Polymerization With Metallocene Catalysts Patents (Class 526/943)
  • Patent number: 8623976
    Abstract: The present invention provides a novel catalyst composition comprising a metallocene complex, and a novel producing method for various polymer compounds. Preferably, the invention provides a novel polymer compound, and a producing method thereof. Specifically, the invention provides a polymerization catalyst composition, comprising: (1) a metallocene complex represented by the general formula (I), including: a central metal M which is a group III metal atom or a lanthanoid metal atom; a ligand Cp* bound to the central metal and including a substituted or unsubstituted cyclopentadienyl derivative; monoanionic ligands Q1 and Q2; and w neutral Lewis base L; and (2) an ionic compound composed of a non-ligand anion and a cation: where w represents an integer of 0 to 3.
    Type: Grant
    Filed: July 6, 2012
    Date of Patent: January 7, 2014
    Assignee: RIKEN
    Inventors: Zhaomin Hou, Yunjie Luo, Xiaofang Li, Jens Baldamus
  • Patent number: 8609793
    Abstract: The present invention provides polymerization processes utilizing a catalyst system containing an ansa-metallocene and a second metallocene compound for the production of olefin polymers.
    Type: Grant
    Filed: April 2, 2012
    Date of Patent: December 17, 2013
    Assignee: Chevron Phillips Chemical Company LP
    Inventors: Richard M. Buck, Qing Yang, Albert P. Masino, Christopher E. Wittner
  • Patent number: 8604141
    Abstract: Ruthenium and osmium carbene compounds that are stable in the presence of a variety of functional groups and can be used to catalyze olefin metathesis reactions on unstrained cyclic and acyclic olefins are disclosed. Also disclosed are methods of making the carbene compounds. The carbene compounds are of the formula where M is Os or Ru; R1 is hydrogen; R is selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl; X and X1 are independently selected from any anionic ligand; and L and L1 are independently selected from any neutral electron donor. The ruthenium and osmium carbene compounds of the present invention may be synthesized using diazo compounds, by neutral electron donor ligand exchange, by cross metathesis, using acetylene, using cumulated olefins, and in a one-pot method using diazo compounds and neutral electron donors.
    Type: Grant
    Filed: April 24, 2012
    Date of Patent: December 10, 2013
    Assignee: California Institute of Technology
    Inventors: Robert H. Grubbs, Peter Schwab, Sonbinh T. Nguyen
  • Patent number: 8603933
    Abstract: The present application aims to provide a process for producing a solid polymerization catalyst component, including the steps of (A) producing a solution with a transition metal compound and a solvent; (B) solidifying a component with the transition metal compound to produce the solid polymerization catalyst component in a solidification stage; (C) recovering from the solidification stage a liquid stream containing a minor amount of the transition metal compound dissolved therein and a solid catalyst stream; and (D) recovering the transition metal component from the liquid stream, characterized in that step (D) may include concentrating the solution to produce a first product stream including the solvent and being essentially free of the transition metal compound and a second product stream including the solvent and the transition metal compound, characterized in that the concentration is conducted within a temperature range of from 0 to 100 degrees Celsius.
    Type: Grant
    Filed: November 11, 2010
    Date of Patent: December 10, 2013
    Assignee: Borealis AG
    Inventors: Pertti Elo, Sameer Vijay, Kimmo Hakala, Soile Rautio, Ismo Lehtiniemi
  • Patent number: 8598242
    Abstract: Disclosed is an expanded polypropylene copolymer resin particle whose base resin is a polypropylene random copolymer resin having a melting point of not more than 145° C., the base resin having a H/W ratio of not more than 8 where H (%) is a maximum height of an elution peak and W (° C.) is a peak width at half a height of the peak in an elution curve obtained from a differential value of eluted content measured by cross fractionation chromatography, and a ratio (Mw/Mn) of a weight-average molecular weight (Mw) and a number-average molecular weight (Mn) being not less than 3.5 in a molecular weight distribution measurement of a whole of eluted components. With such an expanded polypropylene copolymer resin particle, it is possible to provide expanded polypropylene copolymer resin particles which are capable of producing an in-mold expansion-molded article with a low molding heating vapor pressure, and which causes few deformation or shrinkage of an obtained in-mold expansion-molded article (i.e.
    Type: Grant
    Filed: March 30, 2010
    Date of Patent: December 3, 2013
    Assignee: Kaneka Corporation
    Inventor: Kenichi Senda
  • Patent number: 8598241
    Abstract: Provided are polypropylene resin pre-foamed particles including, as base resin, polypropylene resin that satisfies the following requirements (a) through (c): (a) in cross fractionation chromatography, an amount of components eluted at a temperature of not more than 40° C. is not more than 2.0% by weight; (b) a melting point is not less than 100° C. but not more than 160° C.; and (c) propylene monomer units are present in an amount of not less than 90 mol % but not more than 100 mol %, and olefin units each having a carbon number of 2 or 4 or more are present in an amount of not less than 0 mol % but not more than 10 mol %. The polypropylene resin pre-foamed particles can be molded by in-mold foaming molding at a not high molding heating steam pressure, and a polypropylene resin in-mold foaming molded product excellent in dimensional stability at high temperatures can be prepared from the polypropylene resin pre-foamed particles.
