EP1169384A1 - Caoutchoucs en solution contenant des groupes hydroxyle - Google Patents

Caoutchoucs en solution contenant des groupes hydroxyle

Info

Publication number
EP1169384A1
EP1169384A1 EP00920517A EP00920517A EP1169384A1 EP 1169384 A1 EP1169384 A1 EP 1169384A1 EP 00920517 A EP00920517 A EP 00920517A EP 00920517 A EP00920517 A EP 00920517A EP 1169384 A1 EP1169384 A1 EP 1169384A1
Authority
EP
European Patent Office
Prior art keywords
rubber
rubbers
solution
hydroxyl groups
weight
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Withdrawn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
EP00920517A
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 EP1169384A1 publication Critical patent/EP1169384A1/fr
Withdrawn legal-status Critical Current

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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
    • 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
    • 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

Definitions

  • the present invention relates to rubber mixtures containing rubbers polymerized in solution with a secondary hydroxyl group content of 0.1 to
  • 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 and low rolling resistance.
  • Double bond-containing anionically polymerized solution rubbers 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 transition temperature and the molecular branching. In practical use, this results in particular advantages in relation to the wet skid resistance and rolling resistance of the tire.
  • U.S. Patent No. 5,227,425 describes the
  • EP-A 464 478 A process for the hydroxylation of rubbers is described in EP-A 464 478, in which the hydroxylated rubbers differ structurally from those of the present invention.
  • the secondary hydroxyl groups of EP-A 464 478 are in a more unfavorable position in the polymer and are therefore far less effective than the hydroxyl groups of the present invention, which are not further than 4 carbon atoms from the respective side chain end.
  • EP-806 452 A1 also describes hydroxyl group-containing emulsion and solution rubbers, the hydroxyl contents described here for solution rubbers being in a significantly lower range (0.009 to 0.061%) due to the process.
  • the present patent application shows that these contents have no significant influence on the wet slip resistance and that the position of the hydroxyl groups is particularly important.
  • Hydroxyl groups and also not that the hydroxyl groups are not more than 4 carbon atoms away from the respective side chain end.
  • the present invention therefore relates to rubber mixtures comprising one or more rubbers containing hydroxyl groups and polymerized in solution, composed of diolefins and vinylaromatic monomers, containing secondary hydroxyl groups bonded in the range from 0.1 to 5% by weight, characterized in that the secondary hydroxyl groups are not are located more than 4 carbon atoms from the respective side chain end.
  • Another object of the invention is the use of said rubber mixtures for the production of rubber vulcanizates, in particular silica-filled tire treads with particularly high abrasion resistance, particularly high wet skid resistance and low rolling resistance.
  • the vinyl aromatic / diolefin rubbers polymerized in solution advantageously have average molecular weights (number average) of 50,000 to 2,000,000 and glass transition temperatures of -50 ° to + 20 ° C.
  • Preferred Vinvlaromat contents are between 0.01 and 50 particularly preferably between 5 to 40% by weight.
  • Suitable vinyl aromatic monomers are styrene, o-, m- and p-methylstyrene, p-tert-butylstyrene, ⁇ -methylstyrene, vinylnaphthalene, divinylbenzene, trivinylbenzene and divinylnaphthalene. Styrene is particularly preferred.
  • Suitable diolefins are all diolefins known to the person skilled in the art, in particular 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 1-pheny 1-1,3 -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 anionic solution polymerization, i.e. by means of an alkali metal based catalyst, e.g. n-butyllithium, in a hydrocarbon as a solvent.
  • an alkali metal based catalyst e.g. n-butyllithium
  • randomizers and control agents can be used for the microstructure of the polymer.
  • anionic solution polymerizations are known and e.g. in I. Franta Elastomers and Rubber Compounding Materials; Elsevier 1989, pages 73-74, 92-94 and in
  • hydroxyl groups are introduced in a subsequent reaction on the finished polymer.
  • a preferred method for introducing hydroxyl groups is e.g. the addition of hydroxyl-containing mercaptans.
  • alkali metal polymerization catalysts for the purposes of the present invention are lithium, sodium, potassium, rubidium, cesium metal and their hydrocarbon compounds and complex compounds with polar organic compounds.
