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WO2010006889A2 - Agents de couplage pour caoutchoucs chargés - Google Patents

Agents de couplage pour caoutchoucs chargés Download PDF

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Publication number
WO2010006889A2
WO2010006889A2 PCT/EP2009/057753 EP2009057753W WO2010006889A2 WO 2010006889 A2 WO2010006889 A2 WO 2010006889A2 EP 2009057753 W EP2009057753 W EP 2009057753W WO 2010006889 A2 WO2010006889 A2 WO 2010006889A2
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Prior art keywords
electron
acyclic
cyclic
tert
bis
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PCT/EP2009/057753
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WO2010006889A3 (fr
Inventor
Michèle Gerster
Eva Peregi
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Basf Se
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Publication of WO2010006889A3 publication Critical patent/WO2010006889A3/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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K5/0016—Plasticisers
    • 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
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
    • 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/548—Silicon-containing compounds containing sulfur

Definitions

  • the present invention relates to compositions comprising a rubber, a white reinforcing filler, a coupling agent and a coupling agent regulator, to processes for the preparation of a filled rubber compound, respectively, a filler-reinforced vulcanizate from these compositions, and to filled rubber compounds, respectively, filler-reinforced vulcanizates obtained by these processes.
  • Filler-reinforced vulcanizates have broad applications, for example in vehicle tires.
  • EP 1 535 961 A1 describes tires made from a rubber composition comprising silica as filler.
  • the rubber composition used comprises a rubber component, silica, a partial ester compound of maleic anhydride and a polyoxypropylene derivative, and optionally a silane coupling agent.
  • Examples 10 to 16 of EP 1 535 961 A1 describe rubber composition comprising an styrene butadiene copolymer rubber (SBR), silica, mono [POP(5) lauryl ether]maleic acid ester and bis(3-triethoxysilylpropyl)polysulfide (TESPT), a silane coupling agent sold under the tradename Si 69® by Evonik.
  • SBR styrene butadiene copolymer rubber
  • TESPT bis(3-triethoxysilylpropyl)polysulfide
  • compositions are first kneaded at a start temperature of 70 0 C for 4 minutes using a Branbury mixer (compounding step), and then kneaded at a start temperature of 70 0 C in the presence of sulfur and vulcanization accelerators for 1 minute using a Branbury mixer to yield non-vulcanized rubber compositions.
  • the compounding step especially when bis(3-triethoxysilylpropyl)tetrasulfide (TESPT) sold under the tradename Si 69® by Evonik or bis(3-triethoxysilylpropyl)disulfide (TESPD) sold under the tradename Si 75® by Evonik are used as coupling agent, suffer from the drawback that side reactions are prone to occur at the elevated temperatures (usually 160 0 C) required in that step. These side reactions negatively influence the properties of the rubber compound obtained in this step.
  • TESPT bis(3-triethoxysilylpropyl)tetrasulfide
  • TESPD bis(3-triethoxysilylpropyl)disulfide
  • other steps of the process such as the homogenizing step or the curing step or the properties of the rubber compound or of the filler-reinforced vulcanizate prepared from this rubber compound should not be negatively influenced.
  • composition of claim 1 the processes of claims 8 and 10, the rubber compound of claim 9, the filler-reinforced vulcanizate of claim 12, and the mixture of claim 14.
  • composition of the present inventions comprises a) a naturally occurring or synthetic rubber susceptible to oxidative, thermal, dynamic, light-induced and/or ozone-induced degradation, b) a white reinforcing filler, c) a coupling agent selected from the group consisting of organofunctionalized silanes, polysulfide silanes, blocked mercaptosilanes, thio substituted silanes, sulfoxide or sulfone substituted silane coupling agents, and oligomeric hydrolysis product thereof, and d) a coupling agent regulator selected from the group consisting of cyclic or acyclic
  • Rubbers are to be understood as meaning macromolecular materials which after considerable deformation under a small load at room temperature rapidly regain approximately their original shape. See also Hans-Georg Elias, "An Introduction to Polymer Science", Section 12. "Elastomers”, pp. 388-393, 1997, VCH Verlagsgesellschaft mbH, Weinheim, Germany or "Ullmann's Encyclopedia of Industrial Chemistry, fifth, completely revised edition, Volume A 23", pp. 221-440 (1993).
