylene polymers obtainable thereby. The metallocenes may be represented by the formula: ? wherein M1 preferably is zirconium or hafnium; and R12 is different from hydrogen.
    Type: Grant
    Filed: June 29, 2001
    Date of Patent: March 22, 2005
    Assignee: ExxonMobil Chemical Patents Inc.
    Inventors: Terry J. Burkhardt, James R. Hart, William T. Haygood, Robert T. Li
  • Patent number: 6818585
    Abstract: The present invention relates to a cyclic germanium bridged bulky ligand metallocene-type catalyst compound, a catalyst system thereof, and to its use in a process for polymerizing olefin(s) to produce enhanced processability polymers.
    Type: Grant
    Filed: September 18, 2001
    Date of Patent: November 16, 2004
    Assignee: Univation Technologies, LLC
    Inventors: Donna J. Crowther, Phillip T. Matsunaga, Ching-Tai Lue
  • Patent number: 6528596
    Abstract: A modified particles obtained by contacting particles(a) with a metal compound(b) selected from the group consisting of compounds of the Group VI, VII, XIV metal elements and compounds of the lanthanide series, and contacting the particles with a compound(c) having a functional group containing active hydrogen or a non-proton donative Lewis basic functional group and an electron-withdrawing group; a carrier composed of the modified particles; a catalyst component for olefin polymerization composed of said modified particles; a catalyst for olefin polymerization obtained by contacting the modified particles(A) and a transition metal compound(B), or further an organometallic compound(C); and a process for producing an olefin polymer with the catalyst.
    Type: Grant
    Filed: December 22, 2000
    Date of Patent: March 4, 2003
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Kazuo Takaoki, Tatsuya Miyatake
  • Patent number: 6172168
    Abstract: In the case of Ziegler catalysts based on a metallocene as the transition metal component and an aluminoxane as the activator, preactivation of the metallocene with the aluminoxane results in a considerable increase in the activity of the catalyst system. Furthermore, 1-olefin polymers of a high degree of isotacticity and having compact, spherical particles, a very narrow particle size distribution and a high bulk density are obtained by means of a catalyst system of this type.
    Type: Grant
    Filed: December 14, 1999
    Date of Patent: January 9, 2001
    Assignee: Targor GmbH
    Inventors: Andreas Winter, Walter Spaleck
  • Patent number: 6143842
    Abstract: Disclosed herein are novel polymers and copolymers of alphaolefins produced using various Ziegler/Natta and Metallocene catalysts. Commercial production of these polymers is now possible for the first time owing to the polymer harvesting technology also disclosed herein.
    Type: Grant
    Filed: June 29, 1998
    Date of Patent: November 7, 2000
    Assignee: Huntsman Polymers Corporation
    Inventors: Samuel J. Paton, Stephen C. McHaney, Steven L. Oetting, Karl L. Herzog
  • Patent number: 6034192
    Abstract: This invention relates to a process for polymerizing ethylene comprising contacting ethylene and optional comonomers with a catalyst system comprising an activator and a transition metal compound represented by the formula: ##STR1## Wherein R.sub.1 and R2 are independently hydrogen or a group having up to 100 carbon atoms, Cp.sub.1 is a bulky ligand; Cp.sub.2 is a bulky ligand or a heteroatom optionally bound to a C.sub.1 to C.sub.50 hydrocarbyl group, n is the valence state of the transition metal, Tm is a Group 3 to 10 metal, and each X is independently an anionic leaving group.
    Type: Grant
    Filed: December 30, 1998
    Date of Patent: March 7, 2000
    Assignee: Univation Technologies, LLC
    Inventors: Donna J. Crowther, Natalie A. Merrill, Ching-Tai Lue
  • Patent number: 6017841
    Abstract: In the case of Ziegler catalysts based on a metallocene as the transition metal component and an aluminoxane as the activator, preactivation of the metallocene with the aluminoxane results in a considerable increase in the activity of the catalyst system. Furthermore, 1-olefin polymers of a high degree of isotacticity and having compact, spherical particles, a very narrow particle size distribution and a high bulk density are obtained by means of a catalyst system of this type.
