WO2005056665A1 - Composition de caoutchouc pour bande de roulement de pneu - Google Patents

Composition de caoutchouc pour bande de roulement de pneu Download PDF

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WO2005056665A1
WO2005056665A1 PCT/CA2004/002105 CA2004002105W WO2005056665A1 WO 2005056665 A1 WO2005056665 A1 WO 2005056665A1 CA 2004002105 W CA2004002105 W CA 2004002105W WO 2005056665 A1 WO2005056665 A1 WO 2005056665A1
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rubber
rubber composition
compound
compounds
composition according
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PCT/CA2004/002105
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English (en)
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Richard Pazur
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Lanxess Inc.
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Publication of WO2005056665A1 publication Critical patent/WO2005056665A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L13/00—Compositions of rubbers containing carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C08L15/005—Hydrogenated nitrile rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Definitions

  • the present invention relates to a method of improving the wet traction and abrasion resistance while reducing the rolling resistance of a tire tread by adding HXNBR to a rubber composition for a tire tread, in particular a tire tread suitable for a pneumatic tire.
  • HXNBR a rubber composition for a tire tread
  • a tire tread suitable for a pneumatic tire BACKGROUND ART
  • Wet grip and the improvement of the wet grip is an important goal in today's tire industry. It is well known that lowering the rolling resistance of a tire will help to lower vehicle fuel consumption. Reduction of carbon black loading and/or increase in its size will lower rolling resistance but at the expense of both the wear resistance and wet gripping ability of the tire. Wear resistance improvements will increase the longevity of the pneumatic tire.
  • anionically polymerized solution rubbers containing double bonds such as solution polybutadiene and solution styrene/butadiene rubbers, have advantages in the manufacture of tyre treads with a low rolling resistance.
  • the advantages lie inter alia in the ability to control the vinyl content and the associated glass transition temperature and the molecular branching. This gives rise in practical use to particular advantages in the relationship between the wet grip and the rolling resistance of the tyre.
  • EP 0390012A1 claims a tire tread composition consisting of crosslinked rubber containing 20 to 50% ionic and from 80 to 50% covalent crosslinks. These treads exhibit improved wear, lower rolling resistance, lower hysteresis and increased strength properties. All of the aforementionned patent claims use unsaturated carboxylated nitrile rubber and do not teach the use and benefits of a hydrogenated carboxylated nitrile in such applications.
  • rubber blends and vulcanized rubber products with surprisingly improved dynamic damping properties in the temperature range relevant to wet grip and in the temperature range relevant to rolling resistance, as well as improved abrasion behaviour, can be prepared from rubber compounds comprising at least one solution vinylaromatic/diolefin rubber and at least one hydrogenated carboxylated nitrilerubber.
  • the present invention provides a rubber composition comprising at least one solution vinylaromatic/diolefin rubber and at least one hydrogenated carboxylated nitrile rubber.
  • the present invention provides a rubber composition comprising at least one solution vinylaromatic/diolefin rubber and at least one hydrogenated carboxylated nitrile rubber and at least one filler.
  • the present invention provides a rubber composition comprising at least one solution vinylaromatic/diolefin rubber and at least one hydrogenated carboxylated nitrile rubber and at least one vulcanizing agent.
  • the present invention provides a rubber composition comprising at least one solution vinylaromatic/diolefin rubber, at least one hydrogenated carboxylated nitrile rubber, at least one filler and at least one vulcanizing agent.
  • the present invention provides a rubber composition for a tire tread comprising at least one solution vinylaromatic/diolefin rubber, at least one hydrogenated carboxylated nitrile rubber, at least one filler and at least one vulcanizing agent.
  • the present invention provides a method of improving the wet traction of a tire tread comprising at least one solution vinylaromatic/diolefin rubber, at least one filler and at least one vulcanizing agent by adding at least one hydrogenated carboxylated nitrile rubber to the compound and vulcanizing the compound.
  • any known solution vinylaromatic/diolefin rubber suitable for tire manufacture can be used.
  • Suitable vinylaromatic monomers are styrene, o-, m- and p-methylstyrene, p- tert-butylstyrene, -methylstyrene, vinylnaphthalene, divinylbenzene, trivinylbenzene and divinylnaphthalene. Styrene is particularly preferred.
