EP1183305A1 - Caoutchoucs dieniques renfermant des groupes hydroxyle - Google Patents

Caoutchoucs dieniques renfermant des groupes hydroxyle

Info

Publication number
EP1183305A1
EP1183305A1 EP00920733A EP00920733A EP1183305A1 EP 1183305 A1 EP1183305 A1 EP 1183305A1 EP 00920733 A EP00920733 A EP 00920733A EP 00920733 A EP00920733 A EP 00920733A EP 1183305 A1 EP1183305 A1 EP 1183305A1
Authority
EP
European Patent Office
Prior art keywords
rubber
hydroxyl
rubbers
weight
rubber mixtures
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.)
Withdrawn
Application number
EP00920733A
Other languages
German (de)
English (en)
Inventor
Thomas Scholl
Jürgen Trimbach
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.)
Bayer AG
Original Assignee
Bayer AG
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 Bayer AG filed Critical Bayer AG
Publication of EP1183305A1 publication Critical patent/EP1183305A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016—Compositions of the tread
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0025—Compositions of the sidewalls
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/20—Incorporating sulfur atoms into the molecule
    • 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

Definitions

  • the present invention relates to rubber mixtures containing diene rubbers with a primary hydroxyl group content of 0.1 to 2% by weight and one
  • the rubber mixtures according to the invention are suitable for the production of highly reinforced, abrasion-resistant moldings, in particular for the production of tires which have a particularly high wet slip resistance.
  • Solution rubbers containing double bonds such as solution polybutadiene and solution styrene / butadiene rubbers, have advantages over the corresponding emulsion rubbers in the production of low-rolling resistance tire treads.
  • the advantages include in the controllability of the vinyl content and the associated glass temperature, the cis content and the molecular branching. In practical use, this results in particular advantages in relation to abrasion, wet skid resistance and rolling resistance of the tire.
  • US Pat. No. 5,227,425 describes the production of tire treads from a solution SBR rubber and silica. Numerous end group modification methods have been developed to further improve the properties, e.g.
  • solution-diene rubbers such as solution polybutadiene and polyisoprene
  • Rubbers are also described in DE-OS 2,653,144. They own rubbers however, a significantly higher content of hydroxyl groups combined with significantly higher glass transition temperatures.
  • Emulsion and solution rubbers containing hydroxyl groups are also described in EP-806.452 A1, the hydroxyl contents described here for solution rubbers being due to the process in a significantly lower range (0.009 to 0.061%) and, in the case of the emulsion rubbers described, the glass transition temperatures being substantially higher due to the styrene content (> -40 ° C).
  • the present invention therefore relates to rubber mixtures comprising one or more hydroxyl-containing rubbers composed of diolefins, characterized in that the or the hydroxyl-containing rubbers in the Contain range of 0.1 to 2 wt .-% bound primary hydroxyl groups and have a glass transition temperature between -120 to -50 ° C and fillers.
  • Another object of the invention is the use of said rubber mixtures for the production of rubber vulcanizates, in particular tire treads filled with silica with particularly high abrasion resistance, particularly high wet skid resistance and low rolling resistance.
  • Suitable diolefins are in particular 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, l-phenyl-1,3-butadiene and 1,3-hexadiene.
  • 1.3 butadiene and isoprene are particularly preferred.