    Type: Grant
    Filed: May 1, 1997
    Date of Patent: January 25, 2000
    Assignee: Targor GmbH
    Inventors: Andreas Winter, Walter Spaleck
  • Patent number: 5767210
    Abstract: This process is characterized by the fact that at least one of the said monomers is polymerized or copolymerized in bulk, solution, emulsion or suspension, at a temperature that can be as low as 0.degree. C., in the presence of an initiation system including: at least one compound generating radicals, other than bromofluorene, and at least one catalyst consisting of a complex of palladium in the 0 oxidation state, denoted by the following formula (I): Pd(0)L.sup.1 L.sup.2 L.sup.3 L.sup.4 in which each of L.sup.1, L.sup.2, L.sup.3 and L.sup.4, which are identical or different, denotes a ligand which may be a chiral ligand, which is chosen from PRR'R", P(OR)(OR')(OR"), NRR'R", ORR', SRR', SeRR', AsRR'R", SbRR'R", where each of R, R' and R" independently denotes a C.sub.1 -C.sub.14 alkyl group, optionally substituted, or an optionally substituted aromatic group, it being possible for at least two of these ligands to be joined to one another by one or more divalent radicals.
    Type: Grant
    Filed: March 27, 1997
    Date of Patent: June 16, 1998
    Assignee: Elf Atochem, S.A.
    Inventors: Philippe Lecomte, Philippe Dubois, Robert Jerome, Philippe Teyssie, Thierry Senninger
  • Patent number: 5728784
    Abstract: Process for the preparation of crystalline vinylaromatic polymers with a predominantly syndiotactic structure which comprises polymerizing vinylaromatic monomers, alone or mixed with at least one other monomer, in the presence of a catalytic system essentially consisting of:a) a complex of titanium or zirconium selected from those having general formula:MR.sub.1 R.sub.2 R.sub.3 R.sub.4, A.sub.1 MR.sub.1 R.sub.2 R.sub.3, A.sub.1 A.sub.2 MR.sub.1 R.sub.2 (I)b) a co-catalyst selected from an alkylalumoxane and a compound of boron having formula (II):BX.sub.1 X.sub.2 X.sub.3 (II)or one of its salts;c) a derivative of tin having general formula:SnR.sub.5 R.sub.6 R.sub.7 R.sub.
    Type: Grant
    Filed: November 27, 1996
    Date of Patent: March 17, 1998
    Assignee: Enichem S.p.A.
    Inventors: Riccardo Po', Nicoletta Cardi, Roberto Santi
  • 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: 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: 5585509
    Abstract: Metallocene complexes of the general formula I ##STR1## where the substituents Y, M, x, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.6, R.sup.7, R.sup.8, and R.sup.9 are as described in the disclosure, and ligand systems of the general formula II ##STR2## as intermediates.
    Type: Grant
    Filed: March 1, 1995
    Date of Patent: December 17, 1996
    Assignee: BASF Aktiengesellschaft
    Inventors: Franz Langhauser, David Fischer, J urgen Kerth, G unther Schweier, Hans-Herbert Brintzinger, Elke Barsties, Werner Roell
  • 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: 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: 5391661
    Abstract: There are disclosed a catalyst well suited for producing a styrenic polymer having a high degree of syndiotactic configuration which comprises a transition-metal compound such as pentamethylcyclopentadienyltrimethyltitanium and a coordination complex compound comprising an anion in which a plurality of radicals are bonded to a metal and a quaternary ammonium salt, the compound being exemplified by orthocyano-N-methylpyridinium tetra(pentafluorophenyl)borate, or comprises an alkylating agent such as triisobutylaluminum in addition to the above two compounds; and a process for producing a styrenic polymer having a high degree of syndiotactic configuration by polymerizing a styrenic monomer using the aforementioned catalyst. Consequently, a styrenic polymer having a high degree of syndiotactic configuration can be produced effectively without the use of an expensive aluminoxane required in a large amount if used.
    Type: Grant
    Filed: February 2, 1993
    Date of Patent: February 21, 1995
    Assignee: Idemitsu Kosan Co., Ltd.