  • Suitable diolefins are especially 1,3 -butadiene, isoprene, 1,3-pentadiene, 2,3- dimethylbutadiene, 1-phenyl- 1,3 -butadiene and 1,3-hexadiene. 1,3 -Butadiene and isoprene are particularly preferred.
  • the preparation of the vinylaromatic/diolefin rubbers for the rubber blends according to the invention is preferably effected by anionic solution polymerization, i.e. by means of a catalyst based on an alkali metal, e.g. n-butyllithium, in a hydrocarbon as solvent. It is usually advantageous to use the known randomizers and control agents for the microstructure of the polymer.
  • alkali metal polymerization catalysts in terms of the present invention are lithium, sodium, potassium, rubidium, caesium metal and their hydrocarbon compounds and complex compounds with polar organic compounds.
  • solution-polymerized vinylaromatic/diolefin rubbers advantageously have average molecular weights (number-average) of 50,000 to 2,000,000 and glass transition temperatures of -50° to +20°C.
  • Preferred solution-polymerized vinylaromatic/diolefin rubbers include rubbers of the Buna® VSLTM product range available from Bayer AG.
  • Hydrogenated nitrile rubber prepared by the selective hydrogenation of nitrile rubber (NBR, a co-polymer comprising repeating units derived from at least one conjugated diene, at least one unsaturated nitrile and optionally further comonomers), and hydrogenated carboxylated nitrile rubber (HXNBR), prepared by the selective hydrogenation of carboxylated nitrile rubber (XNBR), a, preferably statistical, ter-polymer comprising repeating units derived from at least one conjugated diene, at least one unsaturated nitrile, at least one conjugated diene having a carboxylic group (e.g an alpha-beta-unsaturated carboxylic acid) and optionally further comonomers are specialty rubbers which have very good heat resistance, excellent ozone and chemical resistance, and excellent oil resistance.
  • NBR nitrile rubber
  • HXNBR hydrogenated carboxylated nitrile rubber
  • XNBR hydrogenated carboxyl
  • HXNBR and HNBR have found widespread use in the automotive (seals, hoses, bearing pads) oil (stators, well head seals, valve plates), electrical (cable sheathing), mechanical engineering (wheels, rollers) and shipbuilding (pipe seals, couplings) industries, amongst others.
  • HXNBR and a method for producing it is for example known from WO- 01/77185-A1 which is hereby incorporated by reference with regard to jurisdictions allowing for this procedure.
  • carboxylated nitrile rubber or XNBR is intended to have a broad meaning and is meant to encompass a copolymer having repeating units derived from at least one conjugated diene, at least one alpha,beta-unsaturated nitrile, at least one alpha-beta-unsaturated carboxylic acid or alpha-beta-unsaturated carboxylic acid derivative and optionally further one or more copolymerizable monomers.
  • HXNBR hydrogenated or HXNBR is intended to have a broad meaning and is meant to encompass a XNBR wherein at least 10 % of the residual C-C double bonds (RDB) present in the starting XNBR are hydrogenated, preferably more than 50 % of the RDB present are hydrogenated, more preferably more than 90 % of the RDB are hydrogenated, even more preferably more than 95 % of the RDB are hydrogenated and most preferably more than 99 % of the RDB are hydrogenated.
  • RDB residual C-C double bonds
  • the conjugated diene may be any known conjugated diene in particular a C 4 -C 6 conjugated diene.
  • Preferred conjugated dienes are butadiene, isoprene, piperylene, 2,3- dimethyl butadiene and mixtures thereof. Even more preferred C 4 -C 6 conjugated dienes are butadiene, isoprene and mixtures thereof. The most preferred C 4 -C 6 conjugated diene is butadiene.
  • the alpha,beta-unsaturated nitrile may be any known alpha,beta-unsaturated nitrile, in particular a C 3 -C 5 alpha,beta-unsaturated nitrile.
  • Preferred C 3 -C 5 alpha,beta- unsaturated nitriles are acrylonitrile, methacrylonitrile, ethacrylonitrile and mixtures thereof.
  • the most preferred C 3 -C 5 alpha,beta-unsaturated nitrile is acrylonitrile.
