Contains Nontransition Metal Atom Patents (Class 525/247)
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Patent number: 5519090Abstract: Propylene polymer blends containinga) a propylene homopolymer having a melt flow index of from 0.001 to 5 g/10 min, as determined at 230.degree. C. under a load of 2.16 kg,b) a propylene/ethylene copolymer having an ethylene content of from 5 to 80% w/w, andc) a propylene homopolymer having a melt flow index of from 1 to 10.sup.4 g/10 min, as determined at 230.degree. C. under a load of 2.16 kg,the ratio of the melt flow index of the propylene homopolymer c) to that of the propylene homopolymer a) being within the range 10:1 to 10.sup.7 :1.The blends of the invention are high-flow materials showing a broad molecular weight distribution, and are thus readily processible.Type: GrantFiled: November 4, 1994Date of Patent: May 21, 1996Assignee: BASF AktiengesellschaftInventors: Harald Schwager, Klaus-Dieter Hungenberg
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Patent number: 5514753Abstract: A block copolymer containing a non-polar polymer block and a polar polymer block was prepared by using an anionic polymerization initiator, by reacting an organic compound which can form an ate complex at the active end of the non-polar polymer block, the compound which contains a main group element of II or III group, before the addition of the polar monomer.Type: GrantFiled: June 30, 1994Date of Patent: May 7, 1996Assignee: Bridgestone CorporationInventors: Yoichi Ozawa, Ryota Fujio
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Patent number: 5512635Abstract: 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: GrantFiled: December 15, 1993Date of Patent: April 30, 1996Assignee: Amoco CorporationInventors: Philip O. Nubel, Howard B. Yokelson, Steven A. Cohen, Raymond T. Behrends, William G. Bouslog, James P. Nelson
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Patent number: 5496891Abstract: The invention of this patent application relates to carboxylic acid polymer compositions and in particular relates to concentrates of polymers which are subsequently used to prepare gels formed of diluted and neutralised polymer. Said polymers are currently supplied in a powder form. The polymers prepared by the addition of multivalent cations provide a concentrate which is the invention of this application and can be provided in either an aqueous form or granular or pelletised form which serves to eliminate existing problems in the powder form relating to the dispersion of the powder in water, the development of electrostatic charges in the said powder and the dusting of the powder. The concentrate of the invention provides a polymer for subsequent dilution and neutralisation for use as a gel wherein the conversion from one state to another is greatly improved.Type: GrantFiled: December 29, 1993Date of Patent: March 5, 1996Assignee: Surfachem Group PLCInventors: Stanley G. Stead, Peter E. Minister
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Patent number: 5486572Abstract: A process for preparing propylene block copolymers, comprising a preceding polymerization step in which a crystalline homopolymer of propylene, or a propylene-ethylene copolymer containing 7 wt. % or less of ethylene is produced in the presence of a catalyst comprising the following components (A) and (B), and a succeeding polymerization step in which the polymerization is continued in the presence of at least part of the homopolymer or copolymer, and of the following component (C) further added to give a copolymer with a polymerization ratio (weight ratio) of propylene to ethylene of from 0/100 to 90/10; the polymerization amount at the preceding polymerization step being from 30 to 95 wt.Type: GrantFiled: December 1, 1994Date of Patent: January 23, 1996Assignee: Mitsubishi Chemical CorporationInventors: Takashi Fujita, Toshihiko Sugano
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Patent number: 5480940Abstract: Process for making a polymer and the resultant polymer wherein polymer particles, preferably those having a core and a shell structure, most preferably wherein the core comprises polybutadiene and the shell comprises polymethylmethacrylate, are included in metathesis polymerizable mixtures to provide the resultant polymer with improved resistance to oxidation and greater retention of mechanical properties upon thermal aging, and to toughen the resultant polymer.Type: GrantFiled: March 7, 1995Date of Patent: January 2, 1996Assignee: Metton America, Inc.Inventors: Nitya P. Khasat, Douglas Leach
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Patent number: 5475061Abstract: There are disclosed a styrenic copolymer which comprises at least one structural unit represented by the general formula (I) ##STR1## and a structural unit represented by the general formula (II) ##STR2## or a structural unit represented by the general formula (IX) ##STR3## wherein the symbols are each as previously defined in the specification, the structural unit (II) or (IX) being contained in an amount of 0.01 to 99.9 mol %; and a process for the production of the above copolymer.The above styrenic copolymer has a high degree of syndiotactic configuration in the stereoregularity of the main chain of the structural unit (I) as well as adhesivity and compatibility with a resin of a different type.Type: GrantFiled: June 13, 1994Date of Patent: December 12, 1995Assignee: Idemitsu Kosan Co., Ltd.Inventors: Shuji Machida, Toshinori Tazaki