    Inventors: Shoji Naganuma, Masami Watanabe, Norio Tomotsu
  • Patent number: 5374753
    Abstract: An organometal complex is provided which is represented by the general formula (1) below: ##STR1## wherein Cp.sup.1 and Cp.sup.2 are respectively a substituted or unsubstituted cyclopentadienyl group; R.sup.1 is a group selected from alkylene groups or arylalkylene groups having 1 to 20 carbons, dialkylsilylene groups, dialkylgermanylene groups, alkylphosphinediyl groups, or alkylimino groups and R.sup.1 crosslinking Cp.sup.1 and Cp.sup.2 together; m is 0 or 1; M is selected from titanium, zirconium, and hafnium; R.sup.2, R.sup.3, and R.sup.4 are independently hydrogen, a hydrocarbon group of 1 to 12 carbons, an alkoxyl group, or an aryloxy group; and MAO is a methylalumoxane group. This organometal complex is capable of producing selectively an olefin polymer without use of any other additional catalyst component.
    Type: Grant
    Filed: September 7, 1993
    Date of Patent: December 20, 1994
    Assignee: Tosoh Corporation
    Inventors: Satoru Yamada, Akihiro Yano
  • Patent number: 5319042
    Abstract: This invention relates to a two component catalyst system for the polymerization of metathesis polymerizable cycloolefins, comprising (a) a tungsten compound of the formula WOX.sub.4-x (OAr).sub.x where X is chlorine, bromine or fluorine, Ar is a hindered phenyl ring having 1-5 specified substituents and x = 1, 2 or 3; and (b) an activator compound.Among the preferred molecules or groups that are substituted on the phenyl ring of the tungsten compound are phenyl, chlorine, bromine, methoxy and isopropyl groups. Ar can also represent a multi-substituted phenyl group such as 2,4-dichloro-6-methylphenyl.
    Type: Grant
    Filed: October 18, 1991
    Date of Patent: June 7, 1994
    Assignee: Hercules Incorporated
    Inventor: Andrew Bell
  • Patent number: 5300605
    Abstract: Poly(1-hydro-1-R-1-silapent-3-ene) homopolymers and copolymers contain silane segments with reactive silicon-hydride bonds and contain hydrocarbon segments with cis and trans carbon-carbon double bonds.
    Type: Grant
    Filed: March 19, 1993
    Date of Patent: April 5, 1994
    Assignee: University of Southern California
    Inventors: William P. Weber, Xiugao Liao
  • Patent number: 5278305
    Abstract: A catalyst and process for the polymerization of cyclic olefins, such as dicyclopentadiene, are disclosed. The catalyst comprises the reaction product of a transition metal halide and a 1,4-hydroquinone of the general formula: ##STR1## wherein R is independently selected from the group of hydrogen, C.sub.1-12 alkyl, C.sub.6-20 aryl, halide, and C.sub.1-6 haloalkyl. Optional co-catalysts include borohydrides, organo tin hydrides and organo aluminum compounds. Polymerization can be carried out in a reaction injection molding process to prepare a molded article.
    Type: Grant
    Filed: December 31, 1992
    Date of Patent: January 11, 1994
    Assignee: Shell Oil Company
    Inventor: Donald R. Kelsey
  • Patent number: 5276118
    Abstract: A catalyst and process for the metathesis polymerization of cyclic olefins, such as dicyclopentadiene, are disclosed. The catalyst comprises the reaction product of a transition metal halide preferably tungsten, molybdenum, or tantalum halides and a diaryl carbinol of the formula ##STR1## wherein G is independently C.sub.1-12 alkyl, C.sub.1-12 alkoxy, C.sub.1-12 alkylamino, C.sub.6-20 aryl, halide, or C.sub.1-6 haloalkyl; g is independently 0 to 4; R is independently hydrogen or G or the R's are combined as a single bond or as a bridging group X, where X is CH.sub.2, CH.sub.2 CH.sub.2, O, S, SO, SO.sub.2 or NR.sup.1, and R.sup.1 is H or C.sub.1-6 alkyl. Optional co-catalysts include borohydrides, organo tin hydrides and organo aluminum compounds. Polymerization can be carried out in a reaction injection molding process to prepare a molded article.