  • the alpha,beta-unsaturated carboxylic acid may be any known alpha,beta- unsaturated acid copolymerizable with the diene(s) and the nitrile(s), in particular acrylic, methacrylic, ethacrylic, crotonic, maleic, fumaric or itaconic acid, of which acrylic and methacrylic are preferred.
  • the alpha,beta-unsaturated carboxylic acid derivative may be any known alpha,beta-unsaturated acid derivative copolymerizable with the diene(s) and the nitile(s), in particular esters, amides and anhydrides, preferably esters and anhydrides of acrylic, methacrylic, ethacrylic, crotonic, maleic, fumaric or itaconic acid.
  • the HXNBR comprises in the range of from 39.1 to 80 weight percent of repeating units derived from one or more conjugated dienes, in the range of from 5 to 60 weight percent of repeating units derived from one more unsaturated nitriles and 0.1 to 15 percent of repeating units derived from one or more unsaturated carboxylic acid or acid derivative. More preferably, the HXNBR comprises in the range of from 60 to 70 weight percent of repeating units derived from one or more conjugated dienes, in the range of from 20 to 39.5 weight percent of repeating units derived from one or more unsaturated nitriles and 0.5 to 10 percent of repeating units derived from one or more unsaturated carboxylic acid or acid derivative.
  • the HXNBR comprises in the range of from 56 to 69.5 weight percent of repeating units derived from one or more conjugated dienes, in the range of from 30 to 37 weight percent of repeating units derived from one or more unsaturated nitriles and 0.5 to 7 percent of repeating units derived from one or more unsaturated carboxylic acid or acid derivative.
  • said HXNBR is a statistical co-polymer with in particular the carboxylic functions randomly distributed throughout the polymer chains.
  • the HXNBR may further comprise repeating units derived from one or more copolymerizable monomers.
  • HXNBR are available from Bayer AG under the tradename THERBAN® XTTM VP KA 8889.
  • the composition of the inventive rubber compound may vary in wide ranges and in fact it is possible to tailor the properties of the resulting compound by varying the ratio HXNBR(s)/HNBR(s).
  • the compound preferably comprises in the range of from 0.1-30 wt.%, of HXNBR(s), more preferably from 1-20, most preferably from2 — 10 wt.%
  • the Mooney viscosity of the rubbers can be determined using ASTM test D1646.
  • the HXNBR(s) comprised in the inventive compound are not restricted. However, preferably they have a Mooney viscosity (ML 1+4 @ 100°C) above 30.
  • the solution-polymerized vinylaromatic/diolefin rubbers advantageously have a Mooney viscosity (ML 1+4 @ 100°C) in the range of from 40 - 90.
  • Blending of two or more rubber polymers having a different Mooney viscosity will usually result in a blend having a bi-modal or multi-modal molecular weight distribution.
  • the final blend has preferably at least a bi-modal molecular weight distribution.
  • at least one vulcanizing agent or curing system has to be added.
  • the invention is not limited to a special curing system, however, sulfur curing system(s) are preferred.
  • the preferred amount of sulfur is in the range of from 0.3 to 2.0 phr (parts by weight per hundred parts of rubber).
  • An activator for example zinc oxide, may also be used, in an amount in the range of from 5 parts to 0.5 parts by weight.
  • stearic acid oils (e.g. Sunpar® of Sunoco), antioxidants, or accelerators (e.g. a sulfur compound such as dibenzotliiazyldisulfide (e.g. Nulkacit® DM/C of Bayer AG) may also be added to the compound prior to curing. Sulphur curing is then effected in known manner. See, for instance, chapter 2, “The Compounding and Vulcanization of Rubber", of “Rubber Technology", 3 rd edition, published by Chapman & Hall, 1995.
  • the filler may be in particular: - highly dispersed silicas, prepared e.g.