  • Examples of rubbers which may be present in the compositions of the invention are the following materials or mixtures thereof:
  • Polymers of diolefins for example polybutadiene or polyisoprene.
  • Copolymers of mono- and diolefins with one another or with other vinyl monomers e.g. propylene-isobutylene copolymers, propylene-butadiene copolymers, isobutylene-isoprene copolymers, ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers, acrylonitrile-butadiene copolymers, and also terpolymers of ethylene with propylene and with a diene, such as hexadiene, dicyclopentadiene or ethyli- denenorbornene.
  • a diene such as hexadiene, dicyclopentadiene or ethyli- denenorbornene.
  • Copolymers of styrene or ⁇ -methylstyrene with dienes or with acrylic derivatives e.g. sty- rene-butadiene, styrene-butadiene-alkyl acrylate and styrene-butadiene-alkyl methacrylate; block copolymers of styrene, e.g. styrene-butadiene-styrene, styrene-isoprene-styrene and styrene-ethylenebutylene-styrene, and also adhesives prepared from the latter three.
  • Halogen-containing polymers e.g. polychloroprene, chlorinated rubber, chlorinated or brominated copolymer of isobutylene-isoprene (halobutyl rubber), halogenated copolymers of isobutylene and p-methylstyrene.
  • Aqueous emulsions of natural or synthetic rubbers e.g. natural rubber latex or latices of carboxylated styrene-butadiene copolymers.
  • the rubber component is based on highly unsaturated rubbers such as, for example, natural rubber and/or styrene-butadiene rubber and/or butadiene rubber, S-SBR and E-SBR.
  • highly unsaturated rubbers such as, for example, natural rubber and/or styrene-butadiene rubber and/or butadiene rubber, S-SBR and E-SBR.
  • natural rubbers are used for production of truck tires.
  • Representative of the highly unsaturated polymers that can be employed in the practice of this invention are - A -
  • diene rubbers Such rubbers will ordinarily possess an iodine number of between about 20 to about 450, although highly unsaturated rubbers having a higher or a lower (e.g. of 50 to 100) iodine number can also be employed.
  • diene rubbers that can be utilized are polymers based on conjugated dienes such as, for example, 1 ,3-butadiene; 2-methyl- 1 ,3-butadiene; 1 ,3-pentadiene; 2,3-dimethyl-1 ,3-butadiene; and the like, as well as copolymers of such conjugated dienes with monomers such as, for example styrene, ⁇ -methylstyrene, acetylene, e.g.
  • conjugated dienes such as, for example, 1 ,3-butadiene; 2-methyl- 1 ,3-butadiene; 1 ,3-pentadiene; 2,3-dimethyl-1 ,3-butadiene; and the like, as well as copolymers of such conjugated dienes with monomers such as, for example styrene, ⁇ -methylstyrene, acetylene, e.g.
  • Preferred highly unsaturated rubbers include natural rubber, cis-polyisoprene, polybutadiene, poly(styrene-butadiene), styrene-isoprene copolymers, isoprene-butadiene copolymers, styrene-isoprene-butadiene tripolymers, polychloroprene, chloro-isobutene-isoprene, nitrile- chloroprene, styrene-chloroprene, and poly(acrylonitrile-butadiene).
  • mixtures of two or more highly unsaturated rubbers with polymers or rubbers having less unsaturation such as EPDM or EPR, butyl or
  • the rubbers of interest are preferably natural or synthetic rubbers or mixtures thereof.
  • Reinforcing white filler is to be understood to mean a white filler capable of reinforcing alone, without any means other than an intermediate coupling agent, a rubber composition intended for the manufacture of tires.
  • the reinforcing white filler is capable of replacing admixing a conventional carbon black filler in its reinforcing function.
