WO1989005837A1 - Compositions elastomeres thermoplastiques et procede pour leur preparation - Google Patents

Compositions elastomeres thermoplastiques et procede pour leur preparation Download PDF

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Publication number
WO1989005837A1
WO1989005837A1 PCT/EP1987/000821 EP8700821W WO8905837A1 WO 1989005837 A1 WO1989005837 A1 WO 1989005837A1 EP 8700821 W EP8700821 W EP 8700821W WO 8905837 A1 WO8905837 A1 WO 8905837A1
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WO
WIPO (PCT)
Prior art keywords
component
weight
polymer
rubber
functional group
Prior art date
Application number
PCT/EP1987/000821
Other languages
English (en)
Inventor
Hisao Ono
Masanobu Nagano
Yasuo Ieki
Takumi Miyachi
Original Assignee
Shell Internationale Research Maatschappij B.V.
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
Priority claimed from JP61151197A external-priority patent/JPS638450A/ja
Priority to JP61151197A priority Critical patent/JPS638450A/ja
Priority to ES198787202594T priority patent/ES2033818T3/es
Priority to AU11522/88A priority patent/AU608285B2/en
Priority to EP88900952A priority patent/EP0344175A1/fr
Priority to US07/382,688 priority patent/US5055519A/en
Application filed by Shell Internationale Research Maatschappij B.V. filed Critical Shell Internationale Research Maatschappij B.V.
Priority to EP87202594A priority patent/EP0320538B1/fr
Priority to DE8787202594T priority patent/DE3781280T2/de
Priority to PCT/EP1987/000821 priority patent/WO1989005837A1/fr
Priority to BR8707971A priority patent/BR8707971A/pt
Priority to CA000554947A priority patent/CA1328937C/fr
Publication of WO1989005837A1 publication Critical patent/WO1989005837A1/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
    • C08L19/00—Compositions of rubbers not provided for in groups C08L7/00 - C08L17/00
    • C08L19/006—Rubber characterised by functional groups, e.g. telechelic diene polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene

Definitions

  • the invention relates to thermoplastic elastomer compositions, to a process for the preparation thereof and to articles comprising such compositions.
  • Very well-known block copolymers of an aromatic vinyl compound and a conjugated diene compound are styrene-butadiene block copolymers. They are produced industrially and are used as raw materials for shoe soles and as thermoplastic elastomers for improving the quality of polystyrene.
  • thermoplastic elastomers made of the above mentioned block copolymers are required which may be put to a greater variety of uses and whose elasticity and bending resistance performances are enhanced.
  • thermoplastic elastomer As a method of enhancing the elasticity of the thermoplastic elastomer, there is the method of adding process oil to the thermoplastic elastomer. However, by this method the properties of the product, e.g. its mechanical strength, such as its tensile strength, will decrease and there will occur bleed.
  • Another method to enhance the elasticity is the addition of a rubber substance, but as the thermo ⁇ plastic elastomer and the rubber substance do not blend sufficiently, here too there is the problem of reduced mechanical strength, such as its tensile strength.
  • the present invention offers themopla ⁇ tic elastomer compositions having excellent elasticity, bend resistance and mechanical strength as well as excellent oil resistance owing to the blending in of a special rubber polymer.
  • thermoplastic elastomer compositions characterized in that they have been prepared from the following components:- Component A - a block copolymer of an aromatic vinyl compound and a conjugated diene compound and/or a selectively hydrogenated product thereof,
  • Component B an aromatic vinyl polymer having a functional group which is reactive with the functional group of component (C)
  • Component C - a rubber polymer having at least one functional group chosen from carboxyl, amino, epoxy and hydroxyl groups.
  • an aromatic vinyl polymer containing a reactive functional group (component B) is introduced in order to improve the mutual solubilities of the aromatic vinyl-conjugated diene block copolymer and/or the selectively hydrogenated product thereof (component
  • component B becomes the mutual solubilizer of component A and component C, and the three kinds of polymer (component A) , (component B) and (component C) can become mutually soluble.
  • aromatic vinyl-conjugated diene block copolymer or the selectively hydrogenated product thereof may be represented by the following formula
  • A represents the aromatic vinyl compound polymer
  • B the conjugated diene polymer or copolymer or the hydro ⁇ genated polymer product of the conjugated diene (co)polymer
  • C a residue of a coupling agent.
  • the amount of aromatic vinyl compound present in the afore-mentioned block copolymer is suitably in range of from 7 to 90% by weight, preferably 10 to 70% by weight, its molecular weight suitably in the range of from 30,000 to 1,000,000, preferably 50,000 to 500,000.
  • the aromatic vinyl polymer having a reactive functional group (component B) preferably contains at least one functional group chosen from oxazolinyl, carboxyl, hydroxyl, amino and epoxy groups for the reactive functional group and can be simply obtained by copolymerizing a vinyl monomer containing such a functional group with an aromatic vinyl monomer.
  • vinyl monomers having an oxazolinyl group compounds having e.g. a 2-oxazolinyl group may be mentioned, examples thereof being 2-isopropenyl- 2-oxazoline, 2-isobutenyl-2-oxazoline, 2-isopentenyl-2-oxazoline, 2-vinyl-2-oxazoline.
  • vinyl monomers having a carboxyl group may be mentioned anhydrous maleic acid, maleic acid, acrylic acid, methacrylic acid, fumaric acid and olefinic carboxylic acids of the following general formula
  • Ri- is H or CH_,; R_, is a C_-_-Cfa- alkylene group; R_ is a phenylene, cyclohexylene or C -C ⁇ alkylene group or a bivalent ethylenically unsaturated hydrocarbon group.
  • R is hydrogen or a methyl group
  • R is hydrogen or an alkyl group containing in the range of from 1 to 6 carbon atoms.
  • Acrylates and methacrylates containing an amino group may suitably be such in which the amino group is not directly linked to the double bond of the acrylate group.
  • R is H or CH_ ; ⁇ . and are C.-C , suitably C--C hydrocarbon groups; X is a C_-C. alkylene group.
  • Examples are aminoethyl methacrylate, dimethylamino-ethyl methacrylate, diethylamino-ethyl methacrylate, dipropylamino-ethyl methacrylate, methylethyla ino-ethyl methacrylate, dibutyla ino-ethyl methacrylate, dibutylamino-propyl methacrylate, diethyla ino-butyl methacrylate, dihexylamino-ethyl methacrylate, dioctylamino-ethyl methacrylate.
  • dimethylamino-ethyl methacrylate diethylamino-ethyl methacrylate, dipropylamino-ethyl methacrylate, methylethylamino-ethyl methacrylate, are preferred.
  • unsaturated compounds containing an epoxy group the compounds containing an unsaturated group and an epoxy group in the molecule may be used.
  • Suitable unsaturated compounds containing an epoxy group are those having the general formula (III) following
  • R is a hydrogen atom, an alkyl group having in the range of from 1 to 5 carbon atoms or a glycidyl ester-substituted alkyl group having in the range of from 1 to 5 carbon atoms, and the general formula (IV) following
  • CH2_ C[ - CH2. - O - CH2_ - CH - CH2_ (IV)
  • R has the same meaning as in the general formula III.
  • Suitable examples are glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, allyl glycidyl ether; particularly suitable unsaturated compounds containing an epoxy group are glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether. Of these epoxy-containing unsaturated compounds, one or more than one may be used.
  • the reactive functional group is suitably present in the aromatic vinyl polymer (component B) in a quantity in the range of from 0.01 to 30% by weight, preferably 0.05 to 20% by weight, more preferably 0.1 to 10% by weight, calculated on the total of component B. If the amount of reactive functional group present is smaller than 0.01% by weight, the result will be insufficient, but if the amount of functional group present is larger than 30% by weight, the fluidity of the compositions will decrease, which is economically disadvantageous.
  • Suitable reactive functional groups are oxazolinyl, carbonyl and epoxy groups. Preferred are oxazolinyl and carbonyl groups.
  • aromatic vinyl compounds may be mentioned styrene, alpha- ethylstyrene, o-, m- and p-methylstyrene, 0-, m- and p-ethylstyrene, o-, m- and p-methoxystyrene, o-, m- and p-dimethylaminostyrene, o-, m- and p-i ⁇ opropylstyrene, p-t-butylstyrene, both 4-naphthylstyrenes.
  • styrene, p-methylstyrene and alpha-methylstyrene are preferred.
  • the rubber polymer component (component C) contains at least one functional group chosen from carboxyl, amino, epoxy and hydroxyl groups.
  • Methods of including the afore-mentioned functional groups in the rubber polymer may be the copolymerization of a functional vinyl monomer during the polymerization of the rubber polymer, or the addition of a functional vinyl monomer, a polymer of a functional vinyl monomer or a copolymer of a functional vinyl monomer and another monomer, to the rubber polymer.
  • a functional vinyl monomer containing at least one functional group chosen from carboxyl, amino, epoxy and hydroxyl groups, those enumerated for the aromatic vinyl polymers (component B) may be used.
  • the rubber polymers used may be polymers of such conjugated diene-type compounds as butadiene, isoprene, piperylene, chloroprene, rubber copolymers of said conjugated diene and aromatic vinyl compound, ethylene-propylene rubber, acrylic or methacrylic acid ester rubber polymer and rubber copolymers made up of acrylic or methacrylic acid ester and another monomer.
  • Examples are natural rubber, polyisoprene rubber, styrene-butadiene rubber, polybutadiene rubber, acrylonitrile-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, ethylene-propylene-non- conjugated diene rubber, acryl-type rubber, fluorine rubber. Acryl-type rubber and/or acrylonitrile- butadiene rubber are preferred.
  • the thermoplastic elastomer compositions of the present invention obtained have excellent bending resistance.
  • the acryl-type rubber may be a polymer or copolymer of at least one monomer chosen from such alkyl acrylates as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, amyl acrylate; or a copolymer of another monomer which can be copolymerized with such a monomer, such as styrene, acrylonitrile, butadiene.
  • Suitable alkyl acrylates are n-butyl acrylate, 2-ethylhexyl acrylate.
  • the amount of acrylonitrile present in the acrylonitrile-butadiene rubber is suitably in the range of from 5 to 50% by weight, preferably 10 to 45% by weight, and more specifically 15 to 40% by weight.
  • the content of functional groups in the rubber polymer (component C) is suitably in the range of from 0.01 to 15% by weight, preferably 0.1 to 10% by weight.
  • Suitable functional groups are carboxyl, amino and hydroxyl groups, carboxyl and amino groups being preferred.
  • a cyclic i ino ether group is used as the reactive functional group in component B
  • the choice of a carboxyl, amino or epoxy group as the functional group in component C is effective.
  • component B When a carboxyl group is used as the reactive functional group in component B, the choice of an amino and epoxy group as the functional groups in component C is effective.
  • an amino group is used as the reactive functional group in component B
  • the choice of a carboxyl group and an epoxy group as the functional groups in component C is effective.
  • an epoxy group is used as the reactive functional group in component B
  • the choice of a carboxyl group and a hydroxyl group as the functional groups in component C is effective.
  • the proportion of components A, B and C in the thermoplastic elastomer composition of the present invention is (A) in the range of from 9 to 90% by weight, preferably 25 to 80% by weight, specifically 30 to 70% by weight, (B) in the range of from 1 to 50% by weight , preferably 2 to 40% by weight, specifically 3 to 30% by weight, (C) in the range of from 9 to 90% by weight, preferably 15 to 70% by weight, specifically 20 to 60% by weight, said percentages being calculated on the total of components A, B and C.
  • the mixing temperature In the preparation of the thermoplastic elastomer composition of the invention, the mixing temperature must be raised to 20°C, preferably 40°C above the highest glass transition temperature of each of the components A, 3 and C, for melting and mechanical mixing. And during melting and mixing a catalyst may be added.
  • mixing can well be performed. If the temperature is lower during mixing, the reaction will not proceed sufficiently and moreover the viscosity of the composition will be too high during mixing. And, if the temperature during mixing is 0 too high, the rubber polymer component C will deterio ⁇ rate.
  • the equipment used in the preparation of the thermoplastic elastomer compositions of the invention may be well-known apparatus in which all the components 5 are melted and mixed, such as an open mixing roll, a closed Banbury mixer, an extruder, a kneader, a continuous mixer.
  • the composition of the present invention may include - within a range that will not harm fluidity o and mechanical strength - a filler, e.g. calcium carbo ⁇ nate, calcium silicate, clay, kaolin, talc, silica, diatomaceous earth, mica dust, asbestos, alumina, barium sulfate, aluminium ⁇ ulfate, calcium sulfate, basic magnesium carbonate, molybdenum bisulfide, 5 graphite, carbon fibers, or a colouring agent, e.g. carbon black, ultramarine, titanium oxide, zinc oxide, red oxide, Prussian blue, azo dyes, nitroso dyes, Lake dyes, phthalocyanine dyes.
  • a filler e.g. calcium carbo ⁇ nate, calcium silicate, clay, kaolin, talc, silica, diatomaceous earth, mica dust, asbestos, alumina, barium sulfate, aluminium ⁇ ulfate, calcium sul
  • petroleum rubber softeners so-called Q process oil or extension oil
  • plasticizers such as dioctyl phthalate, dibutyl phthalate, diethyl phthalate, dimethyl phthalate, tricresyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, trimellitic acid ester, 5 dioctyl adipate, dioctyl azelate, dioctyl sebacate, epoxy resin acid ester, may be included in a range which will not damage mechanical strength, in order to enhance fluidity.
  • thermoplastic elastomer compositions of the 5 present invention may be applied for motor car parts, e.g. body panels, bumper parts, side shields, steering wheels, for foot wear, e.g. shoe soles, sandals, for electric wire coverings, for electrical parts, e.g. connectors, cap plugs, for such leisure articles as 0 golf club grips, grips for baseball bats, bicycle and motorbike grips, swimming fins, under-water glasses, and as raw materials for such articles as gaskets, waterproof clothing, garden hoses, belts and the like.
  • Example 1 Example 1
  • Blend composition styrene-butadiene block copolymer 80 50 *1 50 *1 50 *2 100 *1 50 reactive polystyrene (pbw) 5 .*3 .*3 5 10 generally used polystyrene (pbw) .*5 reactive NBR (pbw) 15 45 *6 90 generally used NBR (pbw) 45 *7 45 *7 45
  • JSR TR2000 used (40% by weight styrene) (ex Jap.
  • JSR NBR N230S (AN content : 35% by weight, Mooney visco ⁇ ity 56) ex Jap. Synthetic Rubber *8. ⁇ heet deformation, exact value not sought *9. JIS K6301 *10. A 20x20x1 mm sheet was immer ⁇ ed for 22 h in oil at
  • the propertie ⁇ were evaluated and the re ⁇ ult ⁇ are given in Table 1. Comparative Experiment B
  • Example 4 The composition was prepared in the same way as in Example 1, except that instead of the reactive poly ⁇ styrene of Example 1, a normally used polystyrene (ex Mitsui Toatsu, Toporex 525) was employed. The properties were evaluated and the results are given in Table 1.
  • a normally used polystyrene ex Mitsui Toatsu, Toporex 525.
  • Example 5 The composition was prepared in the same way as in Example 1, except that instead of the styrene-butadiene- styrene block copolymer of Example 1 (JSR TR 2000, 40 %w styrene) , a radial-block-type oil-expanded ⁇ tyrene-buta- diene block copolymer (JSR TR 1000, 40 %w ⁇ tyrene) wa ⁇ employed. The propertie ⁇ were evaluated and the re ⁇ ults are given in Table 1.
  • Example 5 The propertie ⁇ were evaluated and the re ⁇ ults are given in Table 1.
  • the compo ⁇ ition wa ⁇ prepared in the ⁇ ame way as in Example 1, except that in ⁇ tead of the 2-oxazolinyl- containing reactive poly ⁇ tyrene of Example 1, a copolymer of anhydrou ⁇ maleic acid and ⁇ tyrene (10 %w anhydrou ⁇ maleic acid, molecular weight 150000) wa ⁇ employed, and that an amino-containing acrylonitrile- butadiene copolymer (diethyl-amino-ethyl methacrylate, Mooney vi ⁇ cosity ML 1+4, 100 °C 55, 33 %w acrylonitrile) wa ⁇ employed.
  • Example 6 The composition was prepared in the same way as in Example 4, except that instead of the reactive acryl ⁇ onitrile-butadiene copolymer of Example 4, normal NBR (JSR NBR 23OS) was employed. The properties were a ⁇ essed and the results are given in Table 1.
  • composition was prepared in the ⁇ ame way as in Example 1, except that instead of the styrene-butadiene- styrene block copolymer of Example 1 (JSR TR 2000) , a styrene-ethylene-butene-styrene block copolymer (selec ⁇ tively hydrogenated styrene-butadiene- ⁇ tyrene block copolymer, ex Shell Kraton G1650) wa ⁇ employed. The properties were evaluated and the results are given in Table 1.
  • Example 7 Comparative Experiment E
  • compositions were prepared in the same way as in Example 1, the differences being that instead of the carboxyl-containing acrylonitrile-butadiene of
  • Compo ⁇ ition ⁇ were prepared in the ⁇ ame way a ⁇ in 0 Example 1, except that different blend ⁇ of components
  • Example ⁇ 1, 2 and 3 show that when the compositions prepared of styrene-butadiene copolymer, 5 functional-groupcontaining polystyrene and functional-group-containing rubber copolymer, are melted and mixed at a high temperature, thi ⁇ will lead to compositions having high tear resi ⁇ ting ⁇ trength and large pull.
  • thermoplastic elastomer compositions according to the invention have excellent elasticity, bending resistance and mechanical strength, and ⁇ ince they al ⁇ o have excellent oil re ⁇ i ⁇ tance, they can be put to a wider range of u ⁇ e ⁇ than the hitherto known ther o- pla ⁇ tic ela ⁇ tomer ⁇ , ⁇ o that they have a great practical value.

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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)

Abstract

La présente invention décrit des compositions élastomères thermoplastiques préparées à partir: (A) d'un copolymère bloc, d'un composé vinylique aromatique et d'un diène conjugué et/ou d'un produit sélectivement hydrogéné dudit diène, (B) d'un polymère vinylique aromatique comportant un groupe fonctionnel qui réagit avec le groupe fonctionnel du composant C, et (C) d'un polymère de caoutchouc comportant un carboxyle, un amino, un époxy et/ou un groupe hydroxyle. La présente invention décrit également un procédé de préparation de ces compositions par mélange en fusion des trois composants.
PCT/EP1987/000821 1986-06-27 1987-12-18 Compositions elastomeres thermoplastiques et procede pour leur preparation WO1989005837A1 (fr)

Priority Applications (10)

Application Number Priority Date Filing Date Title
JP61151197A JPS638450A (ja) 1986-06-27 1986-06-27 熱可塑性エラストマ−組成物
BR8707971A BR8707971A (pt) 1986-06-27 1987-12-18 Composicoes de elastomero termoplastico,processo para sua preparacao e artigo que as compreende
AU11522/88A AU608285B2 (en) 1986-06-27 1987-12-18 Thermoplastic elastomer compositions and process for the preparation thereof
EP88900952A EP0344175A1 (fr) 1986-06-27 1987-12-18 Compositions elastomeres thermoplastiques et procede pour leur preparation
US07/382,688 US5055519A (en) 1986-06-27 1987-12-18 Thermoplastic elastomer compositions and process for the preparation thereof
ES198787202594T ES2033818T3 (es) 1986-06-27 1987-12-18 Procedimiento para la preparacion de composiciones de elastomeros termoplasticos.
EP87202594A EP0320538B1 (fr) 1986-06-27 1987-12-18 Compositions d'élastomère thermoplastique et leur procédé de préparation
DE8787202594T DE3781280T2 (de) 1986-06-27 1987-12-18 Thermoplastische elastomerzusammensetzungen und verfahren zu deren herstellung.
PCT/EP1987/000821 WO1989005837A1 (fr) 1986-06-27 1987-12-18 Compositions elastomeres thermoplastiques et procede pour leur preparation
CA000554947A CA1328937C (fr) 1986-06-27 1987-12-21 Compositions elastomeres thermoplastiques et procede de preparation

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP61151197A JPS638450A (ja) 1986-06-27 1986-06-27 熱可塑性エラストマ−組成物
PCT/EP1987/000821 WO1989005837A1 (fr) 1986-06-27 1987-12-18 Compositions elastomeres thermoplastiques et procede pour leur preparation
CA000554947A CA1328937C (fr) 1986-06-27 1987-12-21 Compositions elastomeres thermoplastiques et procede de preparation

Publications (1)

Publication Number Publication Date
WO1989005837A1 true WO1989005837A1 (fr) 1989-06-29

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PCT/EP1987/000821 WO1989005837A1 (fr) 1986-06-27 1987-12-18 Compositions elastomeres thermoplastiques et procede pour leur preparation

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996024634A1 (fr) * 1995-02-07 1996-08-15 Basf Aktiengesellschaft Piece moulee a usage medical, notamment element d'un systeme de transmission utile a des fins de perfusion ou de transfusion

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1154914A (fr) * 1955-07-09 1958-04-18 Bayer Ag Compositions de polymères synthétiques thermoplastiques et élastiques et leur procédé de fabrication
FR1493045A (fr) * 1966-07-13 1967-08-25 Nouveaux copolymères à base de dioléfine
EP0128598A1 (fr) * 1983-06-08 1984-12-19 Shell Internationale Researchmaatschappij B.V. Composition de moulage thermoplastique
EP0178752A1 (fr) * 1984-09-14 1986-04-23 Cameron Iron Works, Inc. Elastomère rendu tenace par du caoutchouc liquide

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1154914A (fr) * 1955-07-09 1958-04-18 Bayer Ag Compositions de polymères synthétiques thermoplastiques et élastiques et leur procédé de fabrication
FR1493045A (fr) * 1966-07-13 1967-08-25 Nouveaux copolymères à base de dioléfine
EP0128598A1 (fr) * 1983-06-08 1984-12-19 Shell Internationale Researchmaatschappij B.V. Composition de moulage thermoplastique
EP0178752A1 (fr) * 1984-09-14 1986-04-23 Cameron Iron Works, Inc. Elastomère rendu tenace par du caoutchouc liquide

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996024634A1 (fr) * 1995-02-07 1996-08-15 Basf Aktiengesellschaft Piece moulee a usage medical, notamment element d'un systeme de transmission utile a des fins de perfusion ou de transfusion

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