  • the silicas can optionally also be present as mixed oxides with other metal oxides such as those of Al, Mg, Ca, Ba, Zn, Zr and Ti; - synthetic silicates, such as aluminum silicate and alkaline earth metal silicate like magnesium silicate or calcium silicate, with BET specific surface areas in the range of from 20 to 400 m 2 /g and primary particle diameters in the range of from 10 to 400 nm; - natural silicates, such as kaolin and other naturally occurring silica; - glass fibers and glass fiber products (matting, extrudates) or glass microspheres; - metal oxides, such as zinc oxide, calcium oxide, magnesium oxide and aluminum oxide; - metal carbonates, such as magnesium carbonate, calcium carbonate and zinc carbonate; - metal hydroxides,
  • - carbon blacks are prepared by the lamp black, furnace black or gas black process and have preferably BET (DIN 66 131) specific surface areas in the range of from 20 to 200 m 2 /g, e.g. SAF, ISAF, HAF, FEF or GPF carbon blacks; - rubber gels, especially those based on polybutadiene, butadiene/styrene copolymers, butadiene/acrylonitrile copolymers and polychloroprene; or mixtures thereof.
  • preferred mineral fillers include silica, silicates, clay such as bentonite, gypsum, alumina, titanium dioxide, talc, mixtures of these, and the like. These mineral particles have hydroxyl groups on their surface, rendering them hydrophilic and oleophobic. This exacerbates the difficulty of achieving good interaction between the filler particles and the rubber.
  • the preferred mineral is silica, especially silica made by carbon dioxide precipitation of sodium silicate.
  • Dried amorphous silica particles suitable for use in accordance with the invention may have a mean agglomerate particle size in the range of from 1 to 100 microns, preferably between 10 and 50 microns and most preferably between 10 and 25 microns.
  • a suitable amorphous dried silica moreover usually has a BET surface area, measured in accordance with DIN (Deutsche Industrie Norm) 66131, of in the range of from 50 and 450 square meters per gram and a DBP absorption, as measured in accordance with DIN 53601, of in the range of from 150 and 400 grams per 100 grams of silica, and a drying loss, as measured according to DIN ISO 787/11, of in the range of from 0 to 10 percent by weight.
  • Suitable silica fillers are available under the trademarks HiSil® 210, HiSil® 233 and HiSil® 243 from PPG Industries Inc.
  • Vulkasil® S and Vulkasil® N are also suitable.
  • carbon black is present in the polymer blend in an amount of in the range of from 20 to 200 parts by weight, preferably 30 to 150 parts by weight, more preferably 40 to 100 parts by weight.
  • the vulcanizable rubber compound may further comprise other natural or synthetic rubbers such as BR (polybutadiene), preferably BR of the TakteneTM product family available from Bayer AG, ABR (butadiene/acrylic acid-C;[-C4-alkylester- copolymers), EVM (ethylene vinyl acetate-copolymers), NBR (butadiene/acrylonitrile copolymers), AEM (ethylene acrylate-copolymers), CR (polychloroprene), IR (polyisoprene), butyl, chlorobutyl and bromobutyl rubbers, SBR (styrene/butadiene- copolymers) with styrene contents in the range of 1 to 60 wt%, EPDM (ethylene/propylene/diene-copolymers), FKM (fluoropolymers or fluororubbers), and mixtures of the given polymers.
  • BR polybutadiene
  • a high-cis BR is particularly preferable, and in the case of a combination of the natural rubber (NR) and the high-cis BR, a ratio of the natural rubber (NR) to the high-cis BR is 80/20 to 30/7O, preferably 70/30 to 40/60.
  • the amount of the combination of the natural rubber and the high-cis BR is 70%) by weight or more, preferably 80% by weight or more, more preferably 85% by weight or more.
  • the following rubbers are of particular interest for the manufacture of motor vehicle tyres with the aid of surface-modified fillers: natural rubber, emulsion SBRs and solution SBRs with a glass transition temperature above -50°C, which can optionally be modified with silyl ethers or other fuactional groups, such as those described e.g. in EP-A 447,066, polybutadiene rubber with a high 1,4-cis content (>90%), which is prepared with catalysts based on Ni, Co, Ti or Nd, and polybutadiene rubber with a vinyl content of 0 to 75%, as well as blends thereof.
  • the inventive compound comprises HXNBR and SBR.
  • the preferred SBR content in the compound is in the range of from 50 - 99 phr.
  • the vulcanizable rubber compound according to the invention can contain further auxiliary products for rubbers, such as reaction accelerators, vulcanizing accelerators, vulcanizing acceleration auxiliaries, antioxidants, foaming agents, anti- aging agents, heat stabilizers, light stabilizers, ozone stabilizers, processing aids, plasticizers, tackifiers, blowing agents, dyestuffs, pigments, waxes, extenders, organic acids, inhibitors, metal oxides, and activators such as triethanolamine, polyethylene glycol, hexanetriol, etc., which are known to the rubber industry.