    Type: Grant
    Filed: January 13, 2010
    Date of Patent: December 3, 2013
    Assignee: Kaneka Corporation
    Inventors: Toru Yoshida, Hiroshi Tsuneishi
  • Patent number: 8598287
    Abstract: A process for polymerizing olefin(s) utilizing a cyclic bridged metallocene catalyst system to produce polymers with improved properties is provided. The catalyst system may include a cyclic bridged metallocene, LA(R?SiR?)LBZrQ2, activated by an activator, the activator comprising aluminoxane, a modified aluminoxane, or a mixture thereof, and supported by a support, where: LA and LB are independently an unsubstituted or a substituted cyclopentadienyl ligand bonded to Zr and defined by the formula (C5H4-dRd), where R is hydrogen, a hydrocarbyl substituent, a substituted hydrocarbyl substituent, or a heteroatom substituent, and where d is 0, 1, 2, 3 or 4; LA and LB are connected to one another with a cyclic silicon bridge, R?SiR?, where R? are independently hydrocarbyl or substituted hydrocarbyl substituents that are connected with each other to form a silacycle ring; and each Q is a labile hydrocarbyl or a substituted hydrocarbyl ligand.
    Type: Grant
    Filed: October 9, 2008
    Date of Patent: December 3, 2013
    Assignee: Univation Technologies, LLC
    Inventors: Chi-I Kuo, Dongming Li, Ching-Tai Lue, Francis C. Rix, Mark G Goode, Daniel P. Zilker, Jr., Tae Hoon Kwalk
  • Patent number: 8586497
    Abstract: Olefin polymerization catalyst systems including a high molecular weight catalyst compound and a low molecular weight catalyst compound, and methods of making same are provided. High molecular weight catalysts include metallocene catalysts and low molecular weight catalysts include non-metallocene compounds including biphenyl phenol compounds. Generally catalyst systems may include less than about 5.0 mol % of the high molecular weight catalyst compound relative to said low molecular weight catalyst. Methods for olefin polymerization including the aforementioned catalyst systems, and polyolefins and products made therefrom.
    Type: Grant
    Filed: November 12, 2008
    Date of Patent: November 19, 2013
    Assignee: Univation Technologies, LLC
    Inventors: Rainer Kolb, Dongming Li, Francis C. Rix, Cesar A. Garcia-Franco
  • Patent number: 8580902
    Abstract: Provided are catalyst systems, processes for polymerizing one or more olefins, polymers resulting therefrom, and articles prepared from such polymers. The processes comprise contacting under polymerization conditions one or more olefin monomers, preferably propylene, with a catalyst system comprising a transition metal compound and an activator of the formula (1) or (2) as described herein. The polymer compositions described herein exhibit advantageously narrow composition distributions and high melting points in comparison to conventional polymers having the same comonomer content. The polymers described herein exhibit improved properties, e.g., pellet stability, impact properties, heat seal properties, and structural integrity in film and fabricated parts applications.
    Type: Grant
    Filed: August 14, 2009
    Date of Patent: November 12, 2013
    Assignee: ExxonMobil Chemical Patents Inc.
    Inventors: Donna J. Crowther, Peijun Jiang, Rainer Kolb
  • Patent number: 8575284
    Abstract: Compositions useful for activating catalysts for olefin polymerization, and methods for making same, are provided. Such compositions can be derived from at least: an organoaluminum compound, a carrier, an oxygen source, and, optionally, a Lewis base.
    Type: Grant
    Filed: September 28, 2012
    Date of Patent: November 5, 2013
    Assignee: Albemarle Corporation
    Inventors: Lubin Luo, Samuel A. Sangokoya, Xiao Wu, Steven P. Diefenbach, Brian Kneale
  • Patent number: 8569532
    Abstract: A complex containing a ligand of formula (I): useful in the formation of olefin polymerization catalysts and their use in olefin polymerization.
    Type: Grant
    Filed: June 11, 2012
    Date of Patent: October 29, 2013
    Assignee: Borealis Technology Oy
    Inventors: Alexander Zelmanovich Voskoboynik, Andrei Fyodorovich Asachenko, Dmitry Konanovich, Mikhail V. Nikulin, Alexey Tzarev, Janne Maaranen, Tiina Vanne, Jyrki Kauhanen, Erik Mansner, Esa Kokko, Laura Saarinen
  • Patent number: 8569194
    Abstract: The present invention relates to a supported catalyst composition for polymerization of olefins comprising at least two catalytic components; and a polymerization process using that catalyst composition; and a method for its preparation.