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Patent number: 5473021Abstract: A process for producing ethylene-propylene block copolymer which comprises(1) The first step of reacting propylene or a mixture of propylene and ethylene in the presence of a catalyst composed essentially of(A) a solid catalyst component containing magnesium, titanium and a halogen as the indispensable ingredients,(B) an organoaluminum compound, and(C) a silicon compound (1) represented by the formula R.sup.1 R.sup.2 Si(OR.sup.3).sub.2, wherein R.sup.1 is an alicyclic hydrocarbon group of 5-20 carbon atoms and R.sup.2 and R.sup.Type: GrantFiled: January 3, 1994Date of Patent: December 5, 1995Assignee: Sumitomo Chemical Company, LimitedInventors: Hiroyuki Koura, Takeshi Ebara, Kazuki Wakamatsu, Shozo Kawamata, Yoshizumi Sasaki
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Patent number: 5470900Abstract: This invention provides a thermoplastic elastomer powder produced by a gas polymerization process by the use of a specified catalyst system which is excellent in powder fluidity, retains a high fluidity even in a state where no substantial forming pressure is applied and can be formed by powder molding process, as well as a powder molding process using said elastomer powder and a molded product of said molding process.Type: GrantFiled: May 19, 1994Date of Patent: November 28, 1995Assignee: Sumitomo Chemical Company, LimitedInventors: Toshio Sasaki, Takeshi Ebara, Toshio Igarashi, Masayuki Tatsumi, Kazuki Wakamatsu
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Patent number: 5468810Abstract: A propylene block copolymer having a high rigidity and an excellent impact strength is produced by (1) first polymerizing propylene or a mixture of propylene and another ethylenically unsaturated hydrocarbon monomer in the presence of a catalyst comprising a Ti-containing solid component (A), an organic Al compound-containing component (B) and an alkoxyl silicon compound-containing component (C), and (2) second copolymerizing, in a gas phase, propylene and another ethylenically unsaturated hydrocarbon monomer in the presence of the first crystalline polymer of step (1) by re-using the catalyst of first polymerization, and in the presence of a saturated hydrocarbon with 6 or more carbon atoms, thereby forming an elastomeric fraction incorporated into the crystalline polymeric fraction.Type: GrantFiled: July 26, 1994Date of Patent: November 21, 1995Assignee: Ube Industries, Ltd.Inventors: Tetsuo Hayakawa, Tokuji Inoue, Hiroyuki Asaga
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Patent number: 5461115Abstract: A continuous process for producing a propylene-ethylene block copolymer having well-balanced properties of impact strength, stiffness, processability, etc. using a highly active catalyst, with a superior productivity is provided,which process comprisesa first polymerization step (I), carried out using a catalyst system consisting of [A] a solid catalyst component containing Ti, Mg, halogen and a polyvalent carboxylic acid ester as indispensable components, [B] an organoaluminum compound catalyst component and [C] an electron-donating compound,using two or more continuous polymerization vessels, andfeeding monomer(s) of ethylene/(ethylene+propylene) of 0 to 5% by weight, to carry out polymerization composed mainly of propylene, so as to give 60 to 95% of the total polymerized quantity;a continuous addition of a glycol compound (D) expressed by the formulaR.sup.1 --(OC.sub.m H.sub.2m).sub.n --OR.sup.2wherein m is an integer of 2 or more, n is an integer of 3 or more, R.sup.1 and R.sup.Type: GrantFiled: September 21, 1994Date of Patent: October 24, 1995Assignee: Chisso CorporationInventor: Takahiro Oka
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Patent number: 5459203Abstract: A catalyst system for the polymerization of alpha-olefins comprising a chromium-containing catalyst and an yttrium-containing catalyst wherein the yttrium-containing catalyst is represented by the formula (Cp.sub.2 YX.sub.x).sub.y .multidot.M.sub.z L.sub.n, wherein Cp is cyclopentadienyl or cyclopentadienyl substituted with an alkyl or alkyl silyl radical, X is a halogen, M is an alkali metal, L is a suitable electron donor ligand, x is 1 or 2, y is 1 or 2, z is 0 or 1, and n is a number corresponding to the value needed to form a stable complex, with the proviso that when y is 2, z and n are 0 is provided. Also disclosed is a polymerization process employing such a catalyst system, and novel olefin polymers. Polymers thus produced exhibit high bulk density and a broad molecular weight distribution.Type: GrantFiled: November 8, 1994Date of Patent: October 17, 1995Assignee: Phillips Petroleum CompanyInventors: Rolf L. Geerts, Elizabeth A. Benham, Max P. McDaniel
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Patent number: 5449738Abstract: The present invention relates to a process for producing ethylene propylene block copolymers excellent in appearance, elongation and impact resistance when molded by a gas phase polymerization which can be conducted in a stable manner.The process of the present invention comprises the first step of polymerizing propylene by using a catalyst system composed essentially of(A) a solid catalyst component containing magnesium, titanium, and a halogen as the indispensable ingredients,(B) an organoaluminum compound, and(C) a silicon compound represented by the formula R.sup.1 R.sup.2 Si(OR.sup.3).sub.2, wherein R.sup.1 is an alicyclic hydrocarbon group and R.sup.2 and R.sup.3 are each a hydrocarbon group, to form a propylene homopolymer, and the second step of then polymerizing ethylene and propylene with further addition of a silicon compound represented by the formula R.sup.4 R.sup.5.sub.a Si(OR.sup.6).sub.3-a, wherein R.sup.4 is an aromatic hydrocarbon group, R.sup.Type: GrantFiled: July 1, 1992Date of Patent: September 12, 1995Assignee: Sumitomo Chemical Company, Ltd.Inventors: Hiroyuki Koura, Takeshi Ebara, Kazuki Wakamatsu, Shouzou Kawamata, Yoshizumi Sasaki
