WO1998050462A1 - Composition de caoutchouc a base de noir de carbone ayant de la silice fixee a sa surface et de polymere dienique fonctionnalise ou modifie par des fonctions silanols - Google Patents

Composition de caoutchouc a base de noir de carbone ayant de la silice fixee a sa surface et de polymere dienique fonctionnalise ou modifie par des fonctions silanols Download PDF

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Publication number
WO1998050462A1
WO1998050462A1 PCT/EP1998/002652 EP9802652W WO9850462A1 WO 1998050462 A1 WO1998050462 A1 WO 1998050462A1 EP 9802652 W EP9802652 W EP 9802652W WO 9850462 A1 WO9850462 A1 WO 9850462A1
Authority
WO
WIPO (PCT)
Prior art keywords
silanol
diene polymer
carbon black
silica
chain
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/EP1998/002652
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English (en)
French (fr)
Inventor
Gérard Labauze
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Compagnie Generale des Etablissements Michelin SCA
Original Assignee
Compagnie Generale des Etablissements Michelin SCA
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 Compagnie Generale des Etablissements Michelin SCA filed Critical Compagnie Generale des Etablissements Michelin SCA
Publication of WO1998050462A1 publication Critical patent/WO1998050462A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08CTREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00Chemical modification of rubber
    • C08C19/30Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
    • C08C19/42Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
    • C08C19/44Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups of polymers containing metal atoms exclusively at one or both ends of the skeleton
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B60VEHICLES IN GENERAL
    • B60CVEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016Compositions of the tread
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/02Ingredients treated with inorganic substances
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02TCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00Road transport of goods or passengers
    • Y02T10/80Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86Optimisation of rolling resistance, e.g. weight reduction 