  • the rubber aids are used in conventional amounts, which depend inter alia on the intended use. Conventional amounts are e.g. from 0.1 to 50 phr.
  • the vulcanizable compound comprising said solution blend further comprises in the range of 0.1 to 20 phr of one or more organic fatty acids as an auxiliary product, preferably a unsaturated fatty acid having one, two or more carbon double bonds in the molecule which more preferably includes 10% by weight or more of a conjugated diene acid having at least one conjugated carbon-carbon double bond in its molecule.
  • those fatty acids have in the range of from 8-22 carbon atoms, more preferably 12-18.
  • silane compounds examples include stearic acid, palmitic acid and oleic acid and their calcium-, zinc-, magnesium-, potassium- and ammonium salts. Further addition of silane compounds may be advantageous, especially in combination with highly active fillers.
  • the silane compound may be a sulfur-containing silane compound. Suitable sulfur-containing silanes include those described in United States patent 4,704,414, in published European patent application 0,670,347 Al and in published German patent application 4435311 Al.
  • One suitable compound is a mixture of bis[3-(triethoxysilyl)propyl]-monosulfane, bis[3-(triethoxysilyl)propyl] disulfane, bis[3-(triethoxysilyl)propyl]trisulfane and bis[3-(triethoxysilyl)propyl]tetrasulfane and higher sulfane homologues available under the trademarks Si-69 (average sulfane 3.5), SilquestTM A-1589 (from CK Witco)or Si-75 (from Degussa) (average sulfane 2.0).
  • Another example is bis[2-(triethoxysilyl)ethyl]-tetrasulfane, available under the trademark Silquest RC-2.
  • Non-limiting illustrative examples of other sulfur-containing silanes include the following: bis [3 -(triethoxysilyl)propyl] disulfane, bis [2-(trimethoxysilyl)ethyl]tetrasulfane, bis[2-(triethoxysilyl)ethyl]trisulfane, bis[3-(trimethoxysilyl)propyl]disulfane, 3-mercaptopropyltrimethoxysilane, 3 -mercaptopropylmethyldiethoxysilane, and 3-mercaptoethylpropylethoxymethoxysilane.
  • Other preferred sulfur-containing silanes include those disclosed in published
  • German patent application 44 35 311 Al the disclosure of which is incorporated by reference.
  • the silane is usually applied in amounts in the range of from 2 to 6 phr.
  • the ingredients of the final vulcanizable rubber compound comprising said rubber compound are often mixed together, suitably at an elevated temperature that may range from 25 °C to 200 °C. Normally the mixing time does not exceed one hour and a time in the range from 2 to 30 minutes is usually adequate.
  • Mixing is suitably carried out in an internal mixer such as a Banbury mixer, or a Haake or Brabender miniature internal mixer.
  • a two roll mill mixer also provides a good dispersion of the additives within the elastomer.
  • An extruder also provides good mixing, and permits shorter mixing times.
  • HXNBR a compound suitable for a tire tread comprising at least one solution vinylaromatic/diolefin rubber, at least one filler and at least one vulcanizing agent vulcanizing the compound results in improving the wet traction and abrasion resistance while reducing the rolling resistance of said tire tread.
  • Dynamic Mechanical property measurements at the correct strain conditions have been shown to correlate to both wet traction and rolling resistance behaviour of the tire tread.
  • the measurement of tan delta at 0°C predicts the wet grip characteristics while the same measurement at 60°C is routinely used to measure rolling resistance of a tire.
  • the latter can also be estimated by measuring the loss modulus G" at the same temperature.
  • Cure rheometry Vulcanization was followed on a Moving Die Rheometer (MDR 2000(E)) using a frequency of oscillation of 1.7 Hz and a l°arc at 170°C for 30 minutes total run time. The test procedure follows ASTM D-5289.
  • Haake Extrusion with Garvey die VX' diameter screw and 10" screw length.
  • the barrel temperature was set at 100°C while the Garvey die was at 105°C.
  • the single screw was turning at 45 r.p.m.. Testing was carried out according to ASTM D-2230.