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Patent number: 5432236Abstract: According to the present invention, in a vapor phase polymerization of olefins, there is provided an efficient polyolefin manufacturing process capable of preventing the formation of a sheet-like polymer and allowing an olefin polymerization reaction to be started stably.Type: GrantFiled: February 18, 1994Date of Patent: July 11, 1995Assignee: Nippon Oil Company, LimitedInventors: Akira Sano, Kunimichi Kubo, Kazuo Matsuura
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Patent number: 5432009Abstract: A film for a first-aid sticking plaster consisting of polypropylene resin having a weight average molecular weight within a range of 80,000 to 500,000, with resin elution quantities according to cross fractionation chromatograph in ranges of 45 to 80 percent by weight at 0.degree. to 10.degree. C., 5 to 35 percent by weight at 10.degree. to 70.degree. C., 1 to 30 percent by weight at 70.degree. to 95.degree. C., and 5 to 35 percent by weight at 95.degree. to 125.degree. C.Type: GrantFiled: June 14, 1994Date of Patent: July 11, 1995Assignee: Sekisui Kagaku Kogyo Kabushiki KaishaInventors: Hironori Tabata, Masao Ogasa, Kiyomi Uenomachi, Hideshi Matsumoto
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Patent number: 5428110Abstract: A process for producing a copolymer of propylene and other .alpha.-olefins in the presence of a catalyst comprising a titanium-containing solid catalyst component and an organoaluminum compound is disclosed. The process comprises (1) a first step in which propylene is homopolymerized or propylene and a minor proportion of other .alpha.-olefin are copolymerized to prepare polymer particles having a pore volume of from 0.15 to 0.30 cm.sup.3 /g, and (2) a second step in which propylene and other .alpha.-olefin are copolymerized in the presence of said polymer particles. The resulting propylene copolymer particles have improved fluidity and high bulk density.Type: GrantFiled: December 21, 1993Date of Patent: June 27, 1995Assignee: Mitsubishi Kasei CorporationInventors: Yumito Uehara, Hideshige Kato, Hidehito Kato, Kouzou Kitayama
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Patent number: 5422400Abstract: The invention relates to a method for producing an ethylenic polymer composition, suitable for molding, at high catalytic efficiency. The ethylenic polymer composition produced has as a high melt tension when melted, and a high melt modulus (die swell ratio). The process comprises a three step polymerization of an olefin employing a transition metal catalyst, the catalyst being produced in a specific manner.Type: GrantFiled: August 3, 1994Date of Patent: June 6, 1995Assignee: Maruzen Polymer Company, Ltd.Inventors: Sakae Kamiyama, Masao Kawahara, Kunihiro Inamatsu, Keizo Kase, Kouji Mizokami, Tsuyoshi Matsumoto
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Patent number: 5418276Abstract: There are disclosed a graft copolymer formed by grafting a styrenic monomer onto a high polymer having double bonds in the side chain to constitute highly syndiotactic polystyrenic chain as the graft component, the graft copolymer having a content of graft component of 0.005 to 99% by weight and a reduced viscosity of 0.01 to 30 dl/g as measured at a concentration of 0.05 g/dl in 1,2,4-trichlorobenzene at 135.degree. C. or a melt index of 0.001 to 500 g/10 minutes as measured at 300.degree. C. under a load of 2.16 kg; a process for efficiently producing the above graft copolymer using a catalyst comprising specific components; and a resin composition comprising the above graft copolymer, a highly syndiotactic styrenic polymer or other thermoplastic resin and, when necessary, an inorganic or organic filler. The above graft copolymer and resin composition are excellent in resistance to heat and chemicals, electrical properties, moldability, compatibility, impact resistance, etc.Type: GrantFiled: July 26, 1994Date of Patent: May 23, 1995Assignee: Idemitsu Kosan Co., Ltd.Inventors: Shuji Machida, Noriyuki Tani
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Patent number: 5405901Abstract: A gas phase process for the production of a polyethylene blend comprising contacting ethylene and at least one alpha-olefin comonomer having 3 to 8 carbon atoms with a magnesium/titanium based catalyst system including an activator and a cocatalyst in each of two fluidized bed reactors connected in series, under polymerization conditions, with the provisos that:(a) the mixture of ethylene copolymer matrix and active catalyst formed in the first reactor in the series is transferred to the second reactor in the series;(b) other than the active catalyst referred to in proviso (a) and the cocatalyst referred to in proviso (e), no additional catalyst is introduced into the second reactor;(c) in the first reactor in which a low melt index copolymer is made:(1) the alpha-olefin is present in a ratio of about 0.01 to about 0.4 mole of alpha-olefin per mole of ethylene;(2) optionally, hydrogen is present in a ratio of about 0.001 to about 0.Type: GrantFiled: July 6, 1994Date of Patent: April 11, 1995Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Paul T. Daniell, Michael W. Tilston, Thomas E. Spriggs, Burkhard E. Wagner, Arakalgud V. Ramamurthy
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Patent number: 5399622Abstract: A catalyst system for the polymerization of alpha-olefins comprising a chromium-containing catalyst and an yttrium-containing catalyst wherein the yttrium-containing catalyst is represented by the formula (Cp.sub.2 YX.sub.x).sub.y.M.sub.z L.sub.n, wherein Cp is cyclopentadienyl or cyclopentadienyl substituted with alkyl or alkyl silyl radical or radicals, X is a halogen, M is an alkali metal, L is a suitable electron donor ligand, x is 1 or 2, y is 1 or 2, z is 0 or 1, and n is a number corresponding to the value needed to form a stable complex, with the proviso that when y is 2, z and n are 0 is provided. Also disclosed is a polymerization process employing such a catalyst system, and novel olefin polymers. Polymers thus produced exhibit high bulk density and a broad molecular weight distribution.Type: GrantFiled: November 17, 1993Date of Patent: March 21, 1995Assignee: Phillips Petroleum CompanyInventors: Rolf L. Geerts, Elizabeth A. Benham, Max P. McDaniel