    Type: Grant
    Filed: August 11, 2006
    Date of Patent: October 29, 2013
    Assignee: Saudi Basic Industries Corporation
    Inventors: Wei Xu, Syriac J. Palackal, Atieh Abu-Ruqabah, Maneet Muktibodh, Bing Wang, Nicolaas Hendrika Friederichs
  • Patent number: 8563671
    Abstract: Method employing a supported metallocene catalyst composition in the production of an isotactic ethylene propylene co-polymer. The composition comprises a metallocene component supported on a particulate silica support having average particle size of 10-40 microns, a pore volume of 1.3-1.6 ml/g, a surface area of 200-400 m2/g. An alkylalumoxane cocatalyst component is incorporated on the support. The isospecific metallocene is characterized by the formula: B(CpRaRb)(FlR?2)MQn??(1) or by the formula: B?(Cp?R?aR?b)(Fl?)M?Q?n???(2) In the formulas Cp and Cp? are substituted cyclopentadienyl groups, Fl and Fl? are fluorenyl groups, and B and B? are structural bridges. R? are substituents at the 2 and 7 positions, Ra and R?a are substituents distal to the bridge, and Rb and R?b are proximal to the bridge. M and M? are transition metals, Q? is a halogen or a C1-C4 alkyl group; and n? is an integer of from 0-4.
    Type: Grant
    Filed: September 18, 2012
    Date of Patent: October 22, 2013
    Assignee: Fina Technology, Inc.
    Inventors: William Gauthier, David Rauscher, Jun Tian, Nathan Williams
  • Patent number: 8557924
    Abstract: The present invention deals with polymer compositions suitable for making pipes. The compositions comprise a multimodal copolymer of ethylene and one or more alpha-olefins having from 4 to 10 carbon atoms wherein the multimodal ethylene copolymer has a density of from 924 to 935 kg/m3, a melt index MFR5 of from 0.5 to 6.0 g/10 min, a melt index MFR2 of from 0.1 to 2.0 g/10 min and a shear thinning index SHI2.7/210 of from 2 to 50.
    Type: Grant
    Filed: May 25, 2009
    Date of Patent: October 15, 2013
    Assignee: Borealis AG
    Inventors: Mats Bäckman, Carl-Gustaf Ek, Anneli Pakkanen, Magnus Palmlöf
  • Patent number: 8557935
    Abstract: Bimetallic catalysts, methods of producing bimetallic catalysts comprising a modified Ziegler-Natta catalyst and a metallocene, and methods of olefin polymerization using such catalysts are provided. The method of producing the bimetallic catalyst may include combining (a) a Ziegler-Natta catalyst comprising a Group 4, 5 or 6 metal halide and/or oxide, optionally including a magnesium compound, with (b) a modifier compound (“modifier”), wherein the modifier compound is a Group 13 alkyl compound, to form a modified Ziegler-Natta catalyst. The modified Ziegler-Natta catalyst is preferably non-activated, that is, it is unreactive towards olefin polymerization alone. The molar ratio of the Group 13 metal (of the modifier) to the Group 4, 5 or 6 metal halide and/or oxide may be less than 10:1. The bimetallic catalysts are useful in producing bimodal polymers, particularly bimodal polyethylene, having a Polydispersity (Mw/Mn) of from 12 to 50, which may be used in pipes and films.
    Type: Grant
    Filed: June 13, 2012
    Date of Patent: October 15, 2013
    Assignee: Univation Technologies, LLC
    Inventors: Sun-Chueh Kao, Michael D. Awe
  • Patent number: 8545980
    Abstract: A polypropylene resin having: (1) a melt flow rate (MFR) of 6 to 100 g/10 minutes, (2) a molecular weight distribution (Mw/Mn), measured by gel permeation chromatography, of 3 to 6, and (3) a 116° C. non-eluted component content (100-W116(%)) of 50% or more and a content of components eluted at 90° C. or less (W90) of 10 to 30%, measured by temperature-rising fractional chromatography (TREF).
    Type: Grant
    Filed: October 31, 2005
    Date of Patent: October 1, 2013
    Assignee: Idemitsu Kosan Co., Ltd.
    Inventors: Takeharu Tajima, Toshitaka Kanai, Tomoaki Takebe, Yutaka Minami
  • Patent number: 8546595
    Abstract: Halogen substituted metallocene compounds are described and comprise one or more monocyclic or polycyclic ligands that are pi-bonded to the metal atom and include at least one halogen substituent directly bonded to an sp2 carbon atom at a bondable ring position of the ligand, wherein the or at least one ligand has one or more ring heteroatoms in its cyclic structure. When combined with a suitable activator, these compounds show activity in the polymerization of olefins, such as ethylene and propylene.
    Type: Grant
    Filed: March 20, 2012
    Date of Patent: October 1, 2013
    Assignee: ExxonMobil Chemical Patents Inc.
    Inventors: Alexander Z. Voskoboynikov, Alexey N. Ryabov, Mikhail V. Nikulin, Alexander V. Lygin, Dmitry V. Uborsky, Catalina L. Coker, Jo Ann M. Canich
  • Patent number: 8530580
    Abstract: The present invention deals with polymer compositions suitable for making pipes. The compositions comprise a multimodal copolymer of ethylene and one or more alpha-olefins having from 4 to 10 carbon atoms wherein the multimodal ethylene copolymer has a density of from 924 to 960 kg/m3, a melt index MFR5 of from 0.5 to 6.0 g/10 min, a melt index MFR2 of from 0.1 to 2.0 g/10 min and a shear thinning index SHI2.7/210 of from 2 to 50. The compositions further have a level of volatile compounds of at most 100 ppm by weight and/or a homogeneity rating of at most 3.
