WO1999003927A1 - Elastomeres thermoplastiques traites par hydrosilylation - Google Patents

Elastomeres thermoplastiques traites par hydrosilylation Download PDF

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Publication number
WO1999003927A1
WO1999003927A1 PCT/US1998/014791 US9814791W WO9903927A1 WO 1999003927 A1 WO1999003927 A1 WO 1999003927A1 US 9814791 W US9814791 W US 9814791W WO 9903927 A1 WO9903927 A1 WO 9903927A1
Authority
WO
WIPO (PCT)
Prior art keywords
rubber
hydrosilylation
composition
thermoplastic
thermoplastic resin
Prior art date
Application number
PCT/US1998/014791
Other languages
English (en)
Inventor
Robert E. Medsker
Jianqun Zhao
Gary W. Gilbertson
Original Assignee
Advanced Elastomer Systems, L.P.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Advanced Elastomer Systems, L.P. filed Critical Advanced Elastomer Systems, L.P.
Priority to JP2000503144A priority Critical patent/JP2001510219A/ja
Priority to BR9810886-7A priority patent/BR9810886A/pt
Priority to AU84093/98A priority patent/AU736139B2/en
Priority to KR1020007000211A priority patent/KR20010021653A/ko
Priority to CA002295508A priority patent/CA2295508A1/fr
Priority to EP98934606A priority patent/EP0996679A4/fr
Priority to IL13408598A priority patent/IL134085A0/xx
Publication of WO1999003927A1 publication Critical patent/WO1999003927A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/22—Thermoplastic resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof

Definitions

  • thermoplastic elastomer compositions prepared using hydrosilylation crosslinking of the elastomer component of the composition.
  • a thermoplastic elastomer is generally defined as a polymer or blend of polymers that can be processed and recycled in the same way as a conventional thermoplastic material, yet has properties and functional performance similar to that of vulcanized rubber at service temperatures. Blends or alloys of plastic and elastomeric rubber have become increasingly important in the production of high performance thermoplastic elastomers, particularly for the replacement of thermoset rubbers in various applications.
  • High performance thermoplastic elastomers in which a highly vulcanized rubbery polymer is intimately dispersed in a thermoplastic matrix are generally known as thermoplastic vulcanizates.
  • Polymer blends which have a combination of both thermoplastic and elastic properties are generally obtained by combining a thermoplastic resin with an elastomeric composition in a way such that the elastomer component is intimately and uniformly dispersed as a discrete particulate phase within a continuous phase of the thermoplastic.
  • vulcanized rubber components include both static vulcanization of the rubber, as well as the technique of dynamic vulcanization wherein a vulcanizable elastomer is dispersed into a molten resinous thermoplastic polymer and the elastomer is cured while continuously mixing and shearing the blend.
  • the resulting composition is a micro-gel dispersion of cured elastomer in an uncured matrix of thermoplastic polymer.
  • U.S. Pat. No. 4,803.244 generally discusses the use of multifunctional organosilicon compounds in conjunction with a catalyst as an agent for crosslinking the rubber component of a thermoplastic elastomer by hydrosilylation.
  • Hydrosilylation involves the addition of a silicon hydride across a multiple bond, often with a transition metal catalyst.
  • This patent describes a rhodium catalyzed hydrosilylation of EPDM rubber in a blend with polypropylene to produce thermoplastic elastomers having a gel content of up to 34% (after correction for the plastic phase). This degree of vulcanization was achieved c ⁇ y with a high level of catalyst.
  • a further modification of hydrosilylation crosslinking of the rubber in a thermoplastic elastomer composition is disclosed in European Patent Application No. 651 ,009.
  • a compatibilizing agent containing in the same molecule a component having an affinity for the rubber and a component having an affinity for the thermoplastic resin is incorporated into the composition, and is said to improve adhesion between the rubber and resin in order to prevent agglomeration.
  • U.S. Pat. No. 5.672,660 discloses the preparation of thermoplastic elastomers using hydrosilylation crosslinking of the rubber component, wherein very low amounts of platinum catalyst are used in conjunction with specific diene containing rubbers, and further discloses the desirability of conducting the reaction in a medium which is free of materials with Lewis base behavior.
  • thermoplastic elastomers prepared using a phenolic curative, and stabilized with a hydrolysis-insensitive HALS compound.
  • the present invention is based on the discovery that selected hindered amine light stabilizers (HALS) can be incorporated into a one pass dynamic vulcanization process, using a platinum-catalyzed hydrosilylation cure, to prepare a thermoplastic elastomer from a blend of thermoplastic resin and unsaturated rubber.
  • HALS hindered amine light stabilizers
  • the resulting thermoplastic elastomers can be fully or partially cured, with desirable tensile and elasticity properties as well as improved resistance to degradation by ultraviolet (UV) light.
  • UV light ultraviolet
  • the preferred structure of HALS compounds for use in the invention is one in which the sterically unhindered amine functionality is minimized.
  • compositions of the present invention have utility as replacements for thermoset rubber compounds in a variety of applications, particularly where molding or extrusion is involved and the combination of thermoplastic and elastomeric properties, as well as UV stability, provide an advantage.
  • Typical uses include molded articles for automobile underhood o parts, engineering and construction materials, mechanical rubber goods, industrial parts such as hose, tubing and gaskets, electrical applications and household goods.
  • Thermoplastic elastomer compositions may generally be prepared by blending a thermoplastic resin and a rubber, then melting the thermoplastic component and mixing the melt until the blend is homogeneous. If a composition of vulcanized rubber in a thermoplastic matrix is desired, crosslinking agents (also referred to as curatives or vulcanizing agents) are added to the blend and crosslinking occurs during the mixing. This latter process is described as dynamic vulcanization.
  • thermoplastic resins and rubbers and/or their mixtures have been used in the preparation of thermoplastic elastomers, including polypropylene.
  • HDPE LDPE.VLDPE.
  • LLDPE cyclic olefin homopolymers or copolymers as well as olefinic block copolymers
  • polystyrene polyphenylene sulfide.
  • EPDM ethylene propylene diene
  • NBR acrylonitrile butadiene
  • SBR styrene butadiene
  • NR natural
  • Hydrosilylation has been disclosed as a crosslinking method.
  • a silicon hydride having at least two SiH groups in the molecule is reacted with the carbon-carbon multiple bonds of the unsaturated (i.e. containing at least one carbon-carbon double bond) rubber component of the thermoplastic elastomer, in the presence of the thermoplastic resin and a hydrosilylation catalyst.
  • Silicon hydrides useful in the process of the invention include methylhydrogen polysiloxanes, methylhydrogen dimethyl-siloxane copolymers. alkylated methyl hydrogen polysiloxanes, bis(dimefhylsilyl)alkanes and bis(dimethylsilyl) benzene.