  • the reinforcing white filler is silica (SiO 2 ) or alumina (AI 2 O 3 ), or a mixture of these two fillers.
  • the silica used may be any reinforcing silica known to the person skilled in the art, in particular any precipitated or pyrogenic silica having a BET surface area and a specific CTAB surface area both of which are less than 450 m 2 /g.
  • the highly dispersable precipitated silicas are preferred, in particular when the invention is used to manufacture tires having a low rolling resistance.
  • “Highly dispersible silica” is understood to mean any silica having a very substantial ability to disagglomerate and to disperse in a polymer matrix, which can be observed in known manner by electron or optical microscopy on thin sections.
  • Non-limiting examples of such preferred highly dispersible silicas include the silica Perkasil KS 430 (RTM) from Akzo, the silica BV 3380 (RTM) from Evonik, the silicas Zeosil 1 165 MP (RTM) and Zeosil 1 115 MP (RTM) from Rh ⁇ ne-Poulenc, the silica Hi-SiI 2000 (RTM) from PPG, the silicas Zeopol 8741 (RTM) or Zeopol 8745 (RTM) from Huber, and treated precipitated silicas such as, for example, the aluminium-"doped" silicas described in EP-A-O 735 088.
  • the reinforcing alumina is a highly dispersable alumina having a BET surface area from 30 to 400 m 2 /g, more preferably 80 to 250 m 2 /g, an average particle size of at most 500 nm, more preferably at most 200 nm, a high amount of reactive AI-OH surface functions, as described in EP-A-O 810 258.
  • Non-limitative examples of such reinforcing aluminas are in particular the aluminas A125 (RTM), CR125 (RTM) and D65CR (RTM) of Baikowski.
  • the physical state in which the reinforcing white filler is present is immaterial, whether it be in the form of a powder, microbeads, granules or balls.
  • the "reinforcing white filler” is also understood to mean mixtures of different reinforcing white fillers, in particular highly disper- sible silicas and/or aluminas such as described above.
  • the reinforcing white filler may also be used in a blend (mixture) with carbon black.
  • Suitable carbon blacks are all the carbon blacks, in particular carbon blacks of the type HAF, ISAF or conventionally used in tires and, particularly, in treads for tires.
  • Non-limiting examples of such blacks include the blacks N115, N134, N220, N234, N339, N347, N375 and N550.
  • the quantity of carbon black present in the total reinforcing filler may vary within wide limits, this quantity preferably being less than the quantity of reinforcing white filler present in the composition.
  • WO-A-2005/059022 and WO-A-2007/039416 disclose coupling agents for silica in rubber.
  • thio substituted silanes as well as sulfoxide or sulfone substituted silane coupling agents are disclosed in WO-A-2007/039416.
  • Preferred examples of thio substituted silanes, sulfoxide or sulfone substituted silane coupling agents are compounds of the formula Ia ?2
  • Ri is hydrogen, CrC 2 5alkyl, d-C 2 5alkyl substituted with furyl, morpholine, Ci-C 4 dialkylamino, Ci-C 4 trialkylammonium or M + O 3 S-; C 2 -C 25 alkyl interrupted by oxygen; C 5 -Ci 2 cycloalkyl, C 2 -C 25 alkenyl, unsubstituted or Ci-C 4 alkyl-substituted phenyl; unsubstituted or with halogen, nitro, Ci-C 4 alkyl or Ci-C 4 alkoxy substituted C 7 -Ci 5 arylalkyl; C 7 -Ci 2 phenoxyalkyl, unsubsti-
