Classifications

• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/01—Hydrocarbons
• • 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
• • 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
  • B60C17/00—Tyres characterised by means enabling restricted operation in damaged or deflated condition; Accessories therefor
  • B60C17/0009—Tyres characterised by means enabling restricted operation in damaged or deflated condition; Accessories therefor comprising sidewall rubber inserts, e.g. crescent shaped inserts
• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
• • 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 patent application relates to rubber mixtures consisting of rubber, filler and a specific sulphurised mineral oil.
• Vulcanisates with surprisingly good reinforcement- and temperature-dependent dynamic damping behaviour which are particularly suitable for producing tires with low-damping treads with a high resistance to wet skidding and for producing tires with low-damping highly reinforced lateral walls can be produced from the rubber mixtures according to the invention.
• a further object of the present invention was to provide mineral oil-containing rubber mixtures and vulcanisates with improved reinforcement behaviour.
• JP-B 47 008 135 describes reaction products of aromatic mineral oils with sulphur monochloride for improving the processing behaviour of rubber mixtures.
• the modified mineral oils are produced by a method which predominantly leads to mono- and disulphide bridges due to the chemical nature of sulphur monochloride.
• the sulphur monochloride used leads to an undesirable residue of bound chlorine in the end product.
• the present invention therefore relates to rubber mixtures consisting of a rubber, a fillet and optionally further rubber auxiliaries and cross-linking agents and 0.1 to 75 parts by weight, based on 100 parts by weight of rubber, of a specific sulphurised mineral oil, the sulphurised mineral oil having been obtained by reacting an aromatic-containing mineral oil with sulphur.
• the sulphurised mineral oil used was produced according to the invention in that an aromatic-containing mineral oil with an aromatic content according to ASTM D 2140 of 5 to 50 wt. % and a viscosity-density constant VDK of 0.82 to 1.05 was reacted with 2.5 to 40 parts by weight of sulphur per 100 parts by weight of mineral oil at temperatures of 130 to 250° C., optionally in the presence of catalysts.
• the sulphurised mineral oils according to the invention have a bound sulphur content of 2.5 to 12.5 wt. %, preferably 4 to 10 wt. %, and a glass transition temperature (determined by DSC) of ⁇ 25 to ⁇ 65° C., preferably ⁇ 35 to ⁇ 55° C., and a density of 0.85 to 1.1 g/cm 3 , preferably 0.92 to 1.03 g/cm 3 (at 20° C.).
• the viscosities are 0.3 to 100 Pa.sec, particularly preferably 0.8 to 20 Pa.sec at 20° C. (plate and cone viscometer, 20 rpm).
• the starting products for producing the sulphurised mineral oils used according to the invention are aromatic-containing mineral oils with an aromatic content (according to ASTM D 2140) of 5 to 50%, preferably 15 to 40%, a viscosity-density constant VDK (according to ASTM D 2501) of 0.82 to 1.05, preferably 0.84 to 1.0.
• Preferred aromatic-containing mineral oils moreover have a density of 0.85 to 1.03 g/cm 3 (at 15° C.), preferably 0.9 to 1.0 g/cm 3 and a pour point (according to ASTM D 97) between ⁇ 20° C. and +30° C., particularly preferably between ⁇ 15° C. and +20° C., and contain less than 0.1 wt.
• Mineral oil products of this type are commercially available; suitable products are, for example, Enerthene® 1849-1 (BP) and Catenex Oil SNR® (Shell). In this regard see Kautschuk, Kunststoffe, 45 (1992), pages 24-29.
• the reaction of aromatic-containing mineral oils with sulphur is preferably carried out with 5 to 20 parts by weight of sulphur per 100 parts by weight of aromatic-containing mineral oils at temperatures of preferably 160 to 220° C., particularly preferably 180 to 210° C., for a time period of a few minutes (5 min) up to several hours (10 hours), optionally in the presence of catalysts.
• Suitable catalysts are acidic or basic catalysts, such as zinc chloride, aluminium chloride, tin chloride, hydrogen sulphide and/or alkyl amines, such as dodecylamine or octadecylamine.
• Suitable quantities of catalysts are 0.01 to 3 parts by weight based on aromatic-containing mineral oil.
• the reaction is preferably carried out without a catalyst.
• residues of hydrogen sulphide and volatile mercaptans can be removed, for example, by applying a vacuum or blowing out with nitrogen or by chemical methods, such as oxidising agents (for example atmospheric oxygen or peroxides). Unreacted sulphur can be removed by filtering off, for example.
• oxidising agents for example atmospheric oxygen or peroxides
• synthetic rubbers are also suitable for producing the rubber mixtures and vulcanisates according to the invention.
• Preferred synthetic rubbers are described, for example, in W. Hofmann, Kautschuktechnologie, Gentner Verlag, Stuttgart 1980 and I. Franta, Elastomers and Rubber Coumpounding Materials, Elsevier, Amsterdam 1989. They include inter alia
• SBR styrene/butadiene copolymers with styrene contents of 1-60, preferably 20-50 wt. %
• NBR butadiene acrylonitrile copolymers with acrylonitrile contents of 5-60, preferably 10-40 wt. %
• HNBR partially or completely hydrogenated NBR rubber
• EPDM ethylene propylene diene copolymers