  • the rubbers according to the invention for the rubber mixtures according to the invention are preferably produced by polymerization using coordination catalysts in the presence of a solvent or anionic solution polymerization.
  • coordination catalysts are understood to mean Ziegler-Natta catalysts, coordination catalysts and monometallic catalyst systems.
  • Preferred coordination catalysts are those based on Ni, Co, Ti or Nd.
  • Catalysts for anionic solution polymerization are based on alkali or alkaline earth metals, e.g. n-butyllithium.
  • Methods for introducing the primary hydroxyl groups are, for example, the addition of primary hydroxyl-containing mercaptans, addition of formaldehyde, reaction with carbon monoxide and subsequent hydrogenation, hydroboration and subsequent oxidative hydrolysis of the borane compound.
  • the hydroxyl groups are preferably introduced by the addition of hydroxyl mercaptans of the general formula (1) and / or hydroxyl group-containing mercaptocarboxylic esters of the general formula (2).
  • the reaction is preferably carried out in solution, if appropriate in the presence of radical initiators.
  • R 1 represents a linear, branched or cyclic C 1 -C 6 -alkylene group which can optionally be substituted by up to 6 further hydroxyl groups or can be interrupted by nitrogen, oxygen or sulfur atoms,
  • R 2 is hydrogen, or a C j -Co alkyl group
  • R 3 represents a linear, branched or cyclic C2-C36 alkylene group which can optionally be substituted by up to 6 further hydroxyl groups or can be interrupted by nitrogen, oxygen or sulfur atoms,
  • OH represents a primary hydroxyl group
  • n is an integer from 1 to 5
  • n is an integer from 1 to 2.
  • C C g -alkylene is understood to mean all linear, cyclic or branched alkylene radicals with 1 to 36 C atoms known to the person skilled in the art, such as methylene,
  • Preferred hydroxyl mercaptans are mercaptoethanol, 1-mercapto-3-propanol, 1-mercapto-4-butanol, 3-mercapto-1, 2-propanediol (thioglycerol), ⁇ -mercapto- ⁇ -hydroxy-oligoethylene oxides, e.g. ⁇ -mercapto- ⁇ -hydroxy-octaethylene glycol or the corresponding ethylene oxide / propylene oxide mixed polyether.
  • Mercapoethanol, thioglycerol and ⁇ -mercapto- ⁇ -hydroxy-oligoethylene oxides are particularly preferred.
  • Preferred hydroxyl group-containing mercaptocarboxylic acid esters are esters of mercaptoacetic acid, mercaptopropionic acid and mercaptobutyric acid with ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, octaethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, methyl terepropylene glycol, methyl terepropylene glycol, and methyl tetra propylene glycol.
  • the corresponding ones are particularly preferred
  • Esters of mercaptoacetic acid and 3-mercaptopropionic acid are esters of mercaptoacetic acid and 3-mercaptopropionic acid.
  • Suitable radical initiators for the attachment of the hydroxyl mercaptans to the hydroxyl-containing rubbers are e.g. Azo initiators, such as azobisisobutyronitrile, azobiscyclohexanenitrile and peroxides, such as dilauroyl peroxide, benzpinakolsilyl ether or photoinitiators in the presence of UV or visible light.
  • Azo initiators such as azobisisobutyronitrile, azobiscyclohexanenitrile and peroxides, such as dilauroyl peroxide, benzpinakolsilyl ether or photoinitiators in the presence of UV or visible light.
  • Diacyl peroxides in particular dilauroyl peroxide, didecanoyl peroxide, di- (3,3,5-trimethylhexanoyl) peroxide, disuccinoyl peroxide, dibenzoyl peroxide and perketals, such as II-di (tert-butylperoxy) -3,3,5-trimethyl- cyclohexane, ll-di (tert-butylperoxy) cyclohexane and 1.1-di (tert-butylperoxy) butane.
  • Diacyl peroxides in particular dilauroyl peroxide, didecanoyl peroxide, di- (3,3,5-trimethylhexanoyl) peroxide, disuccinoyl peroxide, dibenzoyl peroxide and perketals, such as II-di (tert-butylperoxy) -3,3,5-trimethyl- cyclohexane,