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Patent number: 5387749Abstract: Process for the preparation of LLDPE with improved processability by gas phase polymerization performed in two or more reactors, wherein, whatever the order, in one of the reactors a mixture of ethylene and an alpha-olefin CH.sub.2 .dbd.CHR, where R is an alkyl having 1-10 carbon atoms, is polymerized to yield a copolymer containing up to about 20% by mole of the alpha-olefin, and in another reactor a mixture of propylene and an alpha-olefin CH.sub.2 .dbd.CHR', where R' is an alkyl radical having 2-10 carbon atoms, is polymerized to yield a copolymer containing from 5 to 40% by weight of said olefin, in an amount of 5-30% with respect to the total polymer weight and the polymer-catalyst system obtained in the first reactor is fed to the other reactors.Type: GrantFiled: March 5, 1993Date of Patent: February 7, 1995Assignee: Himont IncorporatedInventors: Gabriele Govoni, Massimo Covezzi
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Patent number: 5382634Abstract: The object of the present invention is to provide such a polyolefin that only the terminal of polypropylene or ethylene-propylene random copolymer is modified with a (meth)acrylic derivative unit to give a substantially monodipersed system. The feature thereof consists in such a polyolefin that the terminal of polypropylene or ethylene-propylene random copolymer obtained by living polymerization is modified with a (meth)acrylic derivative unit. As the (meth)acrylic derivative, there are used vinyl methacrylate, allyl methacrylate, trimethylsiloxyethyl methacrylate, 2-trimethylsiloxypropyl methacrylate, N, N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate, glycidyl methacrylate, acrylic acid chloride and like.Type: GrantFiled: April 25, 1994Date of Patent: January 17, 1995Assignee: Tonen CorporationInventors: Naomi Koyama, Miyuki Usui, Hiroyuki Furuhashi, Satoshi Ueki
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Patent number: 5362814Abstract: There are disclosed a graft copolymer formed by grafting a styrenic monomer onto a high polymer having double bonds in the side chain to constitute highly syndiotactic polystyrenic chain as the graft component, the graft copolymer having a content of graft component of 0.005 to 99% by weight and a reduced viscosity of 0.01 to 30 dl/g as measured at a concentration of 0.05 g/dl in 1,2,4-trichlorobenzene at 135.degree. C. or a melt index of 0.001 to 500 g/10 minutes as measured at 300.degree. C. under a load of 2.16 kg; a process for efficiently producing the above graft copolymer using a catalyst comprising specific components; and a resin composition comprising the above graft copolymer, a highly syndiotactic styrenic polymer or other thermoplastic resin and, when necessary, an inorganic or organic filler. The above graft copolymer and resin composition are excellent in resistance to heat and chemicals, electrical properties, moldability, compatibility, impact resistance, etc.Type: GrantFiled: March 3, 1993Date of Patent: November 8, 1994Assignee: Idemitsu Kosan Co., Ltd.Inventors: Shuji Machida, Noriyuki Tani
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Patent number: 5352520Abstract: Disclosed is a propylene-ethylene/butene block copolymer, comprising a polybutene component block-copolymerized with a propylene-ethylene random copolymer component, or with a polypropylene component and a propylene-ethylene random copolymer component, the content of the polybutene component being 0.1 to 10% by weight, the total content of the propylene-ethylene random copolymer component and the polypropylene component being 99.9 to 90% by weight and the content of the polypropylene component being 0 to 30% by weight, wherein the propylene-ethylene random copolymer component is composed of a copolymer comprising 15 to 80 mole % of monomer units based on ethylene and 85 to 20 mole % of monomer units based on propylene, and said block copolymer is a powder having a high molecular weight.Type: GrantFiled: April 15, 1993Date of Patent: October 4, 1994Assignee: Tokuyama CorporationInventors: Yoshiyuki Kitajima, Eitaro Asaeda
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Patent number: 5344885Abstract: Propylene-ethylene copolymers are obtained by two-stage polymerization from the gaseous phase in an agitated fixed bed by means of a Ziegler-Natta catalyst system that contains in addition to a titanium-containing solid component also an aluminum compound as co-catalyst, wherein as Ziegler-Natta catalyst system a system is used which, following the reaction of the titanium-containing solid component with the co-catalyst, is deactivated by reaction with carbon dioxide. The copolymers are used for producing fibers, films and moldings.Type: GrantFiled: February 25, 1993Date of Patent: September 6, 1994Assignee: BASF AktiengesellschaftInventors: Meinolf Kersting, Juergen Kerth, Klaus-Dieter Hungenberg, Patrik Mueller, Peter Koelle
