WO2018121976A1 - Mélanges de caoutchouc - Google Patents

Mélanges de caoutchouc Download PDF

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Publication number
WO2018121976A1
WO2018121976A1 PCT/EP2017/082264 EP2017082264W WO2018121976A1 WO 2018121976 A1 WO2018121976 A1 WO 2018121976A1 EP 2017082264 W EP2017082264 W EP 2017082264W WO 2018121976 A1 WO2018121976 A1 WO 2018121976A1
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rubber
weight
parts
vulcanizable
mixtures according
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PCT/EP2017/082264
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German (de)
English (en)
Inventor
Thomas FRÜH
Walter Leidinger
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Arlanxeo Deutschland Gmbh
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Priority to EP17821851.7A priority Critical patent/EP3562877A1/fr
Publication of WO2018121976A1 publication Critical patent/WO2018121976A1/fr

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    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/16—Ethene-propene or ethene-propene-diene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08J2323/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08J2323/22—Copolymers of isobutene; butyl rubber
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon

Definitions

  • the invention relates to novel, vulcanizable rubber mixtures, their preparation, the vulcanizates obtainable therefrom, their preparation and use.
  • JP-H02-166328 for example, by introducing aramid and / or nylon short fibers up to an amount of 30% by volume in rubbers, in particular properties of the modulus of elasticity, can be anisotropically improved.
  • the short fibers have a length of up to 10 mm.
  • the fibers actually used are only 3 mm long and are used in an amount of only 15% by volume.
  • preferred vulcanizable rubber mixtures according to the invention are those where at least one double bond-containing rubber a) is selected from the group consisting of NR (natural rubber), EPDM (ethylene-propylene-diene rubber), SBR (vinyl aromatic / diene rubber), BR (polybutadiene rubber), IR ( Polyisoprene), SIBR (styrene / isoprene / butadiene rubber), BIR (butadiene / isoprene rubber), HR (butyl rubber, ie isobutene / isoprene rubber), XIIR
  • Halobutyl rubber especially chloro- or bromobutyl rubber
  • NBR nitrile rubber
  • XNBR carboxylated butadiene / acrylonitrile rubber
  • SNBR styrene / butadiene / acrylonitrile rubber
  • XSBR carboxylated styrene / butadiene rubber
  • CR polychloroprene
  • ENR epoxidized natural rubber
  • NR natural rubber
  • EPDM polyethylene glycol dimethacrylate copolymer
  • SBR vinyl aromatic / diene rubbers
  • BR polybutadiene rubber
  • IR polyisoprene
  • IBR isoprene / -
  • EPDM butadiene rubber
  • HR isobutene / isoprene rubber
  • BIR butadiene / isoprene rubber
  • SIBR styrene / isoprene rubber
  • one or more EPDM rubbers may be present in component a) of the mixture according to the invention.
  • the diene monomer provides the double bonds for the subsequent vulcanization ready.
  • the diene monomers predominantly cis, cis-l, 5-cyclooctadiene (COD), exo-dicyclopentadiene (DCP), endo-dicyclopentadiene (EDCP), 1,4-hexadiene (HX), 5-ethylidene-2-norbornene ( ENB), dicyclopentadiene (DCPD) and 5-vinyl-2-norbornene (VNB) use.
  • SBR vinyl aromatic / diene rubbers
  • SBR rubbers are understood to mean rubbers based on vinylaromatics and dienes, both solution SBR rubbers, abbreviated as “L-SBR”, and emulsion SBR rubbers, abbreviated as “E-SBR”.
  • L-SBR rubbers are prepared which are prepared in a solution process based on vinylaromatic compounds and dienes, preferably conjugated dienes (HL Hsieh, RP Quirk, Marcel Dekker Inc. New York-Basel 1996, I. Franta Elastomers and Rubber Compounding Materials Elsevier 1989, pages 73-74, 92-94; Houben-Weyl, Methods of Organic Chemistry, Thieme Verlag,
  • Suitable vinylaromatic monomers are styrene, o-, m- and p-methylstyrene, technical methylstyrene mixtures, p-tert-butylstyrene, ⁇ -methylstyrene, p-methoxystyrene, vinylnaphthalene, divinylbenzene, trivinylbenzene and divinylnaphthalene. Preference is given to styrene.
  • the content of polymerized vinylaromatic is preferably in the range of 5 to 50 wt .-%, particularly preferably in the range of 10 to 40 wt .-%.
  • Suitable diolefins are 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 1-phenyl-1,3-butadiene and 1,3-hexadiene. Preference is given to 1,3-butadiene and isoprene.
  • the content of copolymerized dienes is in the range from 50 to 95% by weight, preferably in the range from 60 to 90% by weight.