  • radical initiators are 0.5 to 20% by weight, based on hydroxyl mercaptan.
  • the average molecular weights of the hydroxyl-containing rubbers are between 50,000 and 2,000,000, preferably between 100,000 and 1,000,000.
  • the Mooney viscosity ML 1 + 4 of the copolymers is between 10 to 200, preferably 30 to 150, measured at 100 ° C.
  • the content of polymerized 1,2-butadiene units (“vinyl content”) is between 0 and 60% by weight, preferably 1 to 50% by weight.
  • the glass transition temperature is between -120 to -50 ° C, preferably -120 to -70 ° C.
  • the glass temperature can be determined using known methods e.g. can be determined by means of DSC (differential scanning calorimetry, heating rate 20 K / min.).
  • the cis-1.4 content of polymerized dienes is between 10 and 100%, preferably between 30 and 99%, particularly preferably between 90 and 99%.
  • the content of primary hydroxyl groups is between 0.1 to 2% by weight, preferably in the range from 0.1 to 1% by weight, particularly preferably in the range from 0.1 to 0.75% by weight, based on rubber .
  • the hydroxyl group content can be determined by known methods, e.g. by spectroscopy, tritrimetry, elemental analysis or by
  • OH number hydroxyl number
  • the rubbers according to the invention with a glass transition temperature of -120 to -50 ° C. and 0.1 to 2% by weight of hydroxyl groups can be used alone, in a blend with aromatic or aliphatic oils or in a mixture with other rubbers.
  • synthetic rubbers are also suitable as additional rubbers for the production of rubber vulcanizates.
  • Preferred synthetic rubbers are for example from W. Hofmann, rubber technology, Gentner Verlag, Stuttgart 1980 and I. Franta, Elastomers and Rubber Compounding Materials, Elsevier, Amsterdam 1989. They include, among others
  • NBR - butadiene / acrylonitrile copolymers with acrylonitrile contents of 5 to 60, preferably 10 to 40% by weight
  • Very particularly preferred rubber mixtures according to the invention contain, in addition to the hydroxyl-containing rubber with a glass transition temperature between -120 ° to -50 ° C, additional rubbers selected from the series natural rubber,
  • the amount of these additional rubbers is usually in the range from 0.5 to 95, preferably 40 to 90,% by weight, based on the total amount of rubber in the rubber mixture.
  • the amount of additionally added rubbers depends again on the particular intended use of the rubber mixtures according to the invention.
  • the rubber mixtures according to the invention contain 5 to 300 parts by weight of an active or inactive filler, such as, for example
  • Silicates or flame hydrolysis of silicon halides with specific surface areas of 5 to 1000, preferably 20 to 400 m 2 / g (BET surface area) and with primary particle sizes of 10 to 400 nm.
  • the silicas can optionally also be mixed oxides with other metal oxides, such as Al, Mg, Ca, Ba, Zn, Zr, Ti oxides are present,
  • synthetic silicates such as aluminum silicate, alkaline earth metal silicate, such as magnesium silicate or calcium silicate, with BET surface areas of 20 to 400 m 2 / g and primary particle diameters of 10 to 400 nm,
  • silicates such as kaolin and other naturally occurring silica
  • Metal oxides such as zinc oxide, calcium oxide, magnesium oxide, aluminum oxide,
  • Metal carbonates such as magnesium carbonate, calcium carbonate, zinc carbonate,
  • Metal hydroxides e.g. Aluminum hydroxide, magnesium hydroxide,
  • the carbon blacks used here are produced using the flame black, furnace or gas black process and have BET surface areas of 20 to 200 m 2 / g, such as SAF, ISAF, HAF, FEF or GPF carbon blacks.
  • Rubber gels especially those based on polybutadiene, butadiene / styrene copolymers, butadiene / acrylonitrile copolymers and polychloroprene.