  • the amount of silicon hydride compound useful in the process of the present invention can range from about 0.1 to about 10.0 mole equivalents of SiH per carbon-carbon double bond in the rubber, and preferably is in the range of about 0.5 to about 5.0 mole equivalents of SiH per carbon-carbon double bond in the rubber component of the thermoplastic elastomer.
  • Thermoplastic resins useful in the compositions produced by the invention include crystalline polyolefin homopolymers and copolymers. They are desirably prepared from monoolefin monomers having 2 to 20 carbon atoms, such as ethylene, propylene. 1-butene, 1-pentene and the like, as well as copolymers derived from linear and cyclic olefins, with propylene being preferred.
  • polypropylene includes homopolymers of propylene as well as reactor copolymers of polypropylene which can contain about 1 to about 20 wt% of ethylene or an olefin comonomer of 4 to 20 carbon atoms, and mixtures thereof.
  • the polypropylene can be crystalline isotactic or syndiotactic. and may be prepared by Ziegler-Natta or metallocene catalysis. Other thermoplastic resins which are substantially inert to the rubber, the silicon hydride and the hydrosilylation catalyst would also be suitable. Blends of thermoplastic resins may also be used.
  • the amount of thermoplastic resin found to provide useful compositions is generally from about 5 to about 90 weight percent, based on the weight of the rubber and resin.
  • the thermoplastic resin content will range from about 20 to about 80 percent by weight of the total polymer.
  • Unsaturated rubbers useful to prepare thermoplastic elastomers according to the invention include monoolefin copolymer rubbers comprising non-polar, rubbery copolymers of two or more -monoolefins, preferably copolymerized with at least one polyene. usually a diene.
  • unsaturated monoolefin rubber such as EPDM rubber is more suitable.
  • EPDM is a polymer of ethylene, propylene and one or more non-conjugated diene or non-conjugated dienes, and the monomer components may be polymerized using Ziegler-Natta or metallocene catalyzed reactions, among others.
  • Satisfactory non-conjugated dienes include 5-ethylidene-2-norbornene (ENB); 1 ,4-hexadiene (HD); 5-methylene-2-norbornene (MNB); 1 ,6-octadiene; 5-methyl-l,4-hexadiene; 3,7-dimethyl-l,6-octadiene; 1.3-cyclopentadiene; 1.4-cyclohexadiene; dicyclopentadiene (DCPD); 5-vinyl-2-norbornene (VNB) and the like, or a combination thereof.
  • ENB 5-ethylidene-2-norbornene
  • HD high
  • MNB 5-methylene-2-norbornene
  • VNB dicyclopentadiene
  • Blends of any of the above rubbers may also be employed, rather than a single olefinic rubber.
  • the amount of rubber generally ranges from about 95 to about 10 weight percent, based on the weight of the rubber and thermoplastic resin.
  • the rubber content will be in the range of from about 80 to about 20 weight percent of total polymer.
  • any catalyst, or catalyst precursor capable of generating a catalyst in situ, which will catalyze the hydrosilylation reaction with the carbon-carbon bonds of the rubber can be used.
  • Such catalysts have included transition metals of Group VIII such as palladium, rhodium, platinum and the like, including complexes of these metals.
  • Chloroplatinic acid has been disclosed as a useful catalyst in U.S. Pat. No. 4,803,244 and European Application No. 651.009. which further disclose that the catalyst may be used at concentrations of 5 to 10,000 parts per million by weight and 100 to 200.000 parts per million by weight based on the weight of rubber, respectively.
  • Platinum-containing catalysts which are useful in the process of the invention are described, for example, in U.S. Pat. No. 4.578.497; U.S. Pat. No. 3,220,972; and U.S. Patent No. 2,823,218 all of which are incorporated herein by this reference.
  • These catalysts include chloroplatinic acid, chloroplatinic acid hexahydrate. complexes of chloroplatinic acid with sym-divinyltetramethyldisiloxane.
  • the thermoplastic elastomer may contain conventional additives, which can be introduced into the composition in the thermoplastic resin, the rubber, or in the blend either before, during or after the hydrosilylation and curing.
  • additives are antioxidants, processing aids, reinforcing and nonreinforcing fillers, pigments, waxes, rubber processing oil, extender oils, antiblocking agents, antistatic agents, plasticizers (including esters), foaming agents, flame retardants and other processing aids known to the rubber compounding art.
  • additives may comprise from about 0.1 to about 300 percent by weight based on the weight of the final thermoplastic elastomer product.
  • Fillers and extenders which can be utilized include conventional inorganics such as calcium carbonate, clays, silica, talc, titanium dioxide, carbon black and the like. Additives, fillers or other compounds which may interfere with the hydrosilylation should be added after curing reaches the desired level.
  • HALS HALS
  • Hindered amine light stabilizers are regularly compounded into materials requiring improved UV resistance. UV protection is provided by the amine functionality of the stabilizer, which is easily oxidized to form nitroxyl amines.
  • transition metal catalyzed hydrosilylation such reactions are sensitive to the presence of Lewis bases. It was thought that these reaction systems should be essentially free of compounds such as amines, sulfides and phosphines. Interference with hydrosilylation reactions by these compounds is believed to be from bonds formed between the non-bonded pairs of electrons donated by the Lewis base and the transition metal center. Since this bond with the metal center is stronger than those that characterize the bonds of "good" ligands. the activity of the catalyst is reduced.
  • HALS crosslinking
  • the rubber component of the thermoplastic elastomer is generally present as small, i.e. micro-size, particles within a continuous thermoplastic resin matrix, although a co-continuous morphology or a phase inversion is also possibl . depending upon the amount of rubber relative to plastic and the degree of cure of the rubber.
  • the rubber is desirably at least partially crosslinked, and preferably is completely or fully crosslinked. It is preferred that the rubber be crosslinked by the process of dynamic vulcanization.