  • Diene ranges from 10 to 90%, the content of 1,4-trans double bonds ranges from 20 to 80% and the content of 1,4-cis double bonds is complementary to the sum of vinyl groups and 1,4 trans-continuous double bonds.
  • the vinyl content of the L-SBR is preferably> 20%.
  • L-SBR is meant both linear and branched or end-group modified rubbers.
  • branching agent used is preferably silicon tetrachloride or tin tetrachloride.
  • the solution polymerized vinyl aromatic / diene rubbers advantageously have Mooney viscosities (ML 1 + 4 at 100 ° C) in the range of 20 to 150 Mooney units, preferably in the range of 30 to 100 Mooney units.
  • Mooney viscosities ML 1 + 4 at 100 ° C
  • the high molecular weight L-SBR types having Mooney viscosities of> 80 ME may contain oils in amounts of 30 to 100 parts by weight based on 100 parts by weight of rubber.
  • Oil-free L-SBR rubbers have glass transition temperatures in the range of -80 ° to + 20 ° C, as determined by differential thermal analysis (DSC).
  • E-SBR is understood as meaning rubbers which are prepared in an emulsion process based on vinylaromatics and dienes, preferably conjugated dienes, and optionally other monomers (Ullmann's Encyclopedia of Industrial Chemistry, Vol. A 23, Rubber 3. Synthetic, VCH Verlagsgesellschaft mbH, D-69451 Weinheim, 1993, pp. 247-251).
  • Vinyl aromatics are styrene, p-methylstyrene and alpha-methylstyrene. Dienes are especially butadiene and isoprene. Further monomers are in particular acrylonitrile.
  • the content of copolymerized vinylaromatic is in the range of 10 to 60 wt.%.
  • the glass transition temperature is usually in the range of -50 ° C to + 20 ° C (determined by DSC) and the Mooney viscosities (ML 1 + 4 at 100 ° C) are in the range of 20 to 150 Mooney units.
  • the high molecular weight E-SBR types having Mooney values> 80 ME may contain oils in amounts of 30 to 100 parts by weight based on 100 parts by weight of rubber.
  • the oil-free E-SBR rubbers have glass transition temperatures of -70 ° to + 20 ° C, determined by differential thermal analysis (DSC).
  • Polybutadiene (BR) in particular comprises two different polybutadiene type classes.
  • the first class has a 1,4-cis content of at least 90% and is produced with the help of Ziegler / Natta catalysts based on transition metals. Preference is given to using catalyst systems based on Ti, Ni, Co and Nd (Houben-Weyl, Methods of Organic Chemistry, Thieme Verlag, Stuttgart, 1987, Volume E 20, pages 798 to 812, Ullmann's Encyclopedia of Industrial Chemistry , Vol A 23, Rubber 3rd Synthetic, VCH Verlagsgesellschaft mbH, D-69451 Weinheim, 1993, pp. 239-364).
  • the glass transition temperature of this polybutadiene is preferably ⁇ -90 ° C. (determined by means of DSC).
  • the second type of polybutadiene is made with Li catalysts and has vinyl contents of 10% to 90%.
  • the glass transition temperatures of these polybutadiene rubbers are in the range of -90 ° C to +20 ° C (determined by DSC).
  • Polyisoprene typically has a 1,4-cis content of at least 70%.
  • the term IR includes both synthetically produced 1,4-cis-polyisoprene and natural rubber, (NR).
  • Synthetically IR is prepared both by lithium and by means of Ziegler / Natta catalysts, preferably with titanium and neodymium catalysts (Houben-Weyl, Methods of Organic Chemistry, Thieme Verlag, Stuttgart, 1987, Volume E 20, pages 822-840 UUmann's Encyclopedia of Industrial Chemistry, Vol. A 23, Rubber 3. Synthetic, VCH Verlagsgesellschaft mbH, D-69451 Weinheim, 1993, p. 239-364).
  • natural rubber is used.
  • 3,4-polyisoprene which has glass transition temperatures in the range of -30 to +30 ° C, falls under IR.
  • carbon fibers such come with a mean fiber length of 5 to 550 ⁇ , preferably from 7 ⁇ to 250 ⁇ particular of 10 ⁇ to 150 ⁇ in question. These can be obtained, for example, by comminuting continuous fibers. Such are already commercially available as Sigrafil® FIL CM80-3.0 / 200-UM or CM150-3.0 / 200-UM from SGL Carbon. Also particularly preferred are recycled carbon fibers such as carboNXT® 100 from Carbonxt GmbH.
  • the average aspect ratio of the carbon fibers is from 10 to 100.
  • the carbon fibers are preferably used in an amount of from 30.1 to 70% by volume, in particular from 30.1 to 55% by volume.