• the rubber mixtures according to the invention contain the fillers known and used in the rubber industry; these include both the active and the inactive fillers, notably:
• fine-particled silicas produced, for example, by precipitation of solutions of silicates or flame hydrolysis of silicon halides with specific surface areas of 5 -1000, preferably 20-400 m 2 /g (BET surface area) and with primary particle sizes of 10-400 nm.
• the silicas can optionally be present as mixed oxides with other metal oxides, such as Al, Mg, Ca, Ba, Zn, Zr, Ti oxides;
• synthetic silicates such as aluminium silicate, alkaline-earth silicate such as magnesium silicate or calcium silicate, with BET surface areas of 20-400 m 2 /g and primary particle diameters of 10-400 nm;
• glass-fibres and glass-fibre products (mats, strands) or glass microbeads;
• metal oxides such as zinc oxide, calcium oxide, magnesium oxide, aluminium oxide
• metal carbonates such as magnesium carbonate, calcium carbonate, zinc carbonate
• metal hydroxides such as for example, aluminium hydroxide, magnesium hydroxide
• carbon blacks are produced by the lamp black, furnace or gas black process and have BET surface areas of 20-200 m 2 /g, for example, SAF, ISAF, HAF, FEF or GPF carbon blacks;
• rubber powder obtained, for example, by size-reduction of rubber vulcanisates. Preferred particle sizes are between 0.001 to 0.5 mm.
• Fine-particle silicas and carbon blacks, optionally together with rubber powder, are preferably used as fillers.
• the fillers mentioned can be used alone or in a mix, specifically in quantities of 1 to 300 parts by weight, preferably 10 to 150 parts by weight based on 100 parts by weight of rubber.
• the rubber mixtures contain as fillers, a mixture of light fillers, such as fine-particled silicas, and carbon blacks, the mixing ratio of light filler to carbon blacks being 1:0.05 to 20, preferably 1:0.1 to 10.
• the rubber mixtures according to the invention can obviously also contain other rubber auxiliaries and cross-linking agents.
• Sulphur or sulphur-supplying compounds or peroxides are used as cross-linking agents.
• Particularly preferred are sulphur or sulphur-supplying compounds in quantities of 0.01 to 3 parts by weight based on rubber.
• the rubber mixtures according to the invention can contain further auxiliary agents, such as the known reaction accelerators, anti-ageing agents, heat stabilisers, light protection agents, ozone protection agents, process aids, reinforcing resins, for example phenolic resins, steel cord bonding agents, such as, for example, silica/resorcinol/hexamethylenetetramine or cobalt-naphthenate, plasticisers, tackifiers, blowing agents, dyes, pigments, waxes, extenders, organic acids, retarding agents, metal oxides and activators.
• auxiliary agents such as the known reaction accelerators, anti-ageing agents, heat stabilisers, light protection agents, ozone protection agents, process aids, reinforcing resins, for example phenolic resins, steel cord bonding agents, such as, for example, silica/resorcinol/hexamethylenetetramine or cobalt-naphthenate, plasticisers, tackifiers, blow
• the rubber auxiliaries are used in the usual, known quantities, the quantity used depending on the subsequent intended purpose of the rubber mixtures.
• normal quantities of rubber auxiliaries are in the range of 2 to 70 parts by weight, based on 100 parts by weight of rubber.
• filler activators are sulphur-containing silyl ethers, in particular bis-(trialkoxysilyl-alkyl)-polysulphides as described in DE-A 2 141 159 and DE-A 2 255 577. Further possibilities are oligomeric and/or polymeric sulphur-containing silyl ethers according to the description in DE-A 4 435 311 and EP-A 670 347.
• Mercapto-alkyltrialkoxysilanes in particular mercaptopropyltriethoxysilane and thiocyanatoalkylsilylethers (see DE-A 19 544 469), amino group-containing silyl ethers, such as for example 3-amino-propyltriethoxysilane and N-oleyl-N-propyl-trimethoxysilane and trimethylolpropane.
• the filler activators are used in the usual quantities, i.e. in quantities of 0.1 to 15 parts by weight, based on 100 parts by weight of rubber.
• the rubber mixtures according to the invention can be produced, for example, by mixing the rubbers with the fillers, rubber auxiliaries and the sulphurised mineral oils in suitable mixing apparatuses, such as kneaders, rollers or extruders, or by mixing the rubber solutions with fillers and the sulphurised mineral oils and removing the solvent, for example by steam distillation.
• the present invention also relates to the use of the rubber mixtures according to the invention for producing vulcanisates which, in turn, are used for the production of highly reinforced rubber shaped articles, in particular for the production of tires.
• 1,045 g of a black oil were obtained with a sulphur content of 5.3 wt.%, viscosity 5 Pa.sec (plate and cone, 20 rpm, 20° C.), glass transition temperature of ⁇ 50° C. (according to DSC) and density 0.97g/cm 3 .

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Tires In General (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=7643323

Family Applications (1)

Country Status (4)

Cited By (39)

• 2000
  • 2000-05-24 DE DE10025625A patent/DE10025625A1/de not_active Withdrawn
• 2001
  • 2001-05-18 CA CA002348177A patent/CA2348177A1/en not_active Abandoned
  • 2001-05-22 US US09/862,149 patent/US20020000280A1/en not_active Abandoned
  • 2001-05-24 JP JP2001155957A patent/JP2002020552A/ja active Pending

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