  • dynamic vulcanization means a vulcanization or curing process for a rubber blended with a thermoplastic resin, wherein the rubber is vulcanized under conditions of shear at a temperature at which the mixture will flow. The rubber is thus simultaneously crosslinked and dispersed as fine particles within the thermoplastic resin matrix, although as noted above other morphologies may exist. Dynamic vulcanization is effected by mixing the thermoplastic elastomer components at elevated temperatures in conventional mixing equipment such as roll mills. Banbury mixers, Brabender mixers, continuous mixers, mixing extruders and the like.
  • compositions can be processed and reprocessed by conventional plastic processing techniques such as extrusion, injection molding and compression molding. Scrap or flashing can be salvaged and reprocessed.
  • corrected initial and final weights are obtained by subtracting from the initial weight the weight of soluble components, other than rubber to be vulcanized, such as extender oils, plasticizers and components of the composition soluble in organic solvent, as well as that rubber component of the product which is not intended to be cured. Any insoluble polyolefins, pigments, fillers, and the like are subtracted from both the initial and final weights.
  • the rubber component can be described as fully cured when less than about 5%. and preferably less than 3%, of the rubber which is capable of being cured by hydrosilylation is extractable from the thermoplastic elastomer product by a solvent for that rubber. Alternatively the degree of cure may be expressed in terms of crosslink density. All of these descriptions are well known in the art, for example in U.S. Pat. Nos. 4.593.062. 5,100,947 and 5,157,081, all of which are fully incorporated herein by this reference.
  • thermoplastic elastomers by the process of the invention, as set forth in the examples.
  • the thermoplastic resin and oil extended rubber were placed in a heated internal mixer, with the hydrosilylation agent, hydrosilylation catalyst and HALS compound.
  • the hydrosilylation agent and catalyst can be incorporated into the composition by any suitable technique, for example by injection as solutions in oil or as neat components, although a dilute catalyst solution is preferred.
  • Additives such as antioxidants, ultraviolet stabilizers and fillers may also be added as a slurry in oil. Masterbatches of the components may also be prepared to facilitate the blending process.
  • the mixture was heated to a temperature sufficient to melt the thermoplastic component, and the mixture was masticated, with added processing oil if desired, until a maximum of mixing torque indicated that vulcanization had occurred. Mixing was continued until the desired degree of vulcanization was achieved.
  • the invention will be better understood by reference to the following examples which serve to illustrate but not limit the present process. In the examples, the following test methods were used to determine the properties of the thermoplastic elastomer products.
  • compositions were prepared by the method of the invention as generally described above, using polypropylene resin and EPDM rubber containing 5-vinyl, 2-norbornene as the diene component.
  • the thermoplastic (41 parts) and rubber (100 parts) were melt mixed in a Brabender mixer at 180°C until the polypropylene was melted.
  • Silicone hydride (alkylated methyl hydrogen polysiloxane) [2 phr] was added dropwise to the melt mix, followed by addition of an oil solution containing 0.75 ppm platinum [platinate (II) hexachloro, dihydrogen reaction product with 2,4,6,8-tetraethenyl-2,4,6,8-tetramethyl cyclotetrasiloxane].
  • the HALS compound was added to the blend neat after silicone hydride addition, in a ratio of 1.5 gram of HALS to 60 grams of plastic/rubber blend.
  • the rubber was dynamically vulcanized by mixing the blend until the maximum torque was reached.
  • the product was removed from the mixer, then returned to the mixer and masticated at 180°C for an additional minute. Plaques were prepared by compression molding the products of the dynamic vulcanization at 200°C to a thickness of 60 mil and cooling under pressure, and the physical properties were determined using these plaques. All of the products were elastomeric, as defined by ASTM D1566, i.e. all had tension set values of less than 50%.
  • Table I The compositions and their properties are set forth in Table I
  • thermoplastic elastomer products with properties essentially the same as the control blend 1 (i.e. without HALS).
  • Compositions prepared using HALS having amine functionality capable of reacting with platinum e.g. structures I, II and III have poor properties compared to the control.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne un élastomère thermoplastique photostabilisé comprenant un mélange de résine thermoplastique et de caoutchouc insaturé. Ce caoutchouc a été préalablement soumis à une vulcanisation dynamique par hydrosilylation en présence d'un composé photostabilisateur amine encombrée qui ne comporte pas de fonctionnalité amine dépourvue d'encombrement stérique.
PCT/US1998/014791 1997-07-17 1998-07-17 Elastomeres thermoplastiques traites par hydrosilylation WO1999003927A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
JP2000503144A JP2001510219A (ja) 1997-07-17 1998-07-17 ヒドロシリル化硬化された熱可塑性エラストマー
BR9810886-7A BR9810886A (pt) 1997-07-17 1998-07-17 Composição de elastÈmero termoplástico estabilizado à luz e, processo para a preparação de um elastÈmero termoplástico estabilizado à luz.
AU84093/98A AU736139B2 (en) 1997-07-17 1998-07-17 Hydrosilylation cured thermoplastic elastomers
KR1020007000211A KR20010021653A (ko) 1997-07-17 1998-07-17 하이드로실릴화 경화된 열가소성 탄성중합체
CA002295508A CA2295508A1 (fr) 1997-07-17 1998-07-17 Elastomeres thermoplastiques traites par hydrosilylation
EP98934606A EP0996679A4 (fr) 1997-07-17 1998-07-17 Elastomeres thermoplastiques traites par hydrosilylation
IL13408598A IL134085A0 (en) 1997-07-17 1998-07-17 Hydrosilylation cured thermoplastic elastomers