  • Die C cut dumbell samples are cut out of a moulded unvulcanized rubber sample and then pulled on a tensile tester at room temperature. The resultant force and elongations are measured upon extension of the dumbell sample.
  • Abrasion resistance is determined according to test method DIN 53 516. The volume loss by rubbing the rubber specimen with an emery paper of defined abrasive power is measured and reported.
  • Pico Abrasion This test method complies with ASTM D-2228 and indicates the cutting abrasion resistance of the vulcanizates.
  • Goodrich Flexometer This device measures the compression fatigue characteristics of a rubber sample under constant load conditions. The method used complies with ASTM D 623-99. The combination of cyclic compression and relaxation causes heat generation and energy loss in the rubber.
  • Cut growth was measured on punctured specimens that were subjected to repeated flexing.
  • the actual test procedure conforms to ASTM D-813 (95).
  • the measurement of fatigue properties of rubber compounds such as tires, belts and footwear is often represented by flex cracking data. Puncture size is 2 mm in length and samples are flexed at a rate of 300 cycles per minute.
  • GABO Eplexor Dynamic properties were determined by means of a GABO Eplexor tester. The test specimen is subjected to a small sinusoidal deformation at a particular frequency and the temperature is varied. The resulting stress and phase difference between the imposed deformation and the reponse are measured and recorded.
  • the results of the physical property testing are given in Table 2. There are no compound Mooney scorch issues for the eight compounds at 125°C. At 135°C, ample processing safety is still available, in particular for the silica filled compounds 5 through 8.
  • Therban XT addition causes the compounds, black or silica filled, to become slightly scorchier due to interactions between the zinc ions and the carboxylate groups producing an ionic crosslinking network. In compounds 1 to 4, Therban XT addition has a slight effect in decreasing compound Mooney viscosity (example 4). In the silica based compounds 5 through 8, a general increase in compound Mooney viscosity is observed primarily on account of interactions between the silica and the carboxylate groups and any ionic crosslinking present in the compound.
  • Therban XT addition to the 8 compounds has a slight effect on cure characteristics.
  • the overall state of cure (MH) decreases in both the black and silica filled compounds.
  • the ML results correlate with the compound Mooney values.
  • Compounds 4 and 7 have lower minimum torque values than the control.
  • Such compounds possess advantages for processing.
  • Tsl values mirror Mooney scorch for the black compounds in that the scorch is not increased upon Therban XT addition.
  • Scorch is slightly increased in the silica compounds 6 to 8 due to Therban XT addition. Time to 50 and to 90% cures are lengthened in the case of the black filled compounds however, little variation is seen in the silica based ones.
  • Therban XT addition to the black filled compounds (2 to 4) does not change the hardness values.
  • its addition ot the silica compounds causes an noticeable decrease in hardness (see 6 to 8).
  • a loss in tensile strength is observed in the black compounds upon Therban XT addition however, tensile is relatively constant in the case of the silica based compounds.
  • Elongation values do not change with Therban XT addition in all compounds.
  • Die B and Die C tear strength tend to higher values in the both the black and silica based compounds upon Therban XT addition.
  • the wear characteristics are particularly important in tread compounds.
  • the DIN abrasion increases only marginally in the black compounds 2 to 4 whereas a slight decrease is noted with the silica bases ones 6 to 8.
  • the Taber abrasion results confmn the tendencies observed in the DIN abrasion. It is clear from these results that abrasion resistance represented by DIN and Taber is improved upon XT addition to a silica based compound.
  • the Pico abrasion on the other hand decreases slightly upon XT addition in both black and silica compounds.
  • Significant heat rise in a tread compound can arise in premature oxidative degradation and subsequent loss of mechanical properties. According to the Goodrich flexometer test results, the heat rise in the black compounds is minimal upon Therban XT addition whereas the heat generation is constant in the case of the silica compounds 6 to 8.
  • the carbon black compounds have a tendency to take on some permanent set.
  • the amount of permanent set in the silica compounds is relatively constant. Fatigue characteristics are quite important in the good functioning of tire tread compound.
  • the DeMattia flex test results illustrate a slightly higher unaged crack growth rate for the both the carbon black (2 to 4) and silica (6 to 8) compounds. It is known that the tan delta measured at 0°C can be correlated to the wet traction characteristics of the tread. In the case of the carbon black filled treads, Therban XT addition has only a small effect (compound 4) in increasing this desirable characteristic.