    Type: Grant
    Filed: May 25, 2009
    Date of Patent: September 10, 2013
    Assignee: Borealis AG
    Inventors: Mats Bäckman, Carl-Gustaf Ek, Anneli Pakkanen, Magnus Palmlöf
  • Patent number: 8524627
    Abstract: The present invention relates to a process for preparing an activating support for metallocene complexes in the polymerization of olefins comprising the steps of: I) providing a support consisting in particles formed from at least one porous mineral oxide; II) optionally fixing the rate of silanols on the surface of the support; III) functionalizing the support with a solution containing a metallic salt; IV) heating the functionalized support of step c) under an inert gas or hydrogen; V) oxidizing the support of step IV by treatment under N2O and then under oxygen; VI) retrieving an active support having a controlled number of OH groups. That activating support is used to activate a metallocene catalyst component for the polymerization of olefins.
    Type: Grant
    Filed: April 29, 2010
    Date of Patent: September 3, 2013
    Assignee: Total Research & Technology Feluy
    Inventors: Gaëlle Pannier, Christophe Boisson, Roger Spitz
  • Patent number: 8524844
    Abstract: Carbon dioxide is used to control the ratio of polymer components in a polyethylene composition made using a combination catalyst comprising a chromium catalyst, a single site catalyst and one or more activators.
    Type: Grant
    Filed: July 22, 2011
    Date of Patent: September 3, 2013
    Assignee: Nova Chemicals (International) S.A.
    Inventors: Yves Lacombe, Victoria Ker, Peter Phung Minh Hoang, Patrick Evans
  • Patent number: 8524626
    Abstract: The present invention provides polymerization catalyst compositions employing novel dinuclear metallocene compounds. Methods for making these new dinuclear metallocene compounds and for using such compounds in catalyst compositions for the polymerization and copolymerization of olefins are also provided.
    Type: Grant
    Filed: November 3, 2011
    Date of Patent: September 3, 2013
    Assignee: Chevron Phillips Chemical Company LP
    Inventors: Rex E. Murray, Kumudini C. Jayaratne, Qing Yang, Joel L. Martin
  • Patent number: 8507621
    Abstract: Catalyst compositions comprising a first metallocene compound, a second metallocene compound, an activator-support, and an organoaluminum compound are provided. An improved method for preparing cyclopentadienyl complexes used to produce polyolefins is also provided.
    Type: Grant
    Filed: October 30, 2012
    Date of Patent: August 13, 2013
    Assignee: Chevron Phillips Chemical Company LP
    Inventors: Kumundini C. Jayaratne, Michael D. Jensen, Qing Yang
  • Patent number: 8507627
    Abstract: This invention relates to an aromatic vinyl compound-conjugated diene compound copolymer capable of giving excellent wear resistance and resistance to wet skid to a tire, and more particularly to an aromatic vinyl compound-conjugated diene compound copolymer obtained by an addition polymerization of an aromatic vinyl compound and a conjugated diene compound in the presence of a polymerization catalyst composition comprising at least one specified metallocene complex selected from the group consisting of a metallocene complex represented by the following general formula (I): (wherein M is a lanthanoid element, scandium or yttrium, and CpR is independently a non-substituted or substituted indenyl, and Ra to Rf are independently an alkyl group having a carbon number of 1-3 or a hydrogen atom, and L is a neutral Lewis base, and w is an integer of 0-3) and so on, wherein a content of cis-1,4 bond in a conjugated diene compound portion is not less than 80%.
    Type: Grant
    Filed: June 4, 2009
    Date of Patent: August 13, 2013
    Assignees: Bridgestone Corporation, Riken
    Inventors: Ryuji Nakagawa, Junko Matsushita, Yoichi Ozawa, Shojiro Kaita, Olivier Tardif
  • Patent number: 8507706
    Abstract: Certain metallocene compounds are provided that, when used as a component in a supported polymerization catalyst under industrially relevant polymerization conditions, afford high molar mass homo polymers or copolymers like polypropylene or propylene/ethylene copolymers without the need for any ?-branched substituent in either of the two available 2-positions of the indenyl ligands. The substituent in the 2-position of one indenyl ligand can be any radical comprising hydrogen, methyl, or any other C2-C40 hydrocarbon which is not branched in the ?-position, and the substituent in the 2-position of the other indenyl ligand can be any C4-C40 hydrocarbon radical with the proviso that this hydrocarbon radical is branched in the ?-position. This metallocene topology affords high melting point, very high molar mass homo polypropylene and very high molar mass propylene-based copolymers. The activity/productivity levels of catalysts including the metallocenes of the present invention are exceptionally high.
    Type: Grant
    Filed: September 6, 2012
    Date of Patent: August 13, 2013
    Assignee: Lummus Novolen Technology GmbH
    Inventors: Anita Dimeska, Ralph-Dieter Maier, Nicola Stephanie Paczkowski, Matthew Grant Thorn, Andreas Winter, Joerg Schulte, Thorsten Sell
  • Patent number: 8501892
    Abstract: Ethylene propylene copolymers, substantially free of diene, are described. The copolymers will have a uniform distribution of both tacticity and comonomer between copolymer chains. Further, the copolymers will exhibit a statistically insignificant intramolecular difference of tacticity. The copolymers are made in the presence of a metallocene catalyst.