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Patent number: 5332789Abstract: Polypropylene based resins and compositions comprising the resin having extremely high stiffness, heat resistance and impact strength, with these properties being well-balanced, are provided. The polypropylene based resins are characterized by comprising:(1) a propylene polymer having a content of alpha-olefin other than propylene of not more than 4 mole percent, and the following properties (2), (3) and (4):(2) a pentad fraction (mmmm fraction) measured by .sup.13 C-NMR of not less than 96.0 percent,(3) a main elution fraction peak position of not less than 118.0.degree. C. and a peak half value width of less than 4.0, these values being measured by the temperature raising separation method, and(4) an intrinsic viscosity of not less than 0.5 dl/g, but not more than 5.0 dl/g; and,(5) a rubber content measured by pulse NMR of more than 25 percent.Type: GrantFiled: February 26, 1993Date of Patent: July 26, 1994Assignee: Idemitsu Petrochemical Co., Ltd.Inventors: Akira Tanaka, Masaru Nakagawa, Hideo Kusuyama, Sueto Miyazaki, Tatsuya Housaki
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Patent number: 5324784Abstract: Propylene is copolymerized with ethylene in solventfree polymerization in two steps where a resinous polymer is produced in the first step and a rubbery polymer is produced in the second step over a Ziegler catalyst whose solid catalyst component comprises a sub-component which is a solid catalyst component for a Ziegler catalyst comprising Ti, Mg and a halogen and which has, in accordance with the present invention, undergone mechanical milling. The solid catalyst components is specified. Less Sticky polymer powder is obtainable.Type: GrantFiled: November 13, 1992Date of Patent: June 28, 1994Assignee: Mitsubishi Petrochemical Company LimitedInventors: Takashi Fujita, Naohiro Yamamoto
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Patent number: 5322902Abstract: A propylene block copolymer having good flow properties and a very good low temperature impact strength is obtained in a high yield if a catalyst which consists of a chiral metallocene, containing a bridge, of the formula I ##STR1## and an aluminoxane is used for the polymerization of propylene and the comonomers.The polymerization is carried out in two stages, a crystalline propylene polymer being prepared in the first stage.Type: GrantFiled: December 19, 1990Date of Patent: June 21, 1994Assignee: Hoechst AktiengesellschaftInventors: Michael Schreck, Andreas Winter, Volker Dolle, Hartmut Kondoch, Martin Antberg, Jurgen Rohrmann
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Patent number: 5314957Abstract: A method for preparing a molded article of a crosslinked polyolefin which comprises the steps of bringing a composition comprising a copolymer of an alkenylsilane and an olefin and a compound having at least two unsaturated bonds into contact with a catalyst selected from the group consisting of salts of rhodium, alkoxy compounds and metallocene compounds of metals in the group IVa of the periodic table, combinations of the metallocene compounds and organic metal compounds, and then molding the composition, or carrying out the contact simultaneously with the molding, or molding the composition, and then bringing the molded article into contact with the catalyst, and if necessary, further heating the molded article to accelerate a crosslinking reaction.The molded article of the crosslinked polyolefin obtained by the method of the present invention has a high crosslinking density and is excellent in mechanical properties, solvent resistance and heat resistance.Type: GrantFiled: December 17, 1992Date of Patent: May 24, 1994Assignee: Mitsui Toatsu Chemicals, Inc.Inventors: Tadashi Asanuma, Kazuhiko Yamamoto
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Patent number: 5283294Abstract: It is sometimes advantageous to disperse crystalline polymers throughout rubbery elastomers. For instance, the cold flow characteristics and green strength of polydiene rubbers can be improved by dispersing syndiotactic-1,2-polybutadiene therein. This invention discloses a process for preparing a highly dispersed blend of a crystalline polymer in a rubbery elastomer which comprises (1) polymerizing at least one diene monomer in an organic solvent under solution polymerization conditions to form a polymer cement of the rubbery elastomer in the organic solvent, (2) polymerizing additional monomers in the polymer cement into the crystalline polymer to form a rubbery cement having the crystalline polymer dispersed therein, and (3) recovering the highly dispersed blend of the crystalline polymer in the rubbery elastomer from the organic solvent in the rubber cement.Type: GrantFiled: June 2, 1992Date of Patent: February 1, 1994Assignee: The Goodyear Tire & Rubber CompanyInventors: Wen-Liang Hsu, Adel F. Halasa
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Patent number: 5280074Abstract: A propylene block copolymer having good flow properties and a very good low temperature impact strength is obtained in a high yield if a catalyst which consists of a chiral metallocene, containing a bridge, of the formula I ##STR1## and an aluminoxane is used for the polymerization of propylene and the comonomers.The polymerization is carried out in two stages, a crystalline propylene polymer in liquid monomers being prepared in the first stage and a copolymer in the gas phase being prepared in the second stage.Type: GrantFiled: October 13, 1992Date of Patent: January 18, 1994Assignee: Hoechst AGInventors: Michael Schreck, Andreas Winter, Walter Spaleck, Hartmut Kondoch, Jurgen Rohrmann