  • Ri is -CN, -SOR 8 , -SO 2 R 8 , -NO 2 or -COR 8 ;
  • Ri is Ci-C 25 alkylene, Ci-C 25 alkylene substituted with Ci-C 4 alkyl; C 2 -C 25 alkylene substituted with Ci-C 4 alkyl and interrupted by oxygen; C 2 -C 25 alkylene interrupted by oxygen, sulfur,
  • R 2 , R3 and R 4 are each independently of the others CrC 2 5alkyl, C 2 -C 2 5alkyl interrupted by oxygen; C 5 -Ci 2 cycloalkyl, C 2 -C 25 alkenyl, unsubstituted or d-C 4 alkyl-substituted phenyl, C 7 -C 9 phenylalkyl, Ci-C 25 alkoxy, C 3 -C 25 alkoxy interrupted by oxygen; C 5 -Ci 2 cycloalkoxy, C 2 -C 25 alkenyloxy, unsubstituted or Ci-C 4 alkyl-substituted phenoxy, C 7 -C 9 phenylalkoxy, halogen, C 2 -C 25 alkanoyloxy or unsubstituted or Ci-C 4 alkyl substituted benzoyloxy; or at least two of R 2 , R 3 and R 4 are -O-R 1 5-O-; or R 2
  • R 3 is additionally
  • R 4 is additionally R 4
  • R 4 is Ci-C 25 alkoxy, C 3 -C 25 alkoxy interrupted by oxygen; C 5 -Ci 2 cycloalkoxy, C 2 -C 25 alkenyl- oxy, unsubstituted or Ci-C 4 alkyl-substituted phenoxy, C 7 -C 9 phenylalkoxy, halogen, C 2 -C 25 al- kanoyloxy or unsubstituted or Ci-C 4 alkyl substituted benzoyloxy; R 5 is Ci-C 25 alkylene, C 5 -Ci 2 cycloalkylene, unsubstituted or Ci-C 4 alkyl substituted phenylene;
  • R 7 is a direct bond or — C-R 1 - ,
  • R 8 is Ci-C 25 alkyl, C 2 -C 25 alkyl interrupted by oxygen; C 5 -Ci 2 cycloalkyl, C 2 -C 25 alkenyl, C 2 -C 25 al- kinyl, C 7 -C 9 phenylalkyl, unsubstituted or d-C 4 alkyl-substituted phenyl,
  • R 9 is Ci-C 5 alkyl
  • Rio is hydrogen or d-C 4 alkyl
  • Rn and Ri 2 are each independently of the other hydrogen, CF 3 , Ci-Ci 2 alkyl or phenyl, or R 11 and R 12 , together with the carbon atom to which they are bonded, form a Cs-Cscycloalkyli- dene ring that is unsubstituted or substituted by from 1 to 3 CrC 4 alkyl groups,
  • R 13 is a direct bond, oxygen or -N(R 14 )-,
  • R 14 is hydrogen or CrC 12 alkyl
  • R 15 is CrC 25 alkylene or CrC 25 alkylene substituted with CrC 25 alkyl
  • R 16 is CrC 25 alkylene or CrC 25 alkylene substituted with CrC 25 alkyl
  • R 17 is hydrogen, halogen, nitro or CrC 4 alkoxy
  • Ri 8 and Ri 9 are each independently of the other hydrogen, d-C ⁇ alkyl, C 3 -Ci 2 alkenyl or phenyl,
  • R 2 0 is hydrogen or d-C 4 alkyl
  • R 21 , R 22 and R 2 3 are each independently of the other hydrogen or d-C 4 alkyl
  • R 24 is hydrogen or Ci-C 4 alkyl
  • R 2 5 is Ci-Ci 2 alkyl
  • R 2 6 is hydrogen or d-C ⁇ alkyl
  • M is sodium, potassium or ammonium, m is 0, 1 or 2; and n is 1 or 2; or an oligomeric hydrolysis product of the compound of the formula Ic.
  • polysulfide silanes are bis(3-triethoxysilylpropyl)tetrasulfide (TESP) sold under the trademark Si 69® by Evonik and bis(3-triethoxysilylpropyl)disulfide (TESPD) sold under the trademark Si 75® by Evonik.
  • 3-octanoylthio-i-propyltriethoxysilane is an example of an organofunctionalized silane, a blocked mercaptosilane and a thio-substituted silane.
  • the coupling agent is a polysulfide silane, an organofunctionalized silane, a blocked mercaptosilane or a thio-substituted silane.