  • suitable crosslinkers are preferably sulfur in the form of elemental sulfur or a sulfur donor, a peroxidic crosslinker, a resin crosslinker or a metal oxide.
  • Elemental sulfur is used as soluble or insoluble sulfur.
  • soluble sulfur is meant the only stable form at ordinary temperatures, the yellow cycloocta sulfur (S 8 ) or ⁇ -S, which consists of typical rhombic crystals and is highly soluble in carbon disulfide. Dissolve at 25 ° C in 100g CS 2 30g ⁇ -S (keyword "Sulfur” of the online Römpp Chemie Lexikon, as of August 2004, Georg Thieme Verlag Stuttgart).
  • insoluble sulfur is meant a sulfur modification which is not prone to blooming on the surface of rubber compounds. This particular sulfur modification is 60-95% insoluble in carbon disulfide.
  • sulfur donors examples include caprolactam disulfide (CLD), dithiomorpholine (DTDM) or 2- (4-Mo ⁇ holinodithio) benzothiazole (MBSS).
  • CLD caprolactam disulfide
  • DTDM dithiomorpholine
  • MBSS 2- (4-Mo ⁇ holinodithio) benzothiazole
  • peroxidic crosslinkers for example, bis (2,4-dichlorobenzyl) peroxide, dibenzoyl peroxide, bis (4-chlorobenzoyl) peroxide, 1, 1 -Bis- (t-butylperoxy) -3,3,5-trimethylcylohexane, tert-butyl perbenzoate, 2 , 2 bis (t-butylperoxy) butene, 4,4-di-tert-butyl peroxynonylvalerate, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, tert-butylcumyl peroxide, l, 3 Bis (t-butylperoxy isopropyl) benzene, di-t-butyl peroxide and 2,5-dimethyl-2,5-di (t-butylperoxy) hexyn-3 or mixtures thereof.
  • crosslinking agents may be advantageous to use, in addition to the peroxidic crosslinking agents, further additives which can be used to increase the crosslinking yield.
  • further additives which can be used to increase the crosslinking yield.
  • the total amount of the crosslinker is usually in the range of 0.1 to 100 parts by weight, preferably in the range of 0.5 to 75 parts by weight, and more preferably in the range of 1 to 50 parts by weight, based on 100 wt .-Parts of the sum of the rubber component a).
  • the amount of peroxidic crosslinking agent, ie active substance is usually in the range from 0.5 to 15 parts by weight, preferably in the range from 1 to 12.5 parts by weight and more preferably in the range from 1.5 to 10 Parts by weight, based on 100 parts by weight of the sum of the rubber component a).
  • Sulfur and / or sulfur donors are preferably used in the rubber mixture according to the invention in an amount in the range of 0.1 to 15 parts by weight, preferably 0.1-10 parts by weight, based on 100 parts by weight of component (s) a) used.
  • resin crosslinker for example, phenolic resins such as e.g. Diphenylamine, preferably in the form of Rhenofit® DDA-70 from Lanxess Deutschland GmbH, preferably in combination with aminic activators, such as e.g. Hexamethylene tetramine, for example in the form of Rhenogran® HEXA-80 of Lanxess Germany GmbH in question.
  • resin crosslinkers are used in an amount of 0.5 to 20 phr.
  • metal oxides for example MgO and / or ZnO can be used.
  • metal oxides are used in an amount of 0.5 to 20 phr.
  • the rubber mixture according to the invention preferably contains at least one filler.
  • Fillers are known to the person skilled in the art and are commercially available. Examples of suitable fillers are those selected from the group consisting of carbon black, silica, barium sulfate, titanium dioxide, zinc oxide, calcium oxide, calcium carbonate, magnesium oxide, aluminum oxide, iron oxide, aluminum hydroxide, magnesium hydroxide, aluminum silicates, diatomaceous earth, talc, kaolins, bentonites, carbon nanotubes, Teflon and silicates.
  • the filler or fillers are in the composition according to the invention preferably in an amount of 5 to 300 parts by weight, preferably from 10 to 200 parts by weight and more preferably from 20 to 150 parts by weight, in each case based on 100 wt. Parts of component (s) a) used.
  • Silica or "silica” (Ullmann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft mbH, D-69451 Weinheim, 1993, "Silica", pp. 635-645), is described in particular as fumed silica (ibid., Pp. 635-642) or as
  • the precipitated silicic acids have a specific surface area of from 5 to 1000 m 2 / g, determined by BET, preferably a specific surface area of from 20 to 400 m 2 / g They are obtained by treatment of waterglass with inorganic acids, sulfuric acid being preferably used.
  • the silicic acids may optionally also be used as mixed oxides with other metal oxides, such as Al, Mg, Ca, Ba, Zn, Zr, Ti. Oxides are present.