    Type: Grant
    Filed: August 26, 2011
    Date of Patent: August 6, 2013
    Assignee: Exxonmobil Chemical Patents Inc.
    Inventors: Sudhin Datta, Bruce A. Harrington, Weiguo Hu, Periagaram S. Ravishankar, George Rodriguez
  • Patent number: 8501654
    Abstract: The present invention provides dual catalyst systems containing a metallocene catalyst and a hydrogen scavenging catalyst, and polymerization processes employing these dual catalyst systems. Due to a reduction in hydrogen levels in the polymerization processes, olefin polymers produced from these polymerization processes may have a higher molecular weight, a lower melt index, and higher levels of unsaturation.
    Type: Grant
    Filed: June 5, 2012
    Date of Patent: August 6, 2013
    Assignee: Chevron Philips Chemical Company LP
    Inventors: Rex E. Murray, William B. Beaulieu, Qing Yang, Errun Ding, Gary L. Glass, Alan L. Solenberger, Steven J. Secora
  • Patent number: 8497330
    Abstract: Methods for gas phase olefin polymerization are provided. The method can include combining a spray dried catalyst system with a diluent to produce a catalyst slurry. The catalyst system can include a metallocene compound. Ethylene, a continuity additive, and the catalyst slurry can be introduced to a gas phase fluidized bed reactor. The reactor can be operated at conditions sufficient to produce a polyethylene. The spray dried catalyst system can have a catalyst productivity of at least 12,000 grams polyethylene per gram of the catalyst system.
    Type: Grant
    Filed: December 22, 2010
    Date of Patent: July 30, 2013
    Assignee: Univation Technologies, LLC
    Inventors: F. David Hussein, Kevin J. Cann, Ann M. Schoeb-Wolters, Phuong A. Cao, Bruce J. Savatsky, Eric J. Markel, Daniel P. Zilker, Jr., Garth R. Giesbrecht
  • Patent number: 8497329
    Abstract: The invention generally provides for methods for controlling polymer properties. In particular, invention provides for methods for controlling the comonomer composition distribution of polyolefins such as ethylene alpha-olefin copolymers by altering at least one or more of the following parameters: the molar ratio of hydrogen to ethylene, the molar ratio of comonomer to ethylene, the partial pressure of ethylene, and the reactor temperature without substantially changing the density and/or the melt index of the copolymer.
    Type: Grant
    Filed: January 18, 2008
    Date of Patent: July 30, 2013
    Assignee: Univation Technologies, LLC
    Inventors: Rainer Kolb, James M. Farley, John F. Szul, Mark P. Ossowski
  • Patent number: 8481665
    Abstract: Use of a metallocene compound of general formula Ind2R?MQ2 as a component of a catalyst system in producing polyethylene, wherein each Ind is the same or different and is indenyl or substituted indenyl; R? is a bridge which comprises a C1 to C4 alkylene radical, a dialkyl germanium or silicon or siloxane, alkyl phosphine or amine, which bridge is substituted or unsubstituted, M is a Group IV metal or vanadium and each Q is hydrocarbyl having 1 to 20 carbon atoms or halogen; and the ratio of meso to racemic forms of the metallocene in the catalyst system is at least 1:3. The metallocene may be supported. The ethylene may be polymerized in a reaction medium that is substantially free of any external comonomer, with comonomer being formed in situ. The produced polyethylene may have long chain branching. The produced polyethylene may be atactic.
    Type: Grant
    Filed: June 26, 2012
    Date of Patent: July 9, 2013
    Assignee: Total Research & Technology Feluy
    Inventors: Abbas Razavi, Liliana Peters
  • Patent number: 8476370
    Abstract: The present invention deals with polymer compositions suitable for making pipes. The compositions comprise a multimodal copolymer of ethylene and one or more alpha-olefins having from 4 to 10 carbon atoms wherein the multimodal ethylene copolymer has a density of from 937 to 950 kg/m3, a melt index MFR5 of from 0.3 to 3.0 g/10 min, a melt index MFR2 of from 0.1 to 2.0 g/10 min and a shear thinning index SHI2.7/210 of from 2 to 30.
    Type: Grant
    Filed: May 25, 2009
    Date of Patent: July 2, 2013
    Assignee: Borealis AG
    Inventors: Mats Backman, Carl-Gustaf Ek, Anneli Pakkanen, Magnus Palmlof, Tarja-Tuulikki Turpeinen, John Severn
  • Patent number: 8470947
    Abstract: Disclosed is an ethylenic polymer having a long characteristic relaxation time. The ethylenic polymer satisfies the following requirements: (a) the ethylenic polymer is a non-crosslinked ethylenic polymer; (b) the number of long-chain branches (LCB) per 1000 carbon atoms is 0.1-1.5 inclusive; (c) the intrinsic viscosity [?] is 1.0-3.0 dl/g inclusive; and (d) the ratio (G?/G?) of the storage modulus (G?) to the loss modulus (G?), determined by dynamic viscoelasticity measurement at 190° C. and at an angular frequency of 0.1 rad/sec is 0.8 or more and 4.0 or less.