  • interesting compositions comprise, as component (c) bis(3-triethoxysilylpropyl)tetrasulfide (TESP) sold under the trademark Si 69® by Evonik, bis(3-triethoxysilylpropyl)disulfide (TESPD) sold under the trademark Si 75® by Evonik or S-octanoylthio-i-propyltriethoxysilane sold under the tradename NXTTM Silane by GE Advanced Materials.
  • TEP bis(3-triethoxysilylpropyl)tetrasulfide
  • TESPD bis(3-triethoxysilylpropyl)disulfide
  • Si 75® by Evonik
  • the coupling agent is polysulfide silane, in particular bis(3-triethoxysilylpropyl)tetrasulfide (TESP) sold under the trademark Si 69® by Evonik or bis(3-triethoxysilylpropyl)disulfide (TESPD) sold under the trademark Si 75® by Evonik. Most preferably, it is bis(3-triethoxysilylpropyl)tetrasulfide (TESP) sold under the trademark Si 69® by Evonik.
  • TEP bis(3-triethoxysilylpropyl)tetrasulfide
  • nent (d) is - R 3 Ri is hydrogen, Ci-C 25 alkyl, with oxygen or sulfur interrupted C 3 -C 25 alkyl; unsubstituted or with Ci-C 4 alkyl substituted phenyl; unsubstituted or with Ci-C 4 alkoxy or Ci-C 4 alkyl substituted C 7 -C 25 phenylalkyl; or C 3 -C 25 alkenyl,
  • R 2 and R 3 are independently of each other hydrogen or Ci-Ci 2 alkyl
  • R 3 is hydroxy, Ci-C 25 alkyl, with oxygen or sulfur interrupted C 3 -C 25 alkyl, unsubstituted or with
  • Ci-C 4 alkyl substituted phenyl Ci-C 4 alkyl substituted phenyl
  • component (d) is unsubstituted or with d-C 4 alkyl substitu- ted phenyl, Ci-C 25 alkoxy, Ci-C 25 alkylthio or — N ⁇ , wherein
  • R 2 and R 3 are independently of each other hydrogen or Ci-Ci 2 alkyl.
  • Alkyl having up to 25 carbon atoms is a branched or unbranched radical, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1 ,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1 ,1 ,3,3-tetra- methylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1 ,1 ,3-trimethylhexyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1 ,1 ,3,3,5,5-hexamethylhe
  • C 3 -C 25 Alkyl interrupted with oxygen or sulfur is, for example, CH 3 -O-CH 2 CH 2 -, CH 3 -O-CH 2 CH 2 -O-CH 2 CH 2 -, CH 3 -(O-CH 2 CH 2 -) 2 O-CH 2 CH 2 -, CH 3 -(O-CH 2 CH 2 -) 3 O-CH 2 CH 2 - , CH 3 -(O-CH 2 CH 2 -) 4 O-CH 2 CH 2 - , CH 3 -S-CH 2 CH 2 -, CH 3 -S-CH 2 CH 2 -S-CH 2 CH 2 -, CH 3 -(S-CH 2 CH 2 -) 2 S-CH 2 CH 2 -, CH 3 -(S-CH 2 CH 2 - ) 3 S-CH 2 CH 2 - or CH 3 -(S-CH 2 CH 2 - ) 4 S-CH 2 CH 2 -.
  • Alkyl-substituted phenyl which contains preferably from 1 to 3, especially 1 or 2, alkyl groups, is, for example, o-, m- or p-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2-methyl-6- ethylphenyl, 4-tert-butylphenyl, 2-ethylphenyl or 2,6-diethylphenyl.
  • Ci-C 2 5Alkylene is a branched or unbranched radical, for example methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene, dodecamethylene or octadecamethylene.
  • Alkoxy containing up to 25 carbon atoms is a branched or unbranched radical, for example methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, pentyloxy, isopentyloxy, hexyl- oxy, heptyloxy, octyloxy, decyloxy, tetradecyloxy, hexadecyloxy or octadecyloxy.