    Type: Grant
    Filed: December 31, 1992
    Date of Patent: January 4, 1994
    Assignee: Shell Oil Company
    Inventor: Donald R. Kelsey
  • Patent number: 5260498
    Abstract: An improved process for the production of 1:1 molar adducts of 4-vinylcyclohexene and cyclopentadiene, primarily 5-(3-cyclohexen-1-yl)-2-norbornene, comprises contacting 4-vinylcyclohexene and dicyclopentadiene at elevated temperature in a suitable reactor, separating the resulting mixture of adducts into light product comprising predominately the 1:1 molar adduct and a heavy product comprising higher adducts and cyclopentadiene oligomers, and recycling the bottoms product to the reactor.
    Type: Grant
    Filed: December 7, 1992
    Date of Patent: November 9, 1993
    Assignee: Shell Oil Company
    Inventor: Robert H. Ellison
  • Patent number: 5218065
    Abstract: An improved olefin metathesis catalyst system comprises a tungsten halide having an average of no more than about one halide substituent and no more than one oxygen substituent per tungsten with the remaining tungsten valences satisfied with phenolic substituents incorporating at least one meta or para electron withdrawing group and a triorganotin hydride and, optionally, a boron halide promoter. The catalyst system forms a relatively stable polymerization mixture with polycycloolefins and effectively polymerizes dicyclopentadiene in the presence of water.
    Type: Grant
    Filed: August 30, 1991
    Date of Patent: June 8, 1993
    Assignee: Shell Oil Company
    Inventors: Donald R. Kelsey, Betty M. Scardino, Dale L. Handlin, Jr.
  • Patent number: 5180867
    Abstract: A process for the production of thermoset copolymers having tailored product properties such as high glass transition temperature and/or increased cross-linking, the process comprising contacting a comonomer mixture with a methathesis catalyst system obtainable by combining at least a catalyst component and an activator component, wherein the comonomer is selected from compounds according to the formulae: ##STR1##
    Type: Grant
    Filed: November 20, 1989
    Date of Patent: January 19, 1993
    Assignee: Shell Oil Company
    Inventors: Willem Sjardijn, Johannes J. M. Snel
  • Patent number: 5143992
    Abstract: An improved thermoset polymer having good mechanical properties and no detectable dicyclopentadiene odor is obtained by the ring-opening polymerization of a novel mixture of adducts comprising divinyl cyclohydrocarbon compound, such as 3,5-divinylcyclopentene and cyclopentadiene, optionally with added cycloolefinic compound, such as dicyclopentadiene, at polymerization conditions in the presence of an olefin metathesis catalyst.
    Type: Grant
    Filed: July 12, 1991
    Date of Patent: September 1, 1992
    Assignee: Shell Oil Company
    Inventor: Donald R. Kelsey
  • Patent number: 5095082
    Abstract: A hard, infusible, crosslinked polymeric product free from detectable cyclopentadiene odor is obtained by contacting, under polymerization conditions, a mixture of Diels-Alder adducts of 4-vinylcyclohexene and cyclopentadiene and Diels-Alder oligomers of cyclopentadiene of at least 3 cyclopentadiene units with an olefin methathesis catalyst.
    Type: Grant
    Filed: June 10, 1991
    Date of Patent: March 10, 1992
    Assignee: Shell Oil Company
    Inventor: Donald R. Kelsey
  • Patent number: 5082909
    Abstract: This invention relates to a two component catalyst system for polymerization of metathesis polymerizable cycloolefins, comprising(a) a tungsten compound of the formula WOCl.sub.4-x (OAr).sub.x wherein Ar represents a hindered phenyl ring having bulky alkyl, alkoxyl halogen or aryl groups in the 2,6 position, i.e., diisopropyl or phenyl group and x=1, 2 or 3; and(b) an activator compound that is triphenyl tin hydride or trialkyl tin hydride, preferably a tributyltin hydride.Among the preferred molecules or groups that are substituted on the phenyl ring of the tungsten compound include chlorine, bromine, phenyl, methoxy and isopropyl. Ar may also represent a multisubstituted phenyl group such as 2,4-dichloro-6-methyl phenyl.