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Abstract

Procédé permettant d'améliorer la traction sur route mouillée et la résistance à l'abrasion, tout en réduisant la résistance au roulement d'une bande de roulement de pneu, qui consiste à ajouter du caoutchouc nitrile hydrogéné carboxylé (HXNBR) à une composition de caoutchouc vinylaromatique / dioléfine pour une bande de roulement de pneu, en particulier une bande de roulement adaptée pour un pneumatique.
PCT/CA2004/002105 2003-12-12 2004-12-10 Composition de caoutchouc pour bande de roulement de pneu WO2005056665A1 (fr)

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CA002452863A CA2452863A1 (fr) 2003-12-12 2003-12-12 Composition de caoutchouc pour bandes de roulement de pneu

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Cited By (7)

* Cited by examiner, † Cited by third party
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WO2009070374A1 (fr) * 2007-11-30 2009-06-04 Services Petroliers Schlumberger Compositions gonflables et leurs procédés et dispositifs de régulation
EP2452831A1 (fr) * 2010-11-11 2012-05-16 The Goodyear Tire & Rubber Company Pneu avec bande de roulement contenant du styrène carboxylé/caoutchouc de butadiène
CN104277253A (zh) * 2014-09-22 2015-01-14 安徽喜洋洋儿童用品有限公司 一种较强韧性的防滑轮胎用橡胶
DE102015214731A1 (de) 2015-08-03 2017-02-09 Continental Reifen Deutschland Gmbh Kautschukmischung und Fahrzeugreifen
CN109021314A (zh) * 2018-06-29 2018-12-18 宁国宁志橡塑科技有限公司 一种高性能橡胶材料及其制备方法
CN110330701A (zh) * 2019-07-18 2019-10-15 成都五一六隔震科技有限公司 一种采用硫化剂的炼胶配方及生产工艺
CN115891508A (zh) * 2022-11-02 2023-04-04 中智途瑞轮胎科技(山东)有限公司 一种静音自密封轮胎用橡胶组合物及制备方法

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CN102115563B (zh) * 2010-12-28 2012-12-12 六安市金赛特橡塑制品有限公司 一种用于高温、高压或高湿环境下电器类使用的密封件原料及其制备方法
CN103665682B (zh) * 2013-11-15 2016-01-20 安徽宏发节能设备有限公司 一种高弹性低压缩形变得橡胶密封垫材料及其制备方法
CN113061296B (zh) * 2021-03-16 2022-06-17 重庆市金盾橡胶制品有限公司 一种碳纳米管胎面胶及其制备方法

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009070374A1 (fr) * 2007-11-30 2009-06-04 Services Petroliers Schlumberger Compositions gonflables et leurs procédés et dispositifs de régulation
EP2452831A1 (fr) * 2010-11-11 2012-05-16 The Goodyear Tire & Rubber Company Pneu avec bande de roulement contenant du styrène carboxylé/caoutchouc de butadiène
US8247487B2 (en) 2010-11-11 2012-08-21 The Goodyear Tire & Rubber Company Tire with tread containing carboxylated styrene/butadiene rubber
CN104277253A (zh) * 2014-09-22 2015-01-14 安徽喜洋洋儿童用品有限公司 一种较强韧性的防滑轮胎用橡胶
DE102015214731A1 (de) 2015-08-03 2017-02-09 Continental Reifen Deutschland Gmbh Kautschukmischung und Fahrzeugreifen
CN109021314A (zh) * 2018-06-29 2018-12-18 宁国宁志橡塑科技有限公司 一种高性能橡胶材料及其制备方法
CN110330701A (zh) * 2019-07-18 2019-10-15 成都五一六隔震科技有限公司 一种采用硫化剂的炼胶配方及生产工艺
CN115891508A (zh) * 2022-11-02 2023-04-04 中智途瑞轮胎科技(山东)有限公司 一种静音自密封轮胎用橡胶组合物及制备方法
CN115891508B (zh) * 2022-11-02 2023-12-19 中智途瑞轮胎科技(山东)有限公司 一种静音自密封轮胎用橡胶组合物及制备方法

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