  • silicic acids having specific surface areas of from 5 to 1000 m 2 / g, more preferably from 20 to 400 m 2 / g, in each case determined by BET.
  • Silicic acid is usually used in an amount of greater than 0 to 150 parts by weight, preferably 1 to 120 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of component (s). used.
  • Carbon blacks used in the rubber mixtures according to the invention are likewise known to the person skilled in the art (see keywords “carbon” or “carbon black” in Ullmann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft mbH, D-69451 Weinheim, 1993, vol A 5 pp. 95-158).
  • N 110, N 115, N 121, N 125 are classified as N 110, N 115, N 121, N 125 according to the new ASTM nomenclature (ASTM D 1765 and D 2516) , N 212, N 220, N 231, N 234, N 242, N 293, N 299, S 315, N 326, N 330, N 332, N 339, N 343, N 347, N 351, N 375, N 472, N 539, N 550, N 582, N 630, N642, N 650, N 660, N 683, N 754, N 762, N 765, N 772, N 774, N 787, N 907, N 908 N 990 , N 991 S 3 etc. are designated.
  • the carbon blacks used according to the invention preferably have BET surface areas of between 5 and 200 m 2 / g.
  • Carbon black is usually added in the composition according to the invention in an amount of from 1 to 250 parts by weight, in particular from 1 to 150 parts by weight, preferably from 1 to 120 parts by weight and more preferably from 5 to 100 phr, in particular from 5 to 50 phr, based on 100 parts by weight of component (s) a) used.
  • the proportion of carbon black in the rubber mixture according to the invention is less than 1 phr, in particular 0 phr.
  • silicates such as aluminum silicate, alkaline earth silicate, such as magnesium silicate or
  • silicates such as kaolin, kieselguhr and other naturally occurring silicas, metal oxides such as alumina, magnesia, calcia,
  • Metal carbonates such as calcium carbonate, magnesium carbonate, zinc carbonate,
  • Metal sulfates such as calcium sulfate, barium sulfate,
  • Metal hydroxides such as aluminum hydroxide and magnesium hydroxide
  • Glass fibers and glass fiber products (slats, strands or glass microspheres),
  • Thermoplastics (polyamide, polyester, aramid, polycarbonate, syndiotactic 1, 2 polybutadiene and trans-I, 4-polybutadiene) as well
  • rubber additives to be added as component (s) e) other than components b) -d) include anti-aging agents, anti-reversion agents, light stabilizers, antiozonants, processing aids, plasticizers such as extender oils, mineral oils, tackifiers, blowing agents, dyes, pigments, waxes, Resins, extenders, organic acids, vulcanization retarders, vulcanization accelerators, sulfur activators, metal oxides, and other filler activators, such as triethanolamine, trimethylolpropane, polyethylene glycol, hexanetriol or other additives known in the rubber industry (Ullmann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft mbH, D Weinheim, 1993, vol.
  • sulfonamides for example, sulfonamides, sulfanilides or phthalimides can be added to the compositions according to the invention. Suitable are e.g.
  • N-trichloromethylsulfenylbenzenesulfanilide N-cyclohexylthiophthalimide, phthalic anhydride (PTA), salicylic acid (SAL), N-nitrosodiphenylamine (NDPA), trichloromelamine (TCM), maleic anhydride (MSA) and N-trichloromethylsulfenylbenzenesulfanilide (the latter commercially available under the name Vulcalent® E).
  • Corresponding vulcanization retarders are likewise mentioned in J. Schnetger, "Encyclopedia of Rubber Technology", 3rd edition, Hüthig Verlag, Heidelberg, 2004, page 590.
  • one or more further vulcanization accelerators which are suitable for sulfur vulcanization can also be used in the rubber mixture according to the invention.
  • vulcanization accelerators are mentioned in J. Schnetger “Lexikon der Kautschuktechnik” 3rd edition, Hüthig Verlag Heidelberg, 2004, pages 514-515, 537-539 and 586-589.
  • vulcanization accelerators can be selected, for example, from the group of xanthates, dithiocarbamates, tetramethylthiuram disulfides, thiurams, thiazoles, thiourea derivatives, amine derivatives such as tetramines, sulfenimides, piperazines, amine carbamates, sulfenamides, bisphenol and triazine. derivatives.
  • Suitable vulcanization accelerators are benzothiazyl-2-cyclohexylsulfenamide (CBS), benzothiazyl-2-tert-butylsulfenamide (TBBS), benzothiazyl-2-dicyclohexylsulfenamide (DCBS), 1,3-diethylthiourea (DETU), 2-mercaptobenzothiazole (MBT).