    Type: Grant
    Filed: October 12, 1990
    Date of Patent: January 21, 1992
    Assignee: Hercules Incorporated
    Inventor: Andrew Bell
  • Patent number: 5081208
    Abstract: A process is described for the polymerization of dicyclopentadiene using a novel catalyst system comprising (a) a tungsten compound which is the reaction product of a tungsten halide with a phenol which is not substituted with a bulky alkyl group at positions ortho with respect to the hydroxyl group, and (b) a trihydrocarbyl tin hydride.
    Type: Grant
    Filed: October 9, 1990
    Date of Patent: January 14, 1992
    Assignee: Shell Oil Company
    Inventor: Willem Sjardijn
  • Patent number: 5019544
    Abstract: This invention is a process for preparing a polymer which comprises contacting pure dicyclopentadiene with a pure tungsten catalyst complex, such as WCl.sub.3 (2,6-diisopropylphenoxy).sub.3, when tributyl tin hydride or triphenyl tin hydride is used as the activator for the polymerization. This process affords a method of polymerization of dicyclopentadiene in which the mixture gels slowly without the use of a rate moderator at 80.degree. C. (in from about 15 seconds to as much as two minutes or more) and furthermore cures quite slowly (in about 3-6 minutes). This delay makes these compositions particularly applicable to reaction injection molding processes. Moreover, both the tungsten complexes and the tin activator compounds employed in this invention are relatively insensitive to oxygen and water.
    Type: Grant
    Filed: August 9, 1990
    Date of Patent: May 28, 1991
    Assignee: Hercules Incorporated
    Inventor: Andrew Bell
  • Patent number: 5011730
    Abstract: Dielectric supports for electronic components, such as circuit boards, are provided which are comprised of two or more bulk polymerized norbornene-type monomers. The monomers may be easily processed into circuit boards, etc. by reaction injection molding. The copolymers obtained exhibit high heat distortion temperatures and good dielectric properties and a balance of properties that make them, for example, well suited for molded wire board materials.
    Type: Grant
    Filed: April 11, 1989
    Date of Patent: April 30, 1991
    Assignee: The B. F. Goodrich Company
    Inventors: Lindwood P. Tenney, David J. Smith, Dennis J. Janda, Dennis A. Barnes
  • Patent number: 4981931
    Abstract: This invention is a process for preparing a polymer which comprises contacting pure dicyclopentadiene with a pure tungsten catalyst complex, such as WCl.sub.3 (2,6-diisopropylphenoxy).sub.3, when tributyl tin hydride or triphenyl tin hydride is used as the activator for the polymerization. This process affords a method of polymerization of dicyclopentadiene in which the mixture gels slowly without the use of a rate moderator at 80.degree. C. (in from about 15 seconds to as much as two minutes or more) and furthermore cures quite slowly (in about 3-6 minutes). This delay makes these compositions particularly applicable to reaction injection molding processes. Moreover, both the tungsten complexes and the tin activator compounds employed in this invention are relatively insensitive to oxygen and water.
    Type: Grant
    Filed: February 24, 1989
    Date of Patent: January 1, 1991
    Assignee: Hercules Incoporated
    Inventor: Andrew Bell
  • Patent number: 4943621
    Abstract: Methods of preparing storage stable components useful for metathesis bulk polymerization of cycloolefin monomers are provided. These components contain cycloolefins with norbornene-functional groups and cocatalysts activated with a halometal compound. In these methods, the cocatalyst is completely formed before the halometal activator is added to prevent the formation of unwanted hydrogen halides, which catalyze undesired crosslinking reactions which destabilize the cocatalyst component. Bulk polymerization systems are provided wherein these storage stable cocatalyst components are paired with catalyst components that together form the complete metathesis catalyst system. For some embodiments, storage stability is aided by the removal of water.
    Type: Grant
    Filed: August 4, 1988
    Date of Patent: July 24, 1990
    Assignee: The B. F. Goodrich Company
    Inventors: Dennis J. Janda, Paul T. Stricharczuk, Robert J. Minchak
  • Patent number: 4933402
    Abstract: Disclosed is a method of delaying the metathesis polymerization of strained ring cycloolefins by addition of certain phosphorus-containing compounds including various aryl phosphates, aliphatic phosphates, aliphatic phosphites, aryl phosphites, aryl phosphines and alkyl phosphines.