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US5288397P 1997-07-17 1997-07-17
US60/052,883 1997-07-17

Publications (1)

Publication Number Publication Date
WO1999003927A1 true WO1999003927A1 (fr) 1999-01-28

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ID=21980539

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1998/014791 WO1999003927A1 (fr) 1997-07-17 1998-07-17 Elastomeres thermoplastiques traites par hydrosilylation

Country Status (9)

Country Link
EP (1) EP0996679A4 (fr)
JP (1) JP2001510219A (fr)
KR (1) KR20010021653A (fr)
CN (1) CN1264405A (fr)
AU (1) AU736139B2 (fr)
BR (1) BR9810886A (fr)
CA (1) CA2295508A1 (fr)
IL (1) IL134085A0 (fr)
WO (1) WO1999003927A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1146082A1 (fr) * 2000-04-13 2001-10-17 Advanced Elastomer Systems, L.P. Procédé pour durcir du caoutchouc butyle / polypropylène avec des composés organosilanes
EP1293534A1 (fr) * 2000-06-20 2003-03-19 Mitsui Chemicals, Inc. Compositions de caoutchouc reticulables et utilisation de celles-ci
EP1574375A1 (fr) * 2004-03-12 2005-09-14 Inalfa Roof Systems Group B.V. Elément constructif
US7714053B2 (en) 2005-09-21 2010-05-11 Carl Freudenberg Kg Rubber compound
DE102005063353B4 (de) * 2005-09-21 2015-10-08 Carl Freudenberg Kg Elastomerblend, Verfahren zur Herstellung und dessen Verwendung

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4364407B2 (ja) * 2000-06-20 2009-11-18 三井化学株式会社 架橋可能なゴム組成物およびその用途
JP5297807B2 (ja) * 2006-09-22 2013-09-25 株式会社カネカ 硬化性組成物

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4130535A (en) * 1975-07-21 1978-12-19 Monsanto Company Thermoplastic vulcanizates of olefin rubber and polyolefin resin
US4803244A (en) * 1987-11-16 1989-02-07 Union Carbide Corporation Process for the preparation of thermoplastic elastomers
US5672660A (en) * 1995-12-01 1997-09-30 Advanced Elastomer Systems, L.P. Hydrosilylation crosslinking

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW273561B (fr) * 1993-10-21 1996-04-01 Sumitomo Bakelite Co

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4130535A (en) * 1975-07-21 1978-12-19 Monsanto Company Thermoplastic vulcanizates of olefin rubber and polyolefin resin
US4803244A (en) * 1987-11-16 1989-02-07 Union Carbide Corporation Process for the preparation of thermoplastic elastomers
US5672660A (en) * 1995-12-01 1997-09-30 Advanced Elastomer Systems, L.P. Hydrosilylation crosslinking

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0996679A4 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1146082A1 (fr) * 2000-04-13 2001-10-17 Advanced Elastomer Systems, L.P. Procédé pour durcir du caoutchouc butyle / polypropylène avec des composés organosilanes
EP1293534A1 (fr) * 2000-06-20 2003-03-19 Mitsui Chemicals, Inc. Compositions de caoutchouc reticulables et utilisation de celles-ci
EP1293534A4 (fr) * 2000-06-20 2003-08-06 Mitsui Chemicals Inc Compositions de caoutchouc reticulables et utilisation de celles-ci
US6743862B2 (en) 2000-06-20 2004-06-01 Mitsui Chemicals, Inc. Crosslinkable rubber compositions and uses thereof
EP1574375A1 (fr) * 2004-03-12 2005-09-14 Inalfa Roof Systems Group B.V. Elément constructif
US7714053B2 (en) 2005-09-21 2010-05-11 Carl Freudenberg Kg Rubber compound
DE102005063353B4 (de) * 2005-09-21 2015-10-08 Carl Freudenberg Kg Elastomerblend, Verfahren zur Herstellung und dessen Verwendung

Also Published As

Publication number Publication date
IL134085A0 (en) 2001-04-30
CN1264405A (zh) 2000-08-23
EP0996679A1 (fr) 2000-05-03
KR20010021653A (ko) 2001-03-15
AU736139B2 (en) 2001-07-26
JP2001510219A (ja) 2001-07-31
BR9810886A (pt) 2000-09-26
EP0996679A4 (fr) 2000-10-04
CA2295508A1 (fr) 1999-01-28
AU8409398A (en) 1999-02-10

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