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Patent number: 5266636Abstract: A process for producing polypropylene, which comprises preliminarily polymerizing 3-methylbutene-1 in the presence of a catalyst system formed from[A] a solid titanium catalyst component containing magnesium, titanium, halogen and polycarboxylic acid esters as essential components,[B] an organoaluminum compound, and[C] an organosilicon compound represented by the general formula R.sub.n Si(OR').sub.4-n wherein R and R' represent a hydrocarbon group, and 0<n<4, the amount of the 3-methylbutene-1 preliminarily polymerized being 0.1 to 100 g per gram of the solid titanium catalyst, and thereafter, polymerizing propylene or copolymerizing propylene and an alpha-olefin in the presence of the catalyst used in the preliminary polymerization to such an extent that the amount of the monomer or monomers polymerized is from 1,000 to 100,000 times the amount of the 3-methylbutene-1 preliminarily polymerized.Type: GrantFiled: August 11, 1992Date of Patent: November 30, 1993Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Mamoru Kioka, Masaya Yamada, Masanobu Ishiyama, Masao Nakano, Akinori Toyota
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Patent number: 5262487Abstract: Propylene is copolymerized with ethylene in solvent-free polymerization in two steps where a resinous polymer is produced in the first step and a rubbery polymer is produced in the second step over a Ziegler catalyst whose solid catalyst component has undergone preliminary polymerization of an .alpha.-olefin in the absence of an organoaluminum compound. The solid catalyst components is specified. Less sticky polymer powder is obtainable.Type: GrantFiled: July 23, 1992Date of Patent: November 16, 1993Assignee: Mitsubishi Petrochemical Company LimitedInventors: Takashi Fujita, Naohiro Yamamoto
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Patent number: 5254629Abstract: A catalyst and process for the polymerization of cyclic olefins, such as dicyclopentadiene, in the presence of an elastomer polymer, are disclosed. The catalyst includes a transition metal compound, a co-catalyst and a boron halide promoter. Polymerization can be carried out at fast reaction times in a reaction injection molding process to prepare a thermoset molded article having high Tg and superior toughness.Type: GrantFiled: April 29, 1992Date of Patent: October 19, 1993Assignee: Shell Oil CompanyInventors: Donald R. Kelsey, Dale L. Handlin, Jr.
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Patent number: 5247020Abstract: Disclosed is a process for producing a styrene polymer composition, which comprises polymerizing styrene monomer using a catalyst comprising (A) aluminoxane and (B) a compound of the group IV B transition metal in the periodic table, in the presence of rubber-like elastomer.The resin composition obtained thereby is superior in heat resistance, and impact strength, and utilized as the starting material for various moldings.Type: GrantFiled: December 28, 1990Date of Patent: September 21, 1993Assignee: Idemitsu Kosan Co., Ltd.Inventors: Akikazu Nakano, Hideo Teshima, Masahiko Kuramoto
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Patent number: 5237013Abstract: Disclosed is a composition of polybutene-1 comprised of a polymer resulting from preliminarily polymerization of a small amount of an .alpha.-olefin, which has an intrinsic viscosity [.eta.]p of 7 dl/gram or lower, as measured at 135.degree. C. in a decalin solution; and a homopolymer of butene-1 or a copolymer of butene-1 and 20% by weight of an .alpha.-olefin other than butene-1, the composition of polybutene-1 having an intrinisic viscosity [.eta.]t of 0.5-7.0 dl/gram, when measured at 135.degree. C. in a decalin solution, and satisfying the following relationship with respect to the intrinsic viscosity [.eta.]p:[.eta.]p.ltoreq.2.5.times.[.eta.]r. The composition provides resulting films with highly improved appearance and with a lesser number of gel and fish eyes.Type: GrantFiled: April 13, 1992Date of Patent: August 17, 1993Assignee: Idemitsu Petrochemical Company LimitedInventors: Masatoshi Toda, Masahiko Kondo, Nobumasa Kita
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Patent number: 5232993Abstract: A polypropylene molding composition having syndiotactic polymer chains is obtained in a high yield by the copolymerization of propylene with ethylene or a 1-olefin of the formula R.sup.a --CH.dbd.CH--R.sup.b in the presence of a catalyst comprising a metallocene of the formula I ##STR1## in which M.sup.1 is titanium, zirconium, hafnium, vanadium, riobium or tantalum, and an aluminoxane. This molding composition has a very high molecular weight, a very narrow molecular-weight distribution and very high syndiotaxy. Shaped articles produced from the molding composition are distinguished by high transparency, flexibility, bear strength and excellent surface luster.Type: GrantFiled: December 19, 1990Date of Patent: August 3, 1993Assignee: Hoechst AGInventors: Andreas Winter, Volker Dolle, Jurgen Rohrmann, Walter Spaleck, Martin Antberg
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Patent number: 5218052Abstract: A multistage method for making a homopolymer or copolymer of an alpha-olefin having increased stiffness and broadened molecular weight distribution.Type: GrantFiled: November 18, 1991Date of Patent: June 8, 1993Assignee: Amoco CorporationInventors: Steven A. Cohen, Nicholas M. Karayannis, Jerome A. Streeky, Benjamin S. Tovrog
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Patent number: 5182330Abstract: In the copolymerization of 4-methyl-1-pentene and at least one alpha olefin under batch polymerization conditions at a temperature of at least about 50.degree. C. wherein 4-methyl-1-pentene is initially polymerized in the absence of comonomer and then comonomer is added to the reaction vessel to permit copolymer formation, the improvement comprising initially forming 4-methyl-1-pentene homopolymer in an amount sufficient to reduce the solubility of the later formed copolymer at the polymerization temperature, said homopolymer being no more than about 5 weight percent of the end product copolymer. Also the products of such polymerizations are disclosed.Type: GrantFiled: August 13, 1991Date of Patent: January 26, 1993Assignee: Phillips Petroleum CompanyInventors: Phil M. Stricklen, Daniel M. Hasenberg, Patrick Rooney