  • CBS benzothiazyl-2-cyclohexylsulfenamide
  • TBBS benzothiazyl-2-tert-butylsulfenamide
  • DCBS benzothiazyl-2-dicyclohexylsulfenamide
  • DETU 1,3-diethylthiourea
  • MTT 2-mercaptobenzothiazole
  • ZMBT zinc salts
  • CDMC copper dimethyldithiocarbamate
  • MCS benzothiazyl-2-sulfenmorpholide
  • DCBS benzothiazyldicyclohexylsulfenamide
  • MBTS 2-mercaptobenzothiazole disulfide
  • MPTD dimethyldiphenylthiuram disulfide
  • TBZTD tetrabenzylthiuram disulfide
  • TMTM tetramethylthioremonosulfide
  • DPTT dipentamethylenethiuram tetrasulphide
  • IBTD tetra-isobutylthiuram disulphide
  • TETD tetraethylthiuram disulphide
  • TMTD zinc N-dimethyldithiocarbamate
  • ZDEC zinc N-dibutyl dithiocarbamate
  • the vulcanization accelerators are preferably used in an amount in the range of 0.1 to 15 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of component (a) a).
  • Sulfur Activators are preferably used in an amount in the range of 0.1 to 15 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of component (a) a).
  • the mixture according to the invention can also be contained zinc oxide as an activator for sulfur vulcanization.
  • zinc oxide as an activator for sulfur vulcanization.
  • the selection of a suitable amount is possible for the skilled person without much effort. If the zinc oxide is used in a slightly higher dosage, this leads to an increased formation of monosulfide bonds and thus to an improved aging resistance.
  • the rubber composition according to the invention also contains stearic acid (octadecanoic acid). This is known to the person skilled in the art that it has a broad spectrum of activity in rubber technology. Thus, one of their effects is that it results in improved dispersion of the vulcanization accelerators. Furthermore, a complex formation with zinc ions occurs in the context of sulfur vulcanization.
  • Zinc oxide is usually in the composition of the invention in an amount of 0.5 to 15 parts by weight, preferably 1 to 7.5 parts by weight, more preferably 1 to 5 wt.%, Based on 100 parts by weight the component (s) a) used.
  • Stearic acid is added in the composition according to the invention in an amount of from 0.1 to 7, preferably from 0.25 to 7 parts by weight, preferably from 0.5 to 5 parts by weight, based on 100 parts by weight of component (n) a) used.
  • component (n) a) used.
  • zinc oxide and stearic acid zinc stearate can be used.
  • an amount of 0.25 to 5 parts by weight, preferably 1 to 3 parts by weight, based in each case on 100 parts by weight of component (a) is usually used.
  • compositions according to the invention may e.g. Mercaptobenzimidazole (MBI), 2-mercaptomethylbenzimidazole (2-MMBI), 3-mercaptomethylbenzimidazole (3-MMBI), 4-
  • anti-aging agents can also be used as further component (s) e), for example in the form of discoloring anti-aging agents with fatigue and ozone protection action, e.g. N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD); discoloring aging inhibitor with fatigue protection, but without ozone protective action, e.g. Phenyl-a-naphthylamine (PAN); discoloring anti-aging agents with little fatigue and without ozone protection, e.g. octylated diphenylamine (ODPA); non-discoloring anti-aging agent with fatigue protection and good heat protection, e.g.
  • IPPD N-isopropyl-N'-phenyl-p-phenylenediamine
  • PAN Phenyl-a-naphthylamine
  • ODPA octylated diphenylamine
  • SPH styrenated phenols
  • BHT 2,6-di-tert-butyl-p-cresol
  • Waxes mixture of special hydrocarbons
  • cyclic acetals cyclic acetals and enol ethers
  • hydrolysis protectants e.g. Polycarbodiimides.
  • compositions according to the invention which are preferably selected from the group consisting of thiophenols, Thiophenolzinksalzen, substituted aromatic disulfides, peroxides, derivatives of thiocarboxylic acids, hydrazine derivatives, nitroso compounds and metal complexes, more preferably Eisenhemiporphyrazin, iron phthalocyanine, Eisenacetonylacetat and its Zn salt.
  • the rubber additives which can be used as further component (s) e) are used in customary amounts, which i.a. according to the intended use, used.
  • Typical amounts of individual rubber additives of component e), preferably other than extender oils, are for example from 0.1 to 50 phr.
  • paraffin As examples of such extender oils paraffin, naphthenic and aromatic extender oils can be used, as are commonly obtained in the fractionation of petroleum in the petrochemical.
  • the extender oils preferably have a dynamic viscosity of 5 to 35 mm 2 / s at 100 ° C.
  • Particularly preferred are paraffin oils.