    Type: Grant
    Filed: September 30, 2010
    Date of Patent: June 25, 2013
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Yasutoyo Kawashima, Takahiro Hino, Taichi Senda
  • Patent number: 8471050
    Abstract: The present invention relates to non-symmetrical organometallic transition metal compounds of the compound of the formula (I) where R8 and R9 are identical or different and each an substituted or unsubstituted organic radical having from 1 to 40 carbon atoms, catalyst systems comprising at least one of the organometallic transition metal compounds of the present invention and a process for preparing polyolefins by polymerization or copolymerization of at least one olefin in the presence of one of the catalyst systems of the present invention.
    Type: Grant
    Filed: July 20, 2010
    Date of Patent: June 25, 2013
    Assignee: Basell Polyolefine GmbH
    Inventors: Fabiana Fantinel, Ilya Nifant'ev, Shahram Mihan
  • Patent number: 8461276
    Abstract: Propylene polymerization processes, polymers and films formed therefrom are described herein. The propylene polymerization processes generally include contacting propylene and an amount of ethylene with a first metallocene catalyst and a second metallocene catalyst within a polymerization reaction vessel to form a propylene based polymer, wherein the amount is an amount effective to form the propylene based polymer including from about 2 wt. % to about 6 wt. % ethylene, the second metallocene catalyst is capable of incorporating a greater amount of ethylene into the propylene based polymer than the first metallocene catalyst and wherein the first metallocene catalyst is capable of forming a propylene/ethylene random copolymer exhibiting a melting temperature that is greater than that of a propylene/ethylene random copolymer formed from the second metallocene catalyst.
    Type: Grant
    Filed: June 18, 2012
    Date of Patent: June 11, 2013
    Assignee: Fina Technology, Inc.
    Inventors: Tim Coffy, Kenneth Blackmon, Joseph Thorman, David Rauscher, Jun Tian, William Gauthier, Nathan Williams
  • Patent number: 8461365
    Abstract: A metallocene complex by which high uptake efficiency of ethylene and/or ?-olefin can be obtained compared with the conventional metallocene catalyst, and robber component having high molecular weight can be polymerized, and polymerization method of olefin. Metallocene complex (metallocene complex having furyl or thienyl group in which substituent exists at 5-position of indenyl ring, and substituent may exist at 2-position of indenyl ring, and the like) represented by the general formula [II], the catalyst for olefin polymerization characterized by comprising said metallocene complex, and polymerization method of olefin characterized that polymerization or copolymerization of olefin is carried out using said polymerization catalyst for olefin, and the like.
    Type: Grant
    Filed: December 14, 2009
    Date of Patent: June 11, 2013
    Assignee: Japan Polypropylene Corporation
    Inventors: Masato Nakano, Hideshi Uchino, Naoshi Iwama, Masami Kashimoto, Tomohiro Kato
  • Patent number: 8455386
    Abstract: The present invention discloses a catalyst system based on a metallocene catalyst component and a new single site catalyst component for the production in a single reactor of improved polyolefins having a bimodal molecular weight distribution.
    Type: Grant
    Filed: March 28, 2012
    Date of Patent: June 4, 2013
    Assignee: Total Research & Technology Feluy
    Inventor: Abbas Razavi
  • Patent number: 8455589
    Abstract: This invention relates to a propylene polymer comprising a component having a crystallinity of 10% or less and a component having a crystallinity of 20% or more, said propylene polymer having: a) a melting point of X° C. or more where X=?0.0038(Tp)2+0.36(Tp)+150, where Tp is the temperature of polymerization in ° C.; b) an Mw of 10,000 g/mol or more; c) a heat of fusion of from 1-70 J/g; d) Stereodefects per 10,000 monomer units of Y or less where Y=2.35(Tp)?100 (where Tp is the temperature of polymerization in ° C.) for the portion of the blend that is insoluble in hexane at 23° C.; e) a dot T-Peel on Kraft paper of 1 N or more; and f) a branching factor of 0.98 or less, where the branching factor is the ratio of g? measured at Mz to g? measured at Mw, and process to produce such polymers.
    Type: Grant
    Filed: February 15, 2012
    Date of Patent: June 4, 2013
    Assignee: ExxonMobil Chemical Patents Inc.
    Inventors: Jo Ann M. Canich, Peijun Jiang
  • Patent number: 8455597
    Abstract: This invention relates to a homogenous process for making a vinyl terminated propylene polymer, wherein the process comprises: contacting, propylene, under polymerization conditions, with a catalyst system comprising an activator and at least one metallocene compound, where the metallocene compound is represented by the formula: where: M is hafnium or zirconium; each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and a combination thereof, (two X's may form a part of a fused ring or a ring system); each R1 is, independently, a C1 to C10 alkyl group; each R2 is, independently, a C1 to C10 alkyl group; each R3 is, independently, hydrogen; each R4, R5, and R6, is, independently, hydrogen or a substituted or unsubstituted hydrocarbyl group, a heteroatom or heteroatom containing group; T is a bridging group; each R7 is, independently, hydrogen, halog
    Type: Grant
    Filed: March 25, 2011
    Date of Patent: June 4, 2013
    Assignee: ExxonMobil Chemical Patents Inc.