  • the fillers mentioned can be used alone or in a mixture.
  • the rubber mixtures contain, as fillers, a mixture of light fillers, such as highly disperse silicas, and carbon blacks, the mixing ratio of light fillers to carbon blacks being from 0.05 to 20, preferably from 0.1 to 10.
  • the fillers are preferably added as solids or as a slurry in water or a solvent to the solution of the hydroxyl-containing rubbers polymerized in solution.
  • the rubber solution can be prepared beforehand, but the solution originating from the polymerization is preferably used directly.
  • the solvent is then removed thermally or preferably with the aid of steam. The conditions of this stripping process can easily be determined by preliminary tests.
  • the fillers for solid hydroxyl groups are also preferred
  • Rubber or a mixture of rubbers and added in a known manner, e.g. with a kneader, mixed in.
  • the rubber mixtures according to the invention optionally also contain crosslinking agents.
  • Sulfur or peroxides can be used as crosslinkers
  • the rubber mixtures according to the invention can contain further auxiliary rubber products, such as reaction accelerators, anti-aging agents, heat stabilizers, light stabilizers, anti-ozone agents, processing aids, plasticizers, tackifiers, blowing agents, dyes, pigments, waxes, extenders, organic acids, retarders, metal oxides and the like Activators such as triethanolamine, polyethylene glycol, hexanetriol etc. which are known to the rubber industry.
  • auxiliary rubber products such as reaction accelerators, anti-aging agents, heat stabilizers, light stabilizers, anti-ozone agents, processing aids, plasticizers, tackifiers, blowing agents, dyes, pigments, waxes, extenders, organic acids, retarders, metal oxides and the like
  • Activators such as triethanolamine, polyethylene glycol, hexanetriol etc. which are known to the rubber industry.
  • Preferred filler activators are sulfur-containing silyl ethers, in particular bis (trialkoxisilyl-alkyl) polysulfides, as described in DE 2,141,159 and DE-AS 2,255,577, oligomeric and / or polymeric sulfur-containing silyl ethers of DE-OS 4,435,311 and EP-A 670.347, mercapatoalkyltrialkoxisilane, in particular mercaptopropyltriethoxisilane and thiocyanatoalkylsilyl ether, such as, for example described in DE-OS 19,544,469.
  • the rubber auxiliaries are used in customary amounts, which depend, among other things, on the intended use. Common amounts are e.g. Amounts from 0.1 to 50 wt .-%, based on rubber.
  • the rubber mixtures according to the invention are outstandingly suitable for the production of moldings of all kinds.
  • Non-limiting examples of these shaped bodies are O-rings, profiles, seals,
  • Tires and tire treads are particularly preferred.
  • a solution of 500 g of solution polybutadiene rubber Buna CB 65 (Bayer AG, Li type, cis-l, 4 content approx. 40%) in 4 1 cyclohexane is at 70 ° C with 12.5 g 1-mer - capto-2-ethanol and 1 g of dilauroyl peroxide were added. The mixture was then stirred at 80 ° C for 8 hours. At this point, 39% of the mercaptoethanol had reacted. Then 2.5 g of the antioxidant Vulkanox 4020 (Bayer AG) were added and the solvent was distilled off with steam (100-110 ° C.). After drying at 70 ° C. in vacuo, 508 g of a colorless rubber with an OH number of 7, an OH content of 0.21% by weight and a cis-1, 4 content of 40% were obtained. Glass temperature: -90 ° C
  • a solution of 500 g of solution polybutadiene rubber Buna VI 47-0 (Bayer AG, Vinyl-BR, content of 1,2-bonded butadiene (“vinyl content”) approx. 47%) in 4 1 cyclohexane is at 12 ° C. with 70 , 5 g of 1-mercapto-2-ethanol and 1 g of dilauroyl peroxide were added, followed by stirring for 4 hours at 80 ° C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Tires In General (AREA)

