WO1989006660A1 - Composition de copolymere bloc et procede de preparation d'une telle composition - Google Patents

Composition de copolymere bloc et procede de preparation d'une telle composition Download PDF

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Publication number
WO1989006660A1
WO1989006660A1 PCT/EP1988/000037 EP8800037W WO8906660A1 WO 1989006660 A1 WO1989006660 A1 WO 1989006660A1 EP 8800037 W EP8800037 W EP 8800037W WO 8906660 A1 WO8906660 A1 WO 8906660A1
Authority
WO
WIPO (PCT)
Prior art keywords
block copolymer
copolymer composition
weight
aromatic vinyl
vinyl compound
Prior art date
Application number
PCT/EP1988/000037
Other languages
English (en)
Inventor
Yasuo Toyama
Yasuo Ieki
Hisao Ono
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 to JP60132687A priority Critical patent/JPS61291610A/ja
Application filed by Shell Internationale Research Maatschappij B.V. filed Critical Shell Internationale Research Maatschappij B.V.
Priority to EP88901246A priority patent/EP0349536A1/fr
Priority to PCT/EP1988/000037 priority patent/WO1989006660A1/fr
Priority to AU12221/88A priority patent/AU605553B2/en
Priority to BR888807423A priority patent/BR8807423A/pt
Priority to EP88200103A priority patent/EP0324992A1/fr
Publication of WO1989006660A1 publication Critical patent/WO1989006660A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/021—Block or graft polymers containing only sequences of polymers of C08C or C08F
    • C08G81/022—Block or graft polymers containing only sequences of polymers of C08C or C08F containing sequences of polymers of conjugated dienes and of polymers of alkenyl aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C08F297/044—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes using a coupling agent