  • Alkylthio containing up to 25 carbon atoms is a branched or unbranched radical, for example methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, pentylthio, isopentyl- thio, hexylthio, heptylthio, octylthio, decylthio, tetradecylthio, hexadecylthio or octadecylthio.
  • compositions comprising, as component (d), the compounds 101 to 172.
  • compositions comprising, as component (d), cyclic and acyclic 1 ,2-disubstituted alkenes bearing 2 electron-withdrawing groups, such as derivatives of maleic anhydride, citraconic anhydride, maleic acid, citraconic acid or fumaric acid.
  • compositions comprising, as component (d), maleic acid dialkyl esters such as the compounds 106, 125, 126, 129, 131 , 137, 140, 143, 157, 160, 162, 164, 167.
  • Preferred compounds (d) are diisooctyl maleate and dioctyl maleate, in particular dioctyl maleate.
  • compound (d) is not a maleic acid mono ester compound (e.g. a partial ester compound of maleic anhydride), in particular not mono [POP(5) lauryl ether] maleic acid ester.
  • Component (b) is usefully added to the rubber in amounts of from 1 to 40% by weight, for example from 1 to 30% by weight, preferably from 5 to 30% by weight, based on the weight of the composition.
  • Component (c) is usefully added to the rubber in amounts of from 0.01 to 10% by weight, for example from 0.1 to 10% by weight, preferably from 0.5 to 5% by weight based on the weight of the composition.
  • Component (d) is usefully added to the rubber in amounts of from 0.01 to 10% by weight, for example from 0.1 to 10% by weight, preferably from 0.5 to 5% by weight, based on the weight of the composition.
  • compositions of the invention may comprise further additives, such as the following:
  • Alkylated monophenols for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di- methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-bu- tyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-( ⁇ -methylcyclohexyl)-4,6-dimethyl- phenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-meth- oxymethylphenol, nonylphenols which are linear or branched in the side chains, for example 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1 '-methylundec
  • Alkylthiomethylphenols for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctyl- thiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4- nonylphenol.
  • Hydroquinones and alkylated hydroquinones for example 2,6-di-tert-butyl-4-methoxy- phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade- cyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-bu- tyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hy- droxyphenyl) adipate.
  • 2,6-di-tert-butyl-4-methoxy- phenol 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amyl
  • Tocopherols for example ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol and mixtures thereof (vitamin E).
  • Hvdroxylated thiodiphenyl ethers for example 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol) ! 4,4'-thiobis(6-tert-butyl-3-methylphenol) ! 4,4'-thiobis(6-tert-butyl-2- methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl)- disulfide.
  • Alkylidenebisphenols for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'- methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-( ⁇ -methylcyclohexyl)- phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4- methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert-butyl- phenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-( ⁇ -methylben- zyl)-4-nonylphenol], 2,2'-methylenebis[6-( ⁇ , ⁇ -dimethyl
  • Hydroxybenzylated malonates for example dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hy- droxybenzyl)malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, di- dodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1 ,1 ,3,3-te- tramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
  • dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hy- droxybenzyl)malonate di-octadecyl-2-(3-tert-butyl-4-
  • Aromatic hydroxybenzyl compounds for example 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxy- benzyl)-2,4,6-trimethylbenzene, 1 ,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetrame- thylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
  • Triazine compounds for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxy- anilino)-1 ,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1 ,3,5-tri- azine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,3,5-triazine, 2,4,6-tris- (3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,2,3-triazine, 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxyben- zyl)isocyanurate, 1 ,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl
  • Benzylphosphonat.es for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphospho- nate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hy- droxybenzylphosphonate, dioctadecyl- ⁇ -tert-butyl ⁇ -hydroxy-S-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
  • Acylaminophenols for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
  • esters of ⁇ -(3,5-di-tert-butyl-4-hvdroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6-hexanediol, 1 ,9- nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethy- lene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hy- droxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol- propane, 4-hydroxy
  • esters of ⁇