    Inventors: Donna J. Crowther, Patrick Brant, Carlos U. De Gracia, Jacqueline A. Lovell
  • Patent number: 8450437
    Abstract: The present techniques relate to catalyst compositions, methods, and polymers encompassing a Group 4 metallocene compound comprising bridging ?5-cyclopentadienyl-type ligands, typically in combination with a cocatalyst, and a activator. The compositions and methods presented herein include ethylene polymers with low melt elasticity.
    Type: Grant
    Filed: January 12, 2012
    Date of Patent: May 28, 2013
    Assignee: Chevron Phillips Chemical Company LP
    Inventors: Qing Yang, Max P. McDaniel, Joel L. Martin, Youlu Yu, David C. Rohlfing, Michael D. Jensen
  • Patent number: 8450436
    Abstract: The present invention provides dual catalyst systems and polymerization processes employing these dual catalyst systems. The disclosed polymerization processes can produce olefin polymers at higher production rates, and these olefin polymers may have a higher molecular weight and/or a lower melt index.
    Type: Grant
    Filed: November 20, 2012
    Date of Patent: May 28, 2013
    Assignee: Chevron Phillips Chemical Company LP
    Inventors: Albert P. Masino, Rex E. Murray, Qing Yang, Steve J. Secora, Kumudini C. Jayaratne, William B. Beaulieu, Errun Ding, Gary L. Glass, Alan L. Solenberger, Ted H. Cymbaluk
  • Patent number: 8445609
    Abstract: An object of the present invention is to provide a method for producing an olefin polymer, with which an olefin polymer having good particle properties can be produced in high activity, fouling inside the polymerization vessel, such as a vessel wall or an impeller, can be effectively prevented, and a long-term stable operation is achieved. A method for producing an olefin polymer according to the present invention is characterized by including (co)polymerizing at least one olefin selected from the group consisting of ethylene and ?-olefins having 3 to 20 carbon atoms in a polymerization vessel in the presence of (A) a solid catalyst component for olefin polymerization, (B) an aliphatic amide, and (C) an organoaluminum compound.
    Type: Grant
    Filed: April 21, 2010
    Date of Patent: May 21, 2013
    Assignees: Mitsui Chemicals, Inc., Prime Polymer Co., Ltd.
    Inventors: Yasushi Tohi, Ken Yoshitsugu, Naoya Akiyama, Toshio Fujita, Masatoshi Chinaka
  • Patent number: 8445608
    Abstract: The present invention discloses a method for preparing long-chain-branched isotactic polypropylene by first oligomerizing propylene with a suitable oligomerization catalyst system and then copolymerizing propylene and the oligomer obtained in situ with a mono-aryl-substituted methylene bridged catalyst system.
    Type: Grant
    Filed: December 14, 2009
    Date of Patent: May 21, 2013
    Assignees: Total Petrochemicals Research Feluy, Centre National de la Recherche Scientifique (CNRS)
    Inventors: Jean-Franøois Carpentier, Evgueni Kirillov, Nicolas Marquet, Abbas Razavi
  • Patent number: 8436114
    Abstract: This invention relates to a process for polymerizing olefins in which the amount of trimethylaluminum in a methylalumoxane solution is adjusted to be from 1 to 25 mol %, prior to use as an activator, where the mol % trimethylaluminum is determined by 1H NMR of the solution prior to combination with any support. This invention also relates to a process for polymerizing olefins in which the amount of an unknown species present in a methylalumoxane solution is adjusted to be from 0.10 to 0.65 integration units prior to use as an activator, where the amount of the unknown species is determined by the 1H NMR spectra of the solution performed prior to combination with any support. Preferably, the methylalumoxane solution is present in a catalyst system also comprising a metallocene transition metal compound.
    Type: Grant
    Filed: October 18, 2011
    Date of Patent: May 7, 2013
    Assignee: ExxonMobil Chemical Patents Inc.
    Inventors: Donna J. Crowther, David M. Fiscus
  • Patent number: 8436112
    Abstract: The invention is directed to a metallocene catalyst system comprising an inert silica support having pores with a peak pore volume of greater than about 0.115 mL/g at a pore diameter between about 250 Angstroms and about 350 Angstroms, and an alumoxane activator, with the metallocene being bound substantially throughout the support. The activator is grafted to the support in a solvent at a reflux temperature of toluene to obtain an aluminoxane on silica, and a metallocene component is added to make a MCS having a metallocene loading of about 2 wt %. This facilitates the production of metallocene catalyst systems having increased catalytic activity than previously recognized that is at least about 20 percent higher than the catalytic activity for a metallocene loading of about 1 wt % where the activator is grafted to the support at room temperature.
    Type: Grant
    Filed: January 14, 2008
    Date of Patent: May 7, 2013
    Assignee: Fina Technology, Inc.