Definitions

  • the present invention relates to a rubber composition which can be used in particular for the manufacture of tire covers, having improved hysteretic and physical properties in the vulcanized state, comprising a diene polymer functionalized or modified with silanol functions and as filler reinforcing, carbon black having silica attached to its surface.
  • compositions containing silica were noted with the publication of patent application EP-A-0 501 227 which discloses a sulfur-vulcanizable rubber composition obtained by the thermomechanical work of a copolymer of conjugated diene and d 'a vinyl aromatic compound and the use of a particular precipitated silica obtained according to the process detailed in patent application EP-A-0 157 703.
  • This composition which presents an excellent compromise between several contradictory properties, allows the manufacture of tires having a tread loaded with particular silica.
  • EP-A-0-556 890 in the form of an addition of specific conductive polymers to the rubber composition constituting the tread of the tires.
  • the invention relates to a vulcanizable rubber composition
  • a vulcanizable rubber composition comprising at least one functionalized or modified diene polymer, carbon black having silica attached to its surface as reinforcing filler and the other usual constituents of such compositions, characterized in that the diene polymer is a functionalized diene polymer carrying at the chain end a silanol function or a polysiloxane block having a silanol end or a diene polymer modified along of its chain by silanol functions.
  • R - R, and R 2 identical or different, represent an alkyl group having from 1 to 8 carbon atoms
  • die polymers capable of being used in the composition in accordance with the invention means any homopolymer obtained by polymerization of a conjugated diene monomer having from 4 to 12 carbon atoms, any copolymer obtained by copolymerization of one or several dienes conjugated together or with one or more vinyl aromatic compounds having from 8 to 20 carbon atoms.
  • conjugated dienes 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di (C 1 -C 5 alkyl) -1,3-butadiene such as, for example, are suitable.
  • Suitable vinyl aromatic compounds include styrene, ortho-, meta, para-methylstyrene, the commercial mixture "vinyltoluene", para-tertiobutylstyrene, methoxystyrenes, vinyl mesitylene, divinylbenzene, vinylnaphthalene, etc.
  • the copolymers can contain between 99% and 20% by weight of diene units and from 1% to
  • the functionalized diene polymers carrying at the chain end a silanol function or a polysiloxane block having a silanol end, or modified along the chain by silanol functions can have any microstructure which is a function of the polymerization conditions used.
  • the polymers can be block, statistical, block, microblock, etc. and can be prepared in dispersion or in solution. When it is an anionic polymerization, the microstructure of these polymers can be determined by the presence or not of a modifying and / or randomizing agent and the quantities of modifying and / or randomizing agent employed.
  • polybutadienes are suitable and in particular those having a content of 1,2 units between 4% and 80%, polyisoprenes, butadiene-styrene copolymers and in particular those having a styrene content between 4 and 50 % by weight and more particularly between 20% and 40% by weight, a content of -1,2 bonds of the butadiene part of between 4% and 65%, a content of trans-1,4 bonds between 30% and 80 %, butadiene-isoprene copolymers and in particular those having an isoprene content of between 5 and 90% by weight and a glass transition temperature (Tg) of - 40 ° C to -80 ° C, isoprene-styrene copolymers and in particular those having a styrene content of between 5 and 50% by weight and a Tg of between -25 ° C and - 50 ° C.
  • Tg glass transition temperature
  • butadiene-styrene-isoprene copolymers those having a styrene content of between 5 and 50% by weight and more particularly of between 10% and 40% and of isoprene of between 15% and 60% by weight and more are suitable.
  • the functionalized functionalized diene polymers carrying at the chain end a silanol function or a polysiloxane block having a silanol end used in the invention can be obtained by analogy by various methods.
  • a first way consists in react as described in Journal of Polymer Science, Part A, Vol. 3, p. 93-103 (1965) the living diene polymer with an organosilane functionalizing agent, preferably at the outlet of the polymerization reactor and at an identical or different temperature and preferably close to the polymerization temperature, to form a diene polymer having at the end to chain a halosilane function and to submit it, as described in the manual “Chemistry and Technology of Silicones, Académie Press, New York, NY (1968) p.
  • R - R ] and R 2 which are identical or different, represent an alkyl group having from 1 to 8 carbon atoms,
  • dihalosilane compounds mention may be made of dichlorodimethylsilane, dichlorodiethylsilane, dichlorodiphenylsilane, dichlorophenylmethylsilane, dichlorovinylmethylsilane.
  • silica As nonlimiting examples of such silica, mention may be made of Perkasil KS 430 silica from AKZO, Zeosil 1165 MP and 85 MP silica from Rhône-Poulenc, HI-Sil 2000 silica from PPG, Zeopol silicas 8741 or 8745 from Huber.
  • composition Cl comprising SBR-C (stopped methanol) at low (G " max 23 "; tg ⁇ max 23 ° ) and at high (PH 60 ° C) deformation without degrading the other properties compared to mixing with the
  • composition Al (with SBR-A functionalized with silanol) comprising the black ECOBLACK CRX2000 exhibits a very large reduction in hysteresis (at low and high deformation) of the order of 30% compared to that obtained from the composition B2 based on carbon black without damaging the other properties.
  • composition A3 using SBR-A (functionalized silanol) has a low hysteresis level (G " max 23 ; tg ⁇ max 23 ° ) and f ° ⁇ e (PH 60 ° C) very low deformation compared to the two other compositions which also include carbon black having silica fixed to its surface as reinforcing filler, without there being any degradation of the other properties.
  • any functionalized polymer suitable for carbon black does not make it possible to obtain an improvement in hysteretic and physical properties when it is used in a composition based on black silica treated (here l 'ECOBLACK CRX2000), no more than the transposition of any polymer functionalized specifically for silica to a composition comprising black treated silica as reinforcing filler.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Tires In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
PCT/EP1998/002652 1997-05-07 1998-05-05 Composition de caoutchouc a base de noir de carbone ayant de la silice fixee a sa surface et de polymere dienique fonctionnalise ou modifie par des fonctions silanols Ceased WO1998050462A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR97/05887 1997-05-07
FR9705887A FR2763074B1 (fr) 1997-05-07 1997-05-07 Composition de caoutchouc a base de noir de carbone ayant de la silice fixee a sa surface et de polymere dyenique fonctionalise ou modifie par des fonctions silanols

Publications (1)

Publication Number Publication Date
WO1998050462A1 true WO1998050462A1 (fr) 1998-11-12

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1998/002652 Ceased WO1998050462A1 (fr) 1997-05-07 1998-05-05 Composition de caoutchouc a base de noir de carbone ayant de la silice fixee a sa surface et de polymere dienique fonctionnalise ou modifie par des fonctions silanols

Country Status (12)