Abstract

L'invention concerne des mélanges de caoutchouc contenant des caoutchoucs diéniques d'une teneur en groupes hydroxyle primaires de 0,1 à 2 % en poids et d'une température de transition vitreuse de -120 à -50 DEG C, ainsi que leurs mélanges avec des charges, éventuellement, avec d'autres caoutchoucs et adjuvants de caoutchouc, et les vulcanisats obtenus à partir de ces produits. Les mélanges de caoutchouc selon l'invention sont utilisés pour la fabrication de pièces profilées hautement renforcées, résistant à l'usure, en particulier pour la fabrication de pneumatiques présentant d'excellentes propriétés d'antidérapage dans les conditions humides.
EP00920733A 1999-05-06 2000-04-20 Caoutchoucs dieniques renfermant des groupes hydroxyle Withdrawn EP1183305A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19920894A DE19920894A1 (de) 1999-05-06 1999-05-06 Hydroxylgruppenhaltige Dienkautschuke
DE19920894 1999-05-06
PCT/EP2000/003617 WO2000068311A1 (fr) 1999-05-06 2000-04-20 Caoutchoucs dieniques renfermant des groupes hydroxyle

Publications (1)

Publication Number Publication Date
EP1183305A1 true EP1183305A1 (fr) 2002-03-06

Family

ID=7907190

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00920733A Withdrawn EP1183305A1 (fr) 1999-05-06 2000-04-20 Caoutchoucs dieniques renfermant des groupes hydroxyle

Country Status (10)

Country Link
US (1) US6696523B1 (fr)
EP (1) EP1183305A1 (fr)
JP (1) JP2002544312A (fr)
KR (1) KR20020010635A (fr)
AU (1) AU4119800A (fr)
BR (1) BR0010333A (fr)
CA (1) CA2372507A1 (fr)
DE (1) DE19920894A1 (fr)
MX (1) MXPA01011278A (fr)
WO (1) WO2000068311A1 (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4817406B2 (ja) * 2001-03-14 2011-11-16 学校法人日本大学 プロピレン−ビニルアルコール共重合体及びその製造方法
JP4071950B2 (ja) * 2001-10-04 2008-04-02 住友ゴム工業株式会社 サイドウォール用ゴム組成物およびそれを用いた空気入りタイヤ
KR100445829B1 (ko) * 2001-11-26 2004-08-30 한국타이어 주식회사 제동성능이 향상된 타이어 트레드용 고무 조성물
JP4602718B2 (ja) * 2004-08-30 2010-12-22 東洋ゴム工業株式会社 タイヤサイドウォール用ゴム組成物および空気入りタイヤ
US7371493B2 (en) * 2005-03-11 2008-05-13 Samsung Electronics Co., Ltd. Charge transport materials having a 1,3,6,8-tetraoxo-1,3,6,8-tetrahydrobenzo[lmn][3,8]phenanthroline-2,7-diyl group
RU2459844C2 (ru) * 2006-12-19 2012-08-27 Стирон Юроп Гмбх Эластомерные полимеры, модифицированные сульфидом
DE102007044175A1 (de) * 2007-09-15 2009-03-19 Lanxess Deutschland Gmbh Funktionalisierte Hochvinyl-Dienkautschuke
JP2010018706A (ja) * 2008-07-10 2010-01-28 Toyo Tire & Rubber Co Ltd ゴム組成物の製造方法
JP5323408B2 (ja) * 2008-07-10 2013-10-23 東洋ゴム工業株式会社 ゴム組成物の製造方法
DE102008052057A1 (de) * 2008-10-16 2010-04-22 Lanxess Deutschland Gmbh Funktionalisierte Dienkautschuke
EP2452952A1 (fr) * 2010-11-16 2012-05-16 LANXESS Deutschland GmbH Polymères modifiés en fin de chaîne par un groupe éther carbinol
EP2657281A1 (fr) 2012-04-27 2013-10-30 Cytec Surface Specialties Germany GmbH Composés de Caoutchouc
MY189909A (en) * 2016-08-29 2022-03-21 Weir Slurry Group Inc Wear-resistant rubber compositions, systems, and methods

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB933749A (en) * 1961-04-21 1963-08-14 Phillips Petroleum Co Compounding of solution polymers
GB1238674A (fr) 1968-11-01 1971-07-07
DE1816394A1 (de) * 1968-12-21 1970-07-02 Basf Ag Verfahren zur Herstellung von modifizierten Butadienpolymerisaten
BE758801A (fr) * 1969-11-17 1971-05-12 Atlantic Richfield Co Compositions de caoutchouc d'ethylene-propylene
DE2653144C2 (de) * 1976-11-23 1984-12-20 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von modifiziertem Polybutadien
CA1338317C (fr) 1988-02-25 1996-05-07 Akio Imai Caoutchoucs de polymeres dieniques modifies
ES2085959T5 (es) 1990-03-02 2001-02-01 Bridgestone Corp Neumaticos.
US5070150A (en) * 1990-07-02 1991-12-03 The Goodyear Tire & Rubber Company Process for the solid state (solventless) hydroxylation of vinyl-containing rubbers using a hydroxymercaptan
FR2673187B1 (fr) 1991-02-25 1994-07-01 Michelin & Cie Composition de caoutchouc et enveloppes de pneumatiques a base de ladite composition.
US6057397A (en) * 1995-01-23 2000-05-02 Nippon Zeon Co., Ltd. Rubber composition and process for preparing the same
EP0974616A1 (fr) * 1998-07-18 2000-01-26 Bayer Aktiengesellschaft Caoutchouc polymérisé en solution contenant des groupes hydroxyl

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0068311A1 *

Also Published As

Publication number Publication date
DE19920894A1 (de) 2000-11-09
WO2000068311A1 (fr) 2000-11-16
BR0010333A (pt) 2002-02-13
MXPA01011278A (es) 2002-04-24
JP2002544312A (ja) 2002-12-24
CA2372507A1 (fr) 2000-11-16
KR20020010635A (ko) 2002-02-04
US6696523B1 (en) 2004-02-24
AU4119800A (en) 2000-11-21

Similar Documents

Publication Publication Date Title
EP1000971B1 (fr) Compositions de caoutchouc comprenant du caoutchouc polymérisé en solution ayant des groupements carboxyl
DE69721151T2 (de) Kieselsäuregefüllte Kautschukzusammensetzungen und ihre Herstellung
EP2177374B1 (fr) Mélanges de caoutchouc dotés de caoutchouc diénique et de microgels fonctionnalisés, leur procédé de fabrication et d'utilisation
EP2193166A1 (fr) Caoutchoucs diéniques à haute teneur en vinyle fonctionnalisés
US6252008B1 (en) Solution rubbers containing hydroxyl groups
EP2640753A1 (fr) Polymères à terminaison carbinol renfermant du silane
EP1183305A1 (fr) Caoutchoucs dieniques renfermant des groupes hydroxyle
EP2640754A1 (fr) Polymères à terminaison carbinol renfermant de l'éther
DE19961522A1 (de) Lösungskautschuke mit unpolaren Seitengruppen
DE10009909A1 (de) Kautschuke mit Polyether-Seitengruppen
EP1183304A1 (fr) Caoutchoucs dieniques renfermant des groupes hydroxyle
EP1169384A1 (fr) Caoutchoucs en solution contenant des groupes hydroxyle
EP1341822A1 (fr) Melanges de caoutchoucs a base de caoutchoucs polyether7diolefine et leur utilisation pour produire des pneus en particulier a faible resistance au roulement
WO2009033997A1 (fr) Caoutchoucs au noir de carbone fonctionnalisés
EP1101794A1 (fr) Mélange caoutchouteux à base de caoutchouc contenant des groupements hydroxyl et/ou carboxyl et des charges hydrophobes de types oxydes ou silicates
WO2002031028A1 (fr) Melanges adhesifs de caoutchoucs en solution contenant des groupes hydroxyl ou carboxyl
EP2640785A1 (fr) Polymères à terminaison trialkylsilyloxy
WO2009138349A1 (fr) Caoutchoucs diéniques fonctionnalisés à forte teneur en composés vinylaromatiques
EP1165641A1 (fr) Melanges de caoutchouc a base de polymeres d'amino-isoprenes et leur utilisation pour produire des bandes de roulement a faible resistance au roulement
DE19832458A1 (de) Verfahren zur Herstellung von Mischungen aus hydroxylgruppenhaltigen Kautschuken und Füllstoffen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20011206

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20040203