Definitions

  • the invention relates to a block copolymer composition.
  • the invention further relates to a process for the preparation of said block copolymer composition.
  • Block copolymers of an aromatic vinyl compound and a conjugated diene compound obtained by anionic polymerization in a hydrocarbon solvent with an alkyllithium compound as an initiator are thermoplastic elastomers which are nowadays much in demand because even without vulcanization they obtain great rubber elasticity, and because they can be moulded generally in a thermoplastic resin moulder, are cheap and can be reclaimed from scrap.
  • shock resistance improvers by suitable blending with a thermoplastic resin, such as polystyrene, as soles for foot wear, such as camper shoes and casual shoes, by blending with a suitable resin, rubber, softener, filler, as tackifiers, binding agents, alphalt improvers, sheets, films and moulding materials.
  • a thermoplastic resin such as polystyrene
  • a suitable resin rubber, softener, filler, as tackifiers, binding agents, alphalt improvers, sheets, films and moulding materials.
  • SBS styrene-butadiene-styrene block copolymers
  • the invention provides a block copolymer composition, characterized in that it contains not less than 30% by weight of an aromatic vinyl compound-conjugated diene compound block copolymer with an aromatic vinyl compound content in the range of from 10-90% by weight, represented by the general formula I
  • A-B n X (I) in which formula A represents a polymer block in which the aromatic vinyl compound is the main component, B represents a polymer block in which the conjugated diene compound is the main component, n is an integer not less than 5 and X is a coupling agent residue, and which block copolymer yields a 25% by weight solution thereof in toluene having a viscosity at a temperature of 25 °C in the range of from 50 to 1000 cP.
  • A is a polymer block in which the aromatic vinyl compound is the main component, the copolymer block being made up of only an aromatic vinyl compound, or of not less than 60% by weight, preferably not less than 80% by weight, of an aromatic vinyl compound and a conjugated diene compound
  • B is a polymer block in which the conjugated diene compound is the main component, the copolymer block being made up of only a conjugated diene compound, or of not less than 60% by weight, preferably not less than 80% by weight, of a conjugated diene compound and an aromatic vinyl compound which may be randomly coupled or form one or more so-called tapered blocks.
  • styrene As the aromatic vinyl compounds, styrene, ⁇ -methylstyrene, o-, m- and p-methylstyrene, the vinylxylenes, the o- , m- and p-chlorostyrene, the dichlorostyrenes, o- m- and p-bromostyrene, the dibromostyrenes, o-, m- and p-furfuro-styrene, p-tert-butylstyrene, o-, m- and p-ethylstyrene, 1- or 2-vinylnaphthalene; of these, one or two or more may be used. Styrene is preferred.
  • Conjugated diene compounds which may be used are 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-neopentyl-l,3-butadiene, 2-chloro-l,3-butadiene, 2-cyano-1,3-butadiene, substituted linear conjugated pentadienes, linear and branched conjugated hexadienes. Of these, 1,3-butadiene is preferred.
  • n represents the number of branches involved in the coupling reaction and is an integer of not less than 5, preferably 5-8. When n is lower than 4, this will lead to considerable shrinkage in the block copolymer.
  • X is the coupling agent residue resulting from the coupling reaction.
  • composition according to the present invention contains at least 30% by weight, suitably at least 50% by weight, preferably at least 70% by weight of the block copolymer of the afore-mentioned structure. When this content is lower than 30% by weight, dimensional stability will be poor.
  • the block copolymer according to the present invention yields a 25% by weight solution thereof in toluene having a viscosity at a temperature of 25 °C in the range of from 50 to 1000 cP, preferably 100 to 800 cP.
  • a viscosity at a temperature of 25 °C in the range of from 50 to 1000 cP, preferably 100 to 800 cP.
  • the total amount of bonded aromatic vinyl compound present in the afore-mentioned block copolymer of the present invention is in the range of from 10 to 90% by weight, suitably in the range of from 20 to 70% by weight, preferably in the range of from 20 to 60% by weight. If the total amount of bonded aromatic vinyl compound lies outside the afore-mentioned range, the mechanical strength will be adversely affected.
  • the invention further provides a process for the preparation of a block copolymer composition according to the present invention which process comprises the following steps:- step 1:- polymerizing monomer A containing an aromatic vinyl compound as the main component in the presence of (a) a hydrocarbon solvent, (b) an organic lithium compound as an initiator and (c) an ether and/or a tertiary amine, until the polymerization is substantially terminated; step 2:- adding monomer B containing a conjugated diene compound as the main component to the mixture formed in step 1 and continuing polymerization, and step 3:- adding at least one coupling agent containing not less than five functional groups to the mixture formed in step 2 and allowing coupling to take place.
  • Exemplary coupling agents of the present invention are
  • the solution viscosity of the block copolymer of the present invention can be controlled through the amount of organic lithium initiator added. By adding a large amount of organic lithium initiator the solution viscosity can be decreased.
  • the block copolymer of the present invention can be blended with the usual thermoplastic resins, rubber or additives.
  • exemplary thermoplastic resins are polystyrene type resins, polyethylene type resins, polypropylene type resins, polybutene t P e resins, poly(vinyl chloride) type resins, poly(vinyl acetate) type resins, polyamide type resins, thermoplastic polyester type resins, polyacetal type resins, polybutadiene type resins, thermoplastic polyurethane type resins, polyester type resins, polycarbonate type resins.
  • Exemplary rubbers are styrene-butadiene rubber, nitrile-butadiene rubber, butadiene rubber, ethylene-propylene rubber, isoprene rubber, nitrile rubber, chloroprene rubber, isobutylene-isoprene rubber, high-styrene rubber (HSR).
  • Additives that may be used are plasticizers, such as phthalic ester compounds, fillers, such as silica, talc, glass fibre or reinforcing agents, as well as oxidation inhibitors, ultraviolet absorbers, antistatic agents, flame retardants, lubricants, blowing agents, colouring agents, pigments, cross-linking agents, cross-linking aids or mixtures thereof.
  • the block copolymer according to the present invention may be mixed with the above-mentioned additives, such as plasticizers and fillers, by well-known means, such as an extruder (with one or two screws), a roll, a Banbury mixer, a kneader, a Henschel mixer.
  • additives such as plasticizers and fillers
  • thermoplastic resin compositions obtained by the afore-mentioned methods may be carried out by known methods, for instance extrusion, injection moulding, mid-air moulding, compression moulding, calendering, to form practically useful mould goods, which may be galvanized or painted, as required.
  • Block copolymers of the present invention find a wide range of uses; they can be suitably used for sole material for foot wear, such as camper shoes, casual shoes, unit soles, or as films, sheets and all kinds of mould goods; for instance household appliances, such as television and stereo sets, vacuum cleaners, motor car parts, such as bumper parts, body pannels, side sheelds, they may be used as raw material for hot melt glues and binding agents, contact glues, spray glues, material for road pavement, waterproof sheets, pipe coating, raw material for asphalt blends and they may also be applied for daily necessities, leisure goods, toys, industrial goods, as well as for all kinds of rubber and thermoplastic resin improvers. They are very suited for use in foot wear and toys.
  • Example 1 the temperature was kept generally at 70°C. After termination of the polymerization, 2,6-di- tert-butyl-p-cresole was added to the polymer solution, after which the cyclohexane was removed by heating to give the block copolymer, which was taken as Example 1.
  • Examples 2-4 and Comparative Experiments A-D were polymerized by using styrene, butadiene, coupling agent in amounts as listed in Table 1.
  • the solution viscosity was determined by the following method. A sample was fully dissolved with 25 %w toluene, and the viscosity found with a B type viscometer (ex Tokyo gauges) at 25 ° C was taken as the solution viscosity.
  • Comparative Experiments B and C had solution viscosities lying within the prescribed range, but as the number of branches was not at least 5 their shrinkage percentages were high. In Comparative Experiment D the solution viscosity was above the prescribed range, but as the number of branches was not at least 5, its shrinkage percentage was extremely high.
  • the shrinkage after moulding of the block copolymer composition of the present invention is very little, as will be seen from the results given in Table 2. Moreover, it has excellent mechanical strength and abrasion properties.
  • a block copolymer in which the number of branches involved in the coupling reaction and the solution viscosity are as specified in the present invention have unprecedentedly good properties and therefore they are materials of high practical value for the industry.