    Type: Grant
    Filed: December 30, 1988
    Date of Patent: June 12, 1990
    Assignee: Hercules Incorporated
    Inventor: Albert S. Matlack
  • Patent number: 4923936
    Abstract: This invention pertains to the use of organoammonium, organophosphonium, organoarsonium heteropolymolybdates and heteropolytungstates, and mixtures thereof, as catalysts in a metathesis catalyst system in polymerization of cycloolefin monomers by ring opening polymerization. Polymerization can be by reaction injection molding in absence of a solvent whereby a thermoset polymer is produced or by solution polymerization in presence of a suitable solvent whereby a thermosetting or a thermoplastic polymer is produced. The cycloolefin monomers are selected from monocycloolefins except cyclohexane, polycycloolefins containing at least one norbornene group, and mixtures thereof.
    Type: Grant
    Filed: February 21, 1989
    Date of Patent: May 8, 1990
    Assignee: The BFGoodrich Company
    Inventors: Brian L. Goodall, Larry F. Rhodes
  • Patent number: 4886861
    Abstract: Free radical polymerization processes employing cobalt(II) chelates of vicinal iminohydroxyimino- and dihydroxyiminoalkanes, N,N'-bis(salicylidene)ethylenediamines and porphyrins as catalytic chain transfer agents, in admixture with certain Lewis bases, for controlling the molecular weight of the homopolymers and copolymers produced.
    Type: Grant
    Filed: April 16, 1987
    Date of Patent: December 12, 1989
    Assignee: E. I. DuPont de Nemours and Company
    Inventor: Andrew H. Janowicz
  • Patent number: 4810762
    Abstract: The invention is a process for preparing a polymer which comprises contacting dicyclopentadiene with a catalyst comprising a phenolic substituted tungsten halide and a trialkyltin hydride or triphenyltin hydride and recovering said polymer. The invention is also a polymer of dicyclopentadiene as prepared in the process of the invention and a catalyst used in the process of the invention to prepare said polymer.
    Type: Grant
    Filed: September 24, 1987
    Date of Patent: March 7, 1989
    Assignee: Shell Oil Company
    Inventors: Willem Sjardijn, Arris H. Kramer
  • Patent number: 4729976
    Abstract: The invention is a process for preparing a polymer which comprises contacting dicyclopentadiene with a catalyst comprising a phenolic substituted tungsten halide and a trialkyltin hydride or triphenyltin hydride and recovering said polymer. The invention is also a polymer of dicyclopentadiene as prepared in the process of the invention and a catalyst used in the process of the invention to prepare said polymer.
    Type: Grant
    Filed: October 27, 1986
    Date of Patent: March 8, 1988
    Assignee: Shell Oil Company
    Inventors: Willem Sjardijn, Arris H. Kramer
  • Patent number: 4701510
    Abstract: Thermoset polycycloolefins are obtained by polymerzing at an elevated temperature a cycloolefin containing at least one norbornene group in the presence of a metathesis catalyst system and also in the presence of an effective amount of a polyfunctional cycloolefin crosslinker containing at least one norbornene group, but preferably two or more, with two or more unsaturated sites, preferably two or more double bonds.
    Type: Grant
    Filed: December 16, 1985
    Date of Patent: October 20, 1987
    Assignee: The B.F. Goodrich Company
    Inventors: Robert J. Minchak, Parley C. Lane, Jr.
  • Patent number: RE35717
    Abstract: A cycloolefin copolymerization method, feed composition and product made from the feed which includes: a nonpolar cycloolefin, a polar cycloolefin and a catalyst. Preferably, the nonpolar cycloolefin is dicyclopentadiene, the catalyst comprises WCl.sub.6, the polar cycloolefin is an ester, and the composition also includes an activator.
    Type: Grant
    Filed: September 17, 1993
    Date of Patent: January 20, 1998
    Assignee: Metton America, Inc.
    Inventor: Steven H. Nahm