Country Link
US (1) US6071995A (https=)
EP (1) EP0877047B1 (https=)
JP (1) JP4394181B2 (https=)
CN (1) CN1202164C (https=)
AT (1) ATE225380T1 (https=)
AU (1) AU733790B2 (https=)
BR (1) BR9801587A (https=)
CA (1) CA2235095A1 (https=)
DE (1) DE69808367T2 (https=)
ES (1) ES2184166T3 (https=)
FR (1) FR2763074B1 (https=)
WO (1) WO1998050462A1 (https=)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011042507A1 (fr) 2009-10-08 2011-04-14 Societe De Technologie Michelin Elastomere dienique fonctionnalise et composition de caoutchouc le contenant.
CN112094434A (zh) * 2020-08-24 2020-12-18 杭州师范大学 一种含硅烷氧基硼硅氧烷改性白炭黑的制备方法及其应用

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JP4105328B2 (ja) * 1999-04-09 2008-06-25 住友ゴム工業株式会社 空気入りタイヤ
US6255404B1 (en) * 1999-07-26 2001-07-03 Bridgestone Corporation Method to control increase in viscosity during aging of siloxane modified polymers
FR2802542A1 (fr) 1999-12-20 2001-06-22 Michelin Soc Tech Composition de caoutchouc vulcanisable pour la fabrication d'un pneumatique et pneumatique dont la bande de roulement comprend une telle composition
FR2804688B1 (fr) * 2000-02-07 2006-08-11 Michelin Soc Tech Utilisation d'une composition de caoutchouc pour retarder lors du roulage l'apparition de l'usure irreguliere sur une bande de roulement de pneumatique destinee a porter de lourdes charges
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KR100806662B1 (ko) 2000-05-22 2008-02-28 소시에떼 드 테크놀로지 미쉐린 타이어 주행 트레드용 조성물 및 이의 제조방법
WO2001092402A1 (fr) 2000-05-26 2001-12-06 Societe De Technologie Michelin Composition de caoutchouc utilisable comme bande de roulement de pneumatique
KR100403089B1 (ko) * 2001-01-03 2003-10-30 금호석유화학 주식회사 말단변성 디엔계 공중합체의 제조방법
US6569942B2 (en) * 2001-03-14 2003-05-27 The Goodyear Tire & Rubber Company Rubber compositions containing silicon coupled oligomers
WO2003046066A1 (fr) 2001-11-26 2003-06-05 Societe De Technologie Michelin Composition de caoutchouc pour bande de roulement de pneu et son procede d'obtention
US20040095244A1 (en) * 2002-05-10 2004-05-20 Kevin Conwell Tire identification label and tire label film with integrated barrier
US7241842B2 (en) 2002-05-31 2007-07-10 Zeon Corporation Conjugated diene rubber, process for producing the same, and rubber composition
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US6998448B2 (en) * 2002-09-16 2006-02-14 The Goodyear Tire & Rubber Company Tire with tread of CIS 1,4-polybutadiene rich rubber composition which contains a functional styrene/butadiene elastomer, silica and coupling agent
US7163975B2 (en) * 2002-09-17 2007-01-16 The Goodyear Tire & Rubber Company Tire with compound of rubber composition comprised of silanol and/or siloxy functionalized elastomer and silica
US7071251B2 (en) * 2002-09-17 2006-07-04 The Goodyear Tire & Rubber Company Tire with component comprised of rubber composite of styrene/butadiene elastomer containing pendent silanol and/or siloxy groups
US7137423B2 (en) * 2003-06-06 2006-11-21 The Goodyear Tire & Rubber Company Tire with component comprised of amine functionalized styrene/diene copolymer elastomer, silanol functionalized carbon black and coupling agent
JP4670639B2 (ja) 2003-09-01 2011-04-13 日本ゼオン株式会社 共役ジエン系ゴム組成物、その製造方法およびゴム架橋物
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JP5547058B2 (ja) * 2008-03-10 2014-07-09 株式会社ブリヂストン 変性共役ジエン(共)重合体の製造方法、変性共役ジエン(共)重合体、並びにそれを用いたゴム組成物及びタイヤ
JP5473360B2 (ja) * 2008-03-10 2014-04-16 株式会社ブリヂストン ゴム組成物及びそれを用いたタイヤ