  • Preferred paraffin oils are, for example, Sunpar® 2280 from Sunoco, Conopure® 12P from ConocoPhillips, white oil such as ParaLux® 6001 from Chevron Texaco. Also in the liquefaction (gas to liquid so GTL) oils such as. Shell's Risella® X 430 are also preferred.
  • extender oils are used in an amount of 0 to 300 phr, particularly preferably 0 to 200 phr, in particular from 0 to 100 phr, based on 100 parts by weight of rubber.
  • Particularly preferred extender oils are used in combination with EPDM or SBR. Both E-SBR and S-SBR can be used in the rubber mixtures according to the invention in oil-hidden form. Suitable are TDAE (Treated Distillates Aromatic Extract), MES (Mild Extraction Solvates) and naphthenic oils.
  • the rubber mixture according to the invention is one containing
  • the abovementioned parts by weight of the components a) to d) are also based in each case on 100 parts by weight of the rubber component (s) a).
  • the vulcanizable rubber composition according to the invention has an anisotropy, preferably a conductivity anisotropy along a spatial axis that is at least 10%, preferably more than 20%, higher than in at least one of the other two spatial axes.
  • Another object of the invention is a process for the preparation of the rubber mixtures of the invention.
  • the preparation of the rubber mixture according to the invention is preferably carried out by mixing the components a) to c) and optionally one or more further component (s), in particular the component (s) d) to e) on a roll or by extrusion through a slot die.
  • the anisotropy is preferably generated by the roller or the slot die.
  • the mixing can be done in one or more stages. Preference is given to a mixing process, preferably in one
  • Internal mixer first the components without the crosslinker c) are mixed, preferably at a temperature of 100 to 200 ° C, and then the crosslinker component c) and optionally further components are added and on a roller, preferably also called “final mixing stage” , is mixed at a temperature ⁇ 120 ° C., preferably ⁇ 110 ° C., in particular from 10 to 80 ° C.
  • the carbon fiber-containing mass premixed without crosslinker is anisotropically aligned by mixing on the roll, preferably with a small gap ,
  • the mixture of the components without crosslinker is preferably carried out at 110 ° C to 160 ° C, preferably 120 ° C to 150 ° C, more preferably 130 ° C to 140 ° C, wherein the mixing times at these temperatures preferably in the range of 1 to 15 Minutes and are chosen so that not already a Vulkanisationsstart takes place.
  • extrude components a) to c) and optionally further components at a temperature below the vulcanization temperature through a slot die.
  • This nozzle is preferably characterized in that the ratio of nozzle width to nozzle height is greater than 10, more preferably greater than 15, even more preferably greater than 20, and particularly preferably greater than 25.
  • the extrusion is carried out at a temperature of ⁇ 100 ° C, especially ⁇ 70 ° C, in particular ⁇ 50 ° C, preferably with a slot die with a ratio of nozzle width to nozzle height of greater than 25.
  • the invention further relates to a process for crosslinking these rubber mixtures to produce the corresponding vulcanizates.
  • the vulcanization of the compositions of the invention is usually carried out at a temperature in the range of 100 to 250 ° C, preferably from 130 to 180 ° C, either under normal pressure (1 bar) or optionally under a pressure of up to 200 bar. Typically, this vulcanization occurs as part of a molding process.
  • Another object of the invention relates to the vulcanizates per se, in particular obtainable by vulcanization of the rubber mixtures according to the invention, in particular in the form of moldings.
  • the invention also relates to vulcanizates containing
  • the vulcanizates may contain the other components d) and e) already described for the rubber mixtures according to the invention in an appropriate amount.
  • the invention furthermore relates to the use of the rubber mixtures according to the invention for producing various tire components, in particular for tire treads, sub-races, carcasses, sidewalls, reinforced sidewalls for run-flat tires and apex mixtures and also for the production of technical rubber articles such as damping elements, roller coverings, conveyor belt linings, belts, spinning cops , Seals, golf ball cores and soles.
  • Particularly suitable are the mixtures for the production of tire treads, Subtreads, carcasses and Apexmisch Institute.
  • Tires or tire parts also include, for example, treads for summer, winter and all-season tires as well as running surfaces of car and truck tires as well as tires for racing cars, motorcycles and bicycles. Examples:
  • the rubber mixtures were prepared in a two-stage mixing process, with an internal mixer with 1.5 l internal volume (GK 1.5 from Werner & Pfleiderer, Stuttgart with intermeshing kneading elements, PS 5A blade geometry) being used for the first mixing stage.
  • the last mixing step was carried out on a roller.
  • the components used in the mixing series are listed in the following tables. All data are parts by weight based on 100 parts by weight of rubber. If oil-stretched EPDM was used in the preparation of the mixture, the phr specifications of the other components are each based on 100 parts by weight of the oil-free rubber.