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Patent number: 5173540Abstract: A catalyst component for producing highly crystalline olefin polymers without causing any operational problems and stably and affording therefrom a film having very few occurrence of voids and a superior transparency, and a process for producing the catalyst component, which catalyst component comprises a linear olefin-non-olefin block copolymer having at least one linear olefin block copolymer and at leaast one non-linear olefin polymer block and (a) a titanium trichloride composition or (b) titanium, magnesium, a halogen and an electron donor as components for a carrier, the content of the linear olefin polymer block being 0.1 to 49.5% by weight, the content of the non-linear olefin polymer block being 0.01 to 49.5% by weight, the ratio by weight of the linear olefin polymer block to the non-linear olefin polymer block being 2/98 to 98/2 and in the case of (a), the content of the titanium trichloride composition being 99.89 to 1.0% by weight.Type: GrantFiled: April 17, 1990Date of Patent: December 22, 1992Assignee: Chisso CorporationInventors: Jun Saito, Akihiko Sanpei
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Patent number: 5162442Abstract: In a process for producing granular propylene block copolymers in two steps wherein a resinous homopolymer of propylene is produced in the first step and an elastomeric copolymer of propylene with ethylene is produced in the second step, the improvement which comprises conducting the second step in the presence of a granular propylene homopolymer added thereby to produce granular propylene copolymers endowed with an improved granulometric properties such as lowered tackiness and thus improving flowing characteristics.Type: GrantFiled: September 14, 1989Date of Patent: November 10, 1992Assignee: Mitsubishi Petrochemical Company LimitedInventors: Mitsuyuki Matsuura, Takashi Fujita
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Patent number: 5162443Abstract: In a process for producing granular propylene block copolymers by Ziegler-Natta polymerization of an .alpha.-olefin wherein the Ziegler-Natta catalyst comprises a granular solid transition metal catalyst component and an organometal component in two steps wherein a resinous homopolymer of propylene is produced in the first step and an elastomeric copolymer of propylene with ethylene is produced in the second step, the improvement which comprises the use as the granular solid transition metal component of a mixture of the solid transition metal components, one made up substantially of particles of particle size of more than 5 microns and the other made up substantially of particles of particle size of 1 to 5 microns thereby to produce granular propylene copolymers endowed with an improved granulometric properties such as lowered tackiness and thus improved flowing characteristics. The component (B) is preferably produced from the particles for the component (A) by reducing the particle size of its particles.Type: GrantFiled: February 26, 1992Date of Patent: November 10, 1992Assignee: Mitsubishi Petrochemical Company LimitedInventors: Mitsuyuki Matsuura, Takashi Fujita
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Patent number: 5159021Abstract: A process for producing polypropylene, which comprises preliminarily polymerizing 3-methylbuten3-1 in the presence of a catalyst system formed from[A] a solid titanium catalyst component containing magnesium, titanium, halogen and polycarboxylic acid esters as essential components,[B] an organoaluminum compound, and[C] an organosilicon compound represented by the general formula R.sub.n Si(OR').sub.4-n wherein R and R' represent a hydrocarbon group, and 0<n<4, the amount of the 3-methylbutene-1 preliminarily polymerized being 0.1 to 100 g per gram of the solid titanium catalyst, and thereafter, polymerizing propylene or copolymerizing propylene and an alpha-olefin in the presence of the catalyst used in the preliminary polymerization to such an extent that the amount of the monomer or monomers polymerized is from 1,000 to 100,000 times the amount of the 3-methylbutene-1 preliminarily polymerized.Type: GrantFiled: December 14, 1988Date of Patent: October 27, 1992Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Mamoru Kioka, Masaya Yamada, Masanobu Ishiyama, Masao Nakano, Akinori Toyota
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Patent number: 5149738Abstract: A process for the in situ blending of polymers comprising continuously contacting, under polymerization conditions, a mixture of ethylene and at least one alpha-olefin having at least 3 carbon atoms with a catalyst in at least two fluidized bed reactors connected in series, said catalyst comprising:(i) a complex consisting essentially of magnesium titanium, a halogen, and an electron donor;(ii) at least one activator compound for the complex having the formula AlR".sub.e X'.sub.f H.sub.g wherein X' is Cl or OR'"; R" and R'" are saturated aliphatic hydrocarbon radicals having 1 to 14 carbon atoms and are alike or different; f is 0 to 1.5; g is 0 or 1; and e+f+g=3; and(iii) a hydrocarbyl aluminum cocatalyst, the polmerization conditions being such that ethylene copolymer having a high melt index in the range of about 0.1 to about 1000 grams per 10 minutes is formed in at least one reactor and ethylene copolymer having a low melt index in the range of about 0.001 to about 1.Type: GrantFiled: July 2, 1991Date of Patent: September 22, 1992Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Kiu H. Lee, Frederick J. Karol, Sari B. Samuels
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Patent number: 5140062Abstract: Continuous processes for producing high melting and viscoelasting polypropylene or ethylene-propylene copolymer are provided.These processes are characterized by (1) using two or more polymerizers connected in series, (2) supplying the whole amount of a catalyst and a molecular weight regulator (hydrogen) in the first tank and (3) a degasification amount of each tank in the second and subsequent tanks being 0.5 to 10 V.sub.1 /Hr (wherein V.sub.1 is a volume of the tank) calculated at 0.degree. C. and 0 Kg/cm.sup.2 G. In the process for producing the copolymer, (4) monomers having an ethylene content of 5 wt % or less are supplied in the first step. According to the processes of the present invention, polymers having a broad molecular weight distribution and good fluidity upon extrusion molding can be obtained and operational control in production is simply made.Type: GrantFiled: September 20, 1990Date of Patent: August 18, 1992Assignee: Chisso CorporationInventors: Hiromasa Chiba, Takahiro Oka, Shunji Kawazoe
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Patent number: 5132369Abstract: A process for preparing a narrow molecular weight distribution syndiotactic block copolymer of an unsaturated carboxylic acid ester (e.g., acrylate of methacrylate) with an .alpha.-olefin (e.g., ethylene) by using, as an initiator, at least one organometallic compound of the group consisting of (a) trivalent organic Y compounds, and (b) trivalent organic lanthanide (La, Ce, Pr, Nd, Pm, Sm, Eu, Ga, Tb, Dy, Ho, Er, Tm, Yb, Lu) compounds, or a combination thereof with an organoaluminum compound.Type: GrantFiled: February 14, 1991Date of Patent: July 21, 1992Assignee: Showa Denko K.K.Inventors: Hajime Yasuda, Akira Nakamura, Shigenobu Miyake
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Patent number: 5126398Abstract: A process for the in situ blending of polymers comprising continuously contacting, under polymerization conditions, a mixture of ethylene and at least one alpha-olefin having at least 3 carbon atoms with a catalyst in at least two fluidized bed reactors connected in series, said catalyst comprising:(i) a complex consisting essentially of magnesium titanium, a halogen, and an electron donor;(ii) at least one activator compound; and(iii) a hydrocarbyl aluminum cocatalyst, the polymerization conditions being such that ethylene copolymer having a high melt index in the range of about 0.1 to about 1000 grams per 10 minutes is formed in at least one reactor and ethylene copolymer having a low melt index in the range of about 0.001 to about 1.0 gram per 10 minutes is formed in at least one other reactor, each copolymer having a density of about 0.860 to about 0.965 gram per cubic centimeter and a melt flow ratio in the range of about 22 to about 70, and being admixed with active catalyst.Type: GrantFiled: July 2, 1991Date of Patent: June 30, 1992Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Kiu H. Lee, Frederick J. Karol, Sari B. Samuels
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Patent number: 5098958Abstract: Vinyl ether copolymers and a method of preparing the same. The vinyl ether is copolymerized with styrene, alkyl-substituted styrenes, alkoxy-substituted styrenes and mixtures thereof. In the process, a cadmium halide is used with hydrogen iodide or a suitable iodine containing electrophile, as the coinitiator.Type: GrantFiled: March 26, 1991Date of Patent: March 24, 1992Assignee: Shell Oil CompanyInventor: Donn DuBois
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Patent number: 5077341Abstract: A process for producing a highly transparent and highly stiff polypropylene affording a superior molded product is provided,which process comprises using a catalyst obtained by combining1 a titanium trichloride composition (III) obtained by reacting TiCl.sub.4 with an organoaluminum compound (A.sub.1) or a reaction product (I) or (A.sub.1) with an electron donor (B.sub.1) to obtain a solid product (II), followed by subjecting the product (II) to a multi-stage polymerization treatment with a linear olefin and a non-linear olefin, each once or more times used, and further reacting the resulting linear olefin-non-linear olefin block copolymer with an electron donor (B.sub.2) and an electron acceptor,2 an organoaluminum compound (A.sub.2); and as a third component,3 an aromatic carboxylic acid ester (E) or an organosilicon compound (S) having a Si--O--C bond and/or a mercapto group.Type: GrantFiled: June 12, 1990Date of Patent: December 31, 1991Assignee: Chisso CorporationInventors: Jun Saito, Akihiko Sanpei
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Patent number: 5061755Abstract: A highly crystalline propylene polymer composition which is obtained by preliminarily polymerizing, in the presence of a catalyst comprising a solid titanium trichloride catalyst complex containing a complexing agent and having an aluminum content of at most 0.15 by atomic ratio of aluminum to titanium and an organoaluminum compound and optionally an electron donative compound, 3-methylbutene-1 in an amount exceeding 10 g per g of the solid titanium trichloride catalyst complex and then polymerizing propylene, or propylene and other .alpha.-olefin having from 2 to 18 carbon atoms, in an amount of at least 500 g per g of the solid titanium trichloride catalyst complex, and which contains from 0.01 to 20% by weight of the 3-methylbutene-1 polymer based on the total weight of the 3-methylbutene-1 polymer-containing propylene polymer composition.Type: GrantFiled: October 24, 1989Date of Patent: October 29, 1991Assignee: Mitsubishi Kasei CorporationInventors: Yoshinori Suga, Eiji Tanaka, Hidehito Katou, Yasuo Maruyama, Eiji Isobe