DE102009023915A1 (de) * 2009-05-27 2010-12-02 Rhein-Chemie Rheinau Gmbh Mischungen aus funktionalisierten Dienkautschuken mit Trimethylolpropan und Fettsäure, ein Verfahren zu deren Herstellung und deren Verwendung
JP5663146B2 (ja) * 2009-05-29 2015-02-04 株式会社ブリヂストン 変性共役ジエン系重合体の製造方法、変性共役ジエン系重合体、ゴム組成物、空気入りタイヤ
IN2012DN02519A (https=) * 2009-08-27 2015-08-28 Columbian Chem
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EP3705538B1 (en) * 2010-12-14 2021-04-28 Cabot Corporation Filler-polymer compositions comprising silicone polymer and a two-phase filler having a silica phase and a carbon phase
CN103282409B (zh) 2010-12-31 2015-08-05 株式会社普利司通 偶联的聚合物及其制备方法
US8680210B2 (en) 2011-05-02 2014-03-25 Bridgestone Corporation Method for making functionalized polymer
US8580886B2 (en) 2011-09-20 2013-11-12 Dow Corning Corporation Method for the preparation and use of bis (alkoxysilylorgano)-dicarboxylates
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JP5996961B2 (ja) * 2012-08-03 2016-09-21 住友ゴム工業株式会社 タイヤ用ゴム組成物及び空気入りタイヤ
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FR3021971B1 (fr) 2014-06-05 2016-06-03 Michelin & Cie Pneumatique a faible resistance au roulement
FR3021972B1 (fr) 2014-06-05 2016-06-03 Michelin & Cie Pneumatique a faible resistance au roulement
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FR3036115B1 (fr) * 2015-05-11 2017-05-19 Michelin & Cie Composition de caoutchouc
FR3061187B1 (fr) 2016-12-22 2019-02-01 Compagnie Generale Des Etablissements Michelin Composition de caoutchouc avec une bonne dispersion de quantites elevees de charge inorganique renforcante
CN108250327B (zh) * 2016-12-28 2020-04-14 北京化工大学 一种链端含硅和羟基的官能化聚合物及其制备方法和支化聚合物
EP3647351B1 (en) * 2017-07-19 2025-07-02 Sumitomo Rubber Industries, Ltd. Rubber composition for tread, and pneumatic tire
WO2019122604A1 (fr) 2017-12-19 2019-06-27 Compagnie Generale Des Etablissements Michelin Bande de roulement de pneumatique dont le systeme de reticulation est a base de peroxyde organique
US20210087370A1 (en) 2017-12-19 2021-03-25 Compagnie Generale Des Etablissements Michelin Tire tread, the crosslinking system of which is based on organic peroxide
US20210079200A1 (en) 2017-12-19 2021-03-18 Compagnie Generale Des Etablissements Michelin Tire tread, the crosslinking system of which is based on organic peroxide
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FR3081162B1 (fr) 2018-05-17 2020-04-24 Compagnie Generale Des Etablissements Michelin Bande de roulement de pneumatique dont le systeme de reticulation est a base de peroxyde organique
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011042507A1 (fr) 2009-10-08 2011-04-14 Societe De Technologie Michelin Elastomere dienique fonctionnalise et composition de caoutchouc le contenant.
US9670291B2 (en) 2009-10-08 2017-06-06 Compagnie Generale Des Etablissements Michelin Functionalized diene elastomer, and rubber composition containing same
CN112094434A (zh) * 2020-08-24 2020-12-18 杭州师范大学 一种含硅烷氧基硼硅氧烷改性白炭黑的制备方法及其应用
CN112094434B (zh) * 2020-08-24 2022-05-27 杭州师范大学 一种含硅烷氧基硼硅氧烷改性白炭黑的制备方法及其应用

Also Published As

Publication number Publication date
CA2235095A1 (fr) 1998-11-07
DE69808367T2 (de) 2003-06-12
JPH10316800A (ja) 1998-12-02
DE69808367D1 (de) 2002-11-07
AU733790B2 (en) 2001-05-24
ES2184166T3 (es) 2003-04-01
CN1202164C (zh) 2005-05-18
BR9801587A (pt) 1999-07-06
EP0877047B1 (fr) 2002-10-02
ATE225380T1 (de) 2002-10-15
AU6477098A (en) 1998-11-12
EP0877047A1 (fr) 1998-11-11
FR2763074A1 (fr) 1998-11-13
JP4394181B2 (ja) 2010-01-06
US6071995A (en) 2000-06-06
CN1226908A (zh) 1999-08-25
FR2763074B1 (fr) 1999-06-25

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