  • the order of mixing ingredients given in the tables corresponds to the order of addition to the internal mixer, each without the crosslinker components.
  • the mixture After reaching an internal temperature of 150 ° C / 6 min. in the internal mixer, the mixture was ejected and cooled on a pre-heated to 40 ° C roller.
  • the addition of the crosslinker components (in the EPDM examples of Rhenogran S-80, Rhenogran MBT-80, Vulkacit Thiuram / C) was carried out at a temperature of ⁇ 90 ° C. after 24 hours of intermediate storage on the roll.
  • the carbon fibers were anisotropically aligned in the rolling direction.
  • the mixture skins obtained in this way are marked so that later the anisotropically aligned fibers correspond to the mark and test pieces can be prepared from the vulcanizates both in the "rolling direction" and "transversely” to the rolling direction.
  • the Mooney viscosity after 4 min. (ML 1 + 4/125 ° C) determined. It is conspicuous and surprising that the Mooney viscosity increases to an unexpectedly small extent. This circumstance enables the high filling levels of carbon fiber while preserving the processability.
  • test pieces necessary for the vulcanization characterization were obtained by press vulcanization of the mixtures at a hydraulic pressure of 120 bar.
  • the rubber blends were vulcanized at 180 ° C for 10 minutes as a result of the vulcanization test.
  • Vulkanisatproben with a length of 100 mm and a width of 100 mm are used.
  • the electrodes used are copper rods. The current flow can be seen from Fig. 2.
  • Rhenogran® ® S-80 Lanxess Germany GmbH (Sulfur 80% strength in polymer binder)
  • Rhengran ® MBT-80 80% 2-mercapto-benzothiazole and 20% polymeric binder and dispersing agent of
  • Rhenofit DDA-70 70% diphenylamine derivative on 30% silica, Lanxess GmbH Rhenogran Hexa-80: 80% hexamethylenetetramine in 20% polymer binder Lanxess Germany
  • Corax N326 soot, smock active, Orion Engineered Carbon, D
  • VivaTec 500 TDAE Oil, H & R Group Hamburg, Germany
  • Vulcanox 4020 / LG N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine (6PPD), Lanxess Germany
  • Rhenogran® IS 90-65 sulfur-based vulcanizing agent for natural and synthetic rubber compounds
  • Vulkacit CZ / EGC N-cyclohexyl-2-benzothiazole sulfenamide, CBS, [CAS No. 95-33-0], Lanxess

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Abstract

L'invention concerne de nouveaux mélanges de caoutchouc vulcanisables, contenant a) au moins un caoutchouc ayant des doubles liaisons, b) au moins 30 % en volume, par rapport au mélange de caoutchouc, de fibres de carbone d'une longueur moyenne de fibres comprise entre 5 et 550 µm et un rapport de forme moyen compris entre 10 et 100, et c) au moins un réticulant.
PCT/EP2017/082264 2016-12-28 2017-12-11 Mélanges de caoutchouc WO2018121976A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110240758A (zh) * 2019-06-18 2019-09-17 宁国市正道橡塑零部件有限公司 一种自润滑耐磨橡胶材料及其制备方法
CN113474399A (zh) * 2019-03-14 2021-10-01 Sika技术股份公司 可热膨胀的组合物和其在焊接密封带中的用途
CN113861522A (zh) * 2021-10-25 2021-12-31 昆明翔鹰机电设备有限公司 一种耐磨的抗疲劳合成橡胶材料
WO2023000097A1 (fr) * 2021-07-21 2023-01-26 ARLANXEO Canada Inc. Polymères de poly(isobutylène-co-paraméthylstyrène) ramifiés

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56104906A (en) 1980-01-25 1981-08-21 Asahi Chem Ind Co Ltd Polymer having reactive end group
DE2034989C2 (fr) 1969-07-17 1988-04-14 Michelin & Cie. (Compagnie Generale Des Etablissements Michelin), Clermont-Ferrand, Fr
JPH02166328A (ja) 1988-12-19 1990-06-27 Kajima Corp 移動用発電、空調システム