    Inventors: Jun Tian, William Gauthier, David Rauscher, Shady Henry
  • Patent number: 8436113
    Abstract: There is provided a method for producing copolymer that is composed of ethylene and alpha-olefin by a solution polymerization, and more specifically, a method for producing copolymer that is composed of ethylene and aromatic monomer as main components by using a transition metal catalyst including a cyclopentadiene derivative, and one or more anionic ligand having aryloxy group in which an aryl derivative is substituted at an ortho-position
    Type: Grant
    Filed: December 14, 2010
    Date of Patent: May 7, 2013
    Assignees: SK Innovations Co., Ltd., SK Global Chemical Co., Ltd.
    Inventors: Hwan Kyu Jung, Young Wook Kim, Byoung Tak Yim, Ho Seong Lee, Myung Ahn Ok, Jong Sok Hahn, Dong Cheol Shin
  • Patent number: 8435911
    Abstract: The present invention relates to a new hybrid catalyst system for the polymerization of olefins and to a polymerization process carried out in the presence of said catalyst. The new hybrid catalyst system comprises a tridendate iron compound and a zirconocene having a bridge of at least three carbon atoms connecting two indenyl ligands.
    Type: Grant
    Filed: September 18, 2009
    Date of Patent: May 7, 2013
    Assignee: Basell Polyolefine GmbH
    Inventors: Harald Schmitz, Shahram Mihan
  • Patent number: 8436101
    Abstract: The purpose of the invention is to provide an ethylene-?-olefin copolymer, which has a high melt tension but a small neck-in, and a molded object produced by extrusion molding of the copolymer. An ethylene-?-olefin copolymer having a monomer unit based on ethylene and a monomer unit based on an ?-olefin having 3 to 20 carbon atoms, which has a melt flow rate (MFR) of 0.1 to 100 g/10 min, a density (d) of 850 to 940 kg/m3, a ratio (Mw/Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn) of 2 to 12, and a value g* defined by the following formula (I) of 0.50 to 0.75: g*=[?]/([?]GPC×gSCB*)??(I).
    Type: Grant
    Filed: November 10, 2009
    Date of Patent: May 7, 2013
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Yoshinobu Nozue, Yasutoyo Kawashima, Naoko Ochi, Takuya Ogane
  • Patent number: 8435914
    Abstract: A polymerization catalyst system and polymerization processes using the catalyst systems are disclosed. The polymerization catalyst systems may include a) a first catalyst compound, and b) a second catalyst compound, wherein the first catalyst compound includes an oxadiazole-containing compound. In some embodiments, the oxadiazole-containing compound has essentially no hydrogen response, thus allowing better and/or tailored control of product properties when producing polymers using the catalyst system.
    Type: Grant
    Filed: May 14, 2010
    Date of Patent: May 7, 2013
    Assignee: Univation Technologies, LLC
    Inventors: Sun-Chueh Kao, Francis C. Rix, Dongming Li, C. Jeff Harlan, Parul A. Khokhani
  • Patent number: 8431659
    Abstract: A method of producing a prepolymerized catalyst for olefin polymerization comprising a fine powder removal step of removing fine particles from olefin-prepolymerized catalyst particles for olefin polymerization. The prepolymerized catalyst having a low fine particle content is applicable suitably to the field of continuous polymerization of olefins.
    Type: Grant
    Filed: December 6, 2011
    Date of Patent: April 30, 2013
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Tomoaki Goto, Yoshimitsu Onodera
  • Patent number: 8431661
    Abstract: This invention relates to a process for polymerizing olefins in which the amount of trimethylaluminum in a methylalumoxane solution is adjusted to be from 6 to 25 mole %, prior to use as an activator, where the mole % trimethylaluminum is determined by 1H NMR of the solution prior to combination with any support. This invention also relates to a process for polymerizing olefins in which the amount of an unknown species present in a methylalumoxane solution is adjusted to be from 0.10 to 0.65 integration units prior to use as an activator, where the unknown species is the peak is identified in the 1H NMR spectra of the solution performed prior to combination with any support. Preferably, the methylalumoxane solution is present in a catalyst system also comprising a metallocene transition metal compound.
    Type: Grant
    Filed: October 21, 2010
    Date of Patent: April 30, 2013
    Assignee: ExxonMobil Chemical Patents Inc.
    Inventors: Donna J. Crowther, David M. Fiscus
  • Patent number: 8431662
    Abstract: This invention relates to a polymacromonomer comprising at least one macromonomer and from 0 to 20 wt % of a C2 to C12 comonomer, wherein the macromonomer has vinyl termination of at least 70%, and wherein the polymacromonomer has: a) a g value of less than 0.6, b) an Mw of greater than 30,000 g/mol, c) an Mn of greater than 20,000 g/mol, d) a branching index (g?)vis of less than 0.5, e) less than 25% vinyl terminations, f) at least 70 wt % macromonomer, based upon the weight of the polymacromonomer, g) from 0 to 20 wt % aromatic containing monomer, based upon the weight of the polymacromonomer and h) optionally, a melting point of 50° C. or more. This invention also relates to processes to make such polymacromonomers.
    Type: Grant
    Filed: August 20, 2012
    Date of Patent: April 30, 2013
    Assignee: ExxonMobil Chemical Patents Inc.
    Inventors: Patrick Brant, Andrew G. Narvaez, Jr., Donna J. Crowther