  • Lithium and sodium hydrocarbon compounds with 2 to 20 carbon atoms are particularly preferred.
  • n-butyllithium. sec-butyllithium. tert-octyllithium.
  • Preferred amounts of catalyst are between 0.2 and 15 mmol / 100 g of polymer.
  • the anionic solution polymerization is carried out in a hydrocarbon or in another solvent which does not adversely affect the catalyst, for example tetrahydrofuran, tetrahydropyran or 1,4-dioxane.
  • Suitable hydrocarbons as solvents are, for example, aliphatic, cycloaliphatic or aromatic hydrocarbons having 2 to 12 carbon atoms.
  • Preferred solvents are propane, butane, pentane, hexane, cyclohexane, propene, butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, benzene, toluene, xylene.
  • the solvents can be used alone or as a mixture.
  • the hydroxyl groups are preferably introduced by the addition of hydroxyl mercaptans of the general formula (1), hydroxyl group-containing mercapto carboxylic esters of the general formula (2) and / or hydroxyl mercaptans (3).
  • the reaction is preferably carried out in solution, if appropriate in the presence of free radical initiators.
  • R 2 represents hydrogen, a Cj-Cg-alkyl group or a group -CO 2 -R 3 -CHOH-R 1 and
  • R 3 represents a linear, branched or cyclic C2-C36 alkyl group which can optionally be substituted by up to 6 further hydroxyl groups or can be interrupted by nitrogen, oxygen or sulfur atoms,
  • OH stands for a secondary hydroxyl group.
  • n, m independently of one another represents an integer from 1 to 7,
  • q represents an integer in the range from 3 to 4.
  • Preferred hydroxyl mercaptans are 1-mercapto-2-propanol and 1-mercapto-2-butanol. l-mercapto-3-butanol, l-mercapto-2-pentanol, l-mercapto-2-hydroxycyclohexane and 1-mercaptopropanediol. 1-Mercapto-2-propanol are particularly preferred. 1-mercapto-2-butanol, 1-mercapto-2-hydroxy-cyclohexane and 1-mercapto-propanediol (thioglycerol).
  • Preferred mercaptocarboxylic acid esters containing hydroxyl groups are monoesters of mercaptoacetic acid, mercaptopropionic acid.
  • the corresponding esters of 3-mercaptopropionic acid are particularly preferred.
  • Hydroxyl mercaptans and hydroxyl group-containing mercaptocarboxylic acid esters which in addition to the special secondary hydroxyl group carry a further hydroxyl group in the 2- or 3-position, such as thioglycerol, are very particularly preferred.
  • Suitable radical initiators for the attachment of the hydroxyl mercaptans to the solution rubbers are e.g. Azo initiators such as azobisisobutyronitrile, azobiscyclohexanenitrile and peroxides such as dilauroyl peroxide, benzpinacols and benzpinacolsilyl ether or photoinitiators in the presence of visible or UV light.
  • Azo initiators such as azobisisobutyronitrile, azobiscyclohexanenitrile and peroxides such as dilauroyl peroxide, benzpinacols and benzpinacolsilyl ether or photoinitiators in the presence of visible or UV light.
  • Diacyl peroxides in particular di- (3,3,5-trimethylhexanoyl) peroxide, didecanoyl peroxide and dilauroyl peroxide, are particularly preferred.
  • radical initiators are in the range from 0.5 to 20% by weight, based on hydroxyl mercaptan.
  • the Mooney viscosity ML 1 + 4 of the copolymers is in the range from 10 to 200, preferably 30 to 150, measured at 100 ° C.
  • the content of polymerized 1,2-butadiene units (“vinyl content”) is in the range from 5 and 60% by weight, preferably 10 to 50% by weight.
  • the copolymerized vinyl aromatic content is in the range of 0.0 40% by weight, preferably 5 to 40% by weight, particularly preferably 10 to 30% by weight.
  • the content of secondary hydroxyl groups is in the range from 0.1 to 5% by weight. preferably in the range from 0.1 to 3% by weight. particularly preferably in the range from 0.1 to 2% by weight, very particularly preferably in the range from 0.1 to 1% by weight. based on rubber.
  • the method according to the invention thus allows a targeted introduction of hydroxyl groups depending on the desired distance from the side chain end.
  • the content of hydroxyl groups can be determined by known methods, for example by spectroscopy, tritrimetry, elemental analysis or by determining the so-called hydroxyl number (OH number), that is to say by conversion with reagents which release acids which can be titrated in contact with OH groups. See also DLN 53 240.
  • the rubbers can also contain further functional groups, such as, for example, Carboxylic acid and carboxylic ester groups.
  • the hydroxyl-containing rubbers polymerized in solution can be used alone, in admixture with aromatic or aliphatic oils or in a mixture with other rubbers.
  • synthetic rubbers are also suitable as additional rubbers for the production of vulcanized rubber.
  • Preferred synthetic rubbers are described, for example, by W. Hofmann, Kautschuktechnologie, Gentner Verlag, Stuttgart 1980 and I. Franta, Elastomers and Rubber Compounding Materials, Elsevier, Amsterdam 1989. They include