JPH04173236A (ja) 1990-11-06 1992-06-19 Bando Chem Ind Ltd 導電異方性構造体
EP1705211A2 (fr) * 2005-03-23 2006-09-27 Nissin Kogyo Co., Ltd Matière composite comprenant des nanofibres de carbone
WO2006123859A1 (fr) * 2005-05-17 2006-11-23 Applied Carbon Nono Technology Co., Ltd. Procedes de fabrication de composites a matrice en metal, polymere ou ceramique contenant des nanofibres reparties de maniere aleatoire ou alignees suivant une direction
EP1749853A2 (fr) * 2005-06-30 2007-02-07 Nissin Kogyo Co., Ltd Matériau composite

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2034989C2 (fr) 1969-07-17 1988-04-14 Michelin & Cie. (Compagnie Generale Des Etablissements Michelin), Clermont-Ferrand, Fr
JPS56104906A (en) 1980-01-25 1981-08-21 Asahi Chem Ind Co Ltd Polymer having reactive end group
JPH02166328A (ja) 1988-12-19 1990-06-27 Kajima Corp 移動用発電、空調システム
JPH04173236A (ja) 1990-11-06 1992-06-19 Bando Chem Ind Ltd 導電異方性構造体
EP1705211A2 (fr) * 2005-03-23 2006-09-27 Nissin Kogyo Co., Ltd Matière composite comprenant des nanofibres de carbone
WO2006123859A1 (fr) * 2005-05-17 2006-11-23 Applied Carbon Nono Technology Co., Ltd. Procedes de fabrication de composites a matrice en metal, polymere ou ceramique contenant des nanofibres reparties de maniere aleatoire ou alignees suivant une direction
EP1749853A2 (fr) * 2005-06-30 2007-02-07 Nissin Kogyo Co., Ltd Matériau composite

Non-Patent Citations (17)

* Cited by examiner, † Cited by third party
Title
"Stichwort Schwefel'' des online Römpp Chemie Lexikons", August 2004, GEORG THIEME VERLAG
"Ullmann's Encyclopedia of Industrial Chemistry", 1993, VCH VERLAGSGESELLSCHAFT MBH, pages: 635 - 645
"Ullmann's Encyclopedia of Industrial Chemistry", vol. A 23, 1993, VCH VERLAGSGESELLSCHAFT MBH, pages: 239 - 364
"Ullmann's Encyclopedia of Industrial Chemistry", vol. A 23, 1993, VCH VERLAGSGESELLSCHAFT MBH, pages: 240 - 364
"Ullmann's Encyclopedia of Industrial Chemistry", vol. A 23, 1993, VCH VERLAGSGESELLSCHAFT MBH, pages: 247 - 251
"Ullmann's Encyclopedia of Industrial Chemistry", vol. A 23, 1993, VCH VERLAGSGESELLSCHAFT MBH, pages: 366 - 417
"Ullmann's Encyclopedia of Industrial Chemistry", vol. A 5, 1993, VCH VERLAGSGESELLSCHAFT MBH, pages: 95 - 158
CHEMICAL ABSTRACTS, Columbus, Ohio, US; abstract no. 1314-13-2
CHEMICAL ABSTRACTS, Columbus, Ohio, US; abstract no. 64742 -62-7
HOUBEN-WEYL: "Methoden der Organischen Chemie", vol. E 20, 1987, THIEME VERLAG, pages: 114 - 134
HOUBEN-WEYL: "Methoden der Organischen Chemie", vol. E 20, 1987, THIEME VERLAG, pages: 798 - 812
HOUBEN-WEYL: "Methoden der Organischen Chemie", vol. E 20, 1987, THIEME VERLAG, pages: 822 - 840
I. FRANTA: "Elastomers and Rubber Compounding Materials", 1989, ELSEVIER, pages: 73 - 74,92-94
J. SCHNETGER: "Lexikon der Kautschuktechnik", 2004, HÜTHIG VERLAG HEIDELBERG, pages: 514 - 515,537-539,586-589
J. SCHNETGER: "Lexikon der Kautschuktechnik", 2004, HÜTHIG VERLAG, pages: 590
K.-H. NORDSIEK; K.-H. KIEPERT, GAK KAUTSCHUK GUMMI KUNSTSTOFFE, vol. 33, no. 4, 1980, pages 251 - 255
W. HOFFMANN: "Kautschuktechnologie", 1980, GENTNER VERLAG, pages: 254 ff

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113474399A (zh) * 2019-03-14 2021-10-01 Sika技术股份公司 可热膨胀的组合物和其在焊接密封带中的用途
CN113474399B (zh) * 2019-03-14 2023-07-25 Sika技术股份公司 可热膨胀的组合物和其在焊接密封带中的用途
CN110240758A (zh) * 2019-06-18 2019-09-17 宁国市正道橡塑零部件有限公司 一种自润滑耐磨橡胶材料及其制备方法
WO2023000097A1 (fr) * 2021-07-21 2023-01-26 ARLANXEO Canada Inc. Polymères de poly(isobutylène-co-paraméthylstyrène) ramifiés
CN113861522A (zh) * 2021-10-25 2021-12-31 昆明翔鹰机电设备有限公司 一种耐磨的抗疲劳合成橡胶材料

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