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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)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

La composition de copolymère bloc décrite contient au moins 30 % en poids d'un copolymère bloc de diène conjugué à un composé de vinyle aromatique, ayant une teneur en composé de vinyle aromatique de 10 à 90 % en poids et représenté par la formule (A-B)nX, dans laquelle "A" représente le bloc du composé de vinyle aromatique, "B" représente le bloc de diène conjugué, n représente un nombre entier supérieur ou égal à 5 et X représente un résidu d'agent de couplage. Un tel copolymère bloc permet de produire une solution, dans du toluène, de 25 % en poids dudit copolymère, dont la viscosité à 25°C est de 50 à 1000 cP.
PCT/EP1988/000037 1985-06-18 1988-01-19 Composition de copolymere bloc et procede de preparation d'une telle composition WO1989006660A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
JP60132687A JPS61291610A (ja) 1985-06-18 1985-06-18 ブロツク共重合体およびその組成物
EP88901246A EP0349536A1 (fr) 1988-01-19 1988-01-19 Composition de copolymere bloc et procede de preparation d'une telle composition
PCT/EP1988/000037 WO1989006660A1 (fr) 1988-01-19 1988-01-19 Composition de copolymere bloc et procede de preparation d'une telle composition
AU12221/88A AU605553B2 (en) 1988-01-19 1988-01-19 Block copolymer composition and process for the preparation thereof
BR888807423A BR8807423A (pt) 1988-01-19 1988-01-19 Composicao de copolimero em bloco,processo para sua preparacao e artigos que a contem
EP88200103A EP0324992A1 (fr) 1985-06-18 1988-01-19 Composition de polymère bloc et sa méthode de préparation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP1988/000037 WO1989006660A1 (fr) 1988-01-19 1988-01-19 Composition de copolymere bloc et procede de preparation d'une telle composition

Publications (1)

Publication Number Publication Date
WO1989006660A1 true WO1989006660A1 (fr) 1989-07-27

Family

ID=8165232

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1988/000037 WO1989006660A1 (fr) 1985-06-18 1988-01-19 Composition de copolymere bloc et procede de preparation d'une telle composition

Country Status (4)

Country Link
EP (1) EP0349536A1 (fr)
AU (1) AU605553B2 (fr)
BR (1) BR8807423A (fr)
WO (1) WO1989006660A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107987741A (zh) * 2017-12-28 2018-05-04 湖北航聚科技有限公司 一种橡胶胶粘剂

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0394229A1 (fr) * 1988-03-24 1990-10-31 Shell Internationale Researchmaatschappij B.V. Composition de copolymere bloc
DE3833759A1 (de) * 1988-10-05 1990-04-12 Huels Chemische Werke Ag Ungesaettigte, elastomere, asymmetrisch gekuppelte blockcopolymere, ein zweitopfverfahren zu ihrer herstellung und ihre verwendung zur herstellung von reifenbauteilen

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1534150A (fr) * 1967-08-10 1968-07-26 Basf Ag Procédé de fabrication de copolymères-bloc styrène-dioléfines
FR2201301A1 (fr) * 1972-10-02 1974-04-26 Goodyear Tire & Rubber
US4405754A (en) * 1982-01-13 1983-09-20 Phillips Petroleum Company Haze-free, clear, impact-resistant resinous polymers
US4408006A (en) * 1979-09-07 1983-10-04 Atlantic Richfield Company Star elastomers in footwear compounds

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1534140A (fr) * 1967-07-31 1968-07-26 Aeg Elotherm Gmbh Dispositif de chauffage par induction pour la trempe entièrement automatique par induction des pièces d'oeuvre de longueurs différentes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1534150A (fr) * 1967-08-10 1968-07-26 Basf Ag Procédé de fabrication de copolymères-bloc styrène-dioléfines
FR2201301A1 (fr) * 1972-10-02 1974-04-26 Goodyear Tire & Rubber
US4408006A (en) * 1979-09-07 1983-10-04 Atlantic Richfield Company Star elastomers in footwear compounds
US4405754A (en) * 1982-01-13 1983-09-20 Phillips Petroleum Company Haze-free, clear, impact-resistant resinous polymers

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107987741A (zh) * 2017-12-28 2018-05-04 湖北航聚科技有限公司 一种橡胶胶粘剂

Also Published As

Publication number Publication date
AU605553B2 (en) 1991-01-17
EP0349536A1 (fr) 1990-01-10
AU1222188A (en) 1989-08-11
BR8807423A (pt) 1990-05-22

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