  • EPDM - ethylene / propylene / diene copolymers as well as mixtures of these rubbers.
  • Natural rubber, emulsion SBR and solution SBR rubbers with a glass transition temperature above -50 ° C., which can optionally be modified with silyl ethers or other functional groups, such as, for example, in EP-A, are particularly suitable for the production of motor vehicle tires - 447 066, polybutadiene rubber with a high 1.4-cis content (> 90%), which is produced with catalysts based on Ni, Co, Ti or Nd, and polybutadiene rubber with a vinyl content of 0 to 75% and mixtures thereof of interest .
  • the rubber mixtures according to the invention contain 5 to 500 parts by weight of an active or inactive filler, such as e.g.
  • finely divided silicas e.g. by precipitation of solutions of silicates or flame hydrolysis of silicon halides with specific
  • the silicas can optionally also be mixed oxides with other metal oxides, such as Al, Mg, Ca, Ba, , Zn, Zr, and 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 from 20 to 400 m 2 / g and primary particle diameters from 10 to 400 nm,
  • silicates such as kaolin and other naturally occurring silica.
  • Glass fibers and glass fiber products (mats, strands) or micro glass balls.
  • metal oxides such as zinc oxide, calcium oxide.
  • Magnesium oxide Alumina.
  • Metal carbonates such as magnesium carbonate, calcium carbonate, zinc carbonate,
  • Metal hydroxides e.g. Aluminum hydroxide, magnesium hydroxide,
  • the carbon blacks to be used here are produced by the flan black, furnace or gas black process and have BET surfaces 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 oxidic and silicate fillers can be activated and / or hydrophobicized with the known filler activators, in particular sulfur-containing silyl ethers and / or known hydrophobizing agents.
  • 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
  • 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 are furthermore preferably added to the solid hydroxyl-containing rubber or a mixture of rubbers and mixed in in a known manner, for example using a kneader.
  • the rubber mixtures according to the invention may also contain
  • Crosslinker Sulfur or peroxides can be used as crosslinking agents, with sulfur being particularly preferred.
  • the rubber mixtures according to the invention can contain further rubber auxiliary products, such as reaction accelerators, anti-aging agents, heat stabilizers, light stabilizers, ozone protection agents. Processing aids, plasticizers, tackifiers, blowing agents, dyes, pigments,
  • Waxes, extenders, organic acids, retarders, metal oxides and activators such as triethanolamine, polyethylene glycol, trimethylolpropane etc. which are known to the rubber industry.
  • filler activators are sulfur-containing silyl ethers, in particular bis- (trialkoxysilyl-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
  • the rubber auxiliaries are used in customary amounts, which depend, among other things, on the intended use. Common amounts are e.g. Quantities from 0.1 to 50% by weight, 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, membranes, tires, tire treads, damping elements and tubes.
  • Tires and tire treads are particularly preferred.
  • a solution of 500 g of solution SBR rubber Buna ® VSL 5025-0 (Bayer AG, content of bound styrene 25% by weight, content of 1,2-linked butadiene 50% by weight) in 4 l of cyclohexane is added 70 ° C with 25 g l-mercapto-2-propanol and 2 g
  • the rubber mixtures were then vulcanized at 170 ° C for 20 minutes.
  • the vulcanizates had the following properties: Vulcanizate comparison comparison comparison invention
  • the rubber compounds were then vulcanized at 170 ° C for 20 minutes.
  • the vulcanizates had the following properties: Vulcanizate property comparative invention. example 5.A Example 5.1
  • the test results show that the damping properties of the rubber according to the invention with a special content and arrangement of the hydroxyl groups are significantly improved compared to the unmodified rubber (comparison 5.A); a significantly lower rebound resilience was measured at room temperature and a higher tan delta at 0 ° C, both of which experience has shown to result in a significant improvement in wet skid resistance.
  • the higher rebound elasticities at 70 ° C and the lower tan delta at 60 ° C of the rubber mixture according to the invention both show a lower rolling resistance compared to the reference rubber mixture without the hydroxyl group content according to the invention.
  • the difference between the rebound elasticities at room temperature and 70 ° C and between the tan delta values at 0 and 60 ° C is The rubber compound is considerably larger, so that the relationship between wet skid resistance and rolling resistance in the tire is also significantly more favorable.

Abstract

L'invention concerne des mélanges de caoutchouc contenant des caoutchoucs polymérisés en solution comprenant entre 0,1 et 5 % en poids de groupes hydroxyle secondaires qui ne se situent pas au-delà de 4 atomes de carbone de chaque extrémité de chaîne latérale. L'invention concerne en outre leurs mélanges contenant des charges, éventuellement d'autres caoutchoucs et auxiliaires appropriés, ainsi que des produits de vulcanisation obtenus à l'aide desdits mélanges. Ces mélanges de caoutchouc s'utilisent pour produire des corps moulés très renforcés résistants à l'usure, notamment pour produire des pneus présentant des propriétés antidérapantes sur chaussée mouillée particulièrement marquées.
EP00920517A 1999-04-01 2000-03-20 Caoutchoucs en solution contenant des groupes hydroxyle Withdrawn EP1169384A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19914848 1999-04-01
DE19914848A DE19914848A1 (de) 1999-04-01 1999-04-01 Hydroxylgruppenhaltige Lösungskautschuke
PCT/EP2000/002452 WO2000059994A1 (fr) 1999-04-01 2000-03-20 Caoutchoucs en solution contenant des groupes hydroxyle

Publications (1)

Publication Number Publication Date
EP1169384A1 true EP1169384A1 (fr) 2002-01-09

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP00920517A Withdrawn EP1169384A1 (fr) 1999-04-01 2000-03-20 Caoutchoucs en solution contenant des groupes hydroxyle

Country Status (7)

Country Link
US (1) US6699937B1 (fr)
EP (1) EP1169384A1 (fr)
JP (1) JP2002541289A (fr)
AU (1) AU4106600A (fr)
CA (1) CA2364587A1 (fr)
DE (1) DE19914848A1 (fr)
WO (1) WO2000059994A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10012407A1 (de) 2000-03-15 2001-09-20 Bayer Ag Polyether enthaltende Kautschukmischungen
DE10135014A1 (de) 2001-07-18 2003-01-30 Bayer Ag 1,4-Butendiol(polyether) enthaltende Kautschukmischungen
DE102008023885A1 (de) * 2008-05-16 2009-11-19 Lanxess Deutschland Gmbh Funktionalisierte hochvinylaromaten-haltige Dienkautschuke
DE102008052057A1 (de) * 2008-10-16 2010-04-22 Lanxess Deutschland Gmbh Funktionalisierte Dienkautschuke
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
JP2018095762A (ja) * 2016-12-15 2018-06-21 東洋ゴム工業株式会社 ゴム組成物
JP7059669B2 (ja) * 2017-02-15 2022-04-26 住友ゴム工業株式会社 トレッド用ゴム組成物およびタイヤ

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US3873489A (en) 1971-08-17 1975-03-25 Degussa Rubber compositions containing silica and an organosilane
DE2653144C2 (de) * 1976-11-23 1984-12-20 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von modifiziertem Polybutadien
JPH01163256A (ja) * 1987-12-21 1989-06-27 Nippon Oil Co Ltd 積層板用樹脂組成物
CA1338317C (fr) 1988-02-25 1996-05-07 Akio Imai Caoutchoucs de polymeres dieniques modifies
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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.
DE4406947A1 (de) 1994-03-03 1995-09-07 Bayer Ag Schwefel-/Silizium-haltige Verstärkungsadditive enthaltende Kautschukmischungen
DE4435311A1 (de) 1994-10-01 1996-04-04 Huels Silicone Gmbh Verstärkungsadditive
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MX9603304A (es) 1995-09-23 1997-03-29 Degussa Proceso para la produccion de mezclas de caucho vulcanizables.
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Also Published As

Publication number Publication date
DE19914848A1 (de) 2000-10-05
AU4106600A (en) 2000-10-23
US6699937B1 (en) 2004-03-02
JP2002541289A (ja) 2002-12-03
WO2000059994A1 (fr) 2000-10-12
CA2364587A1 (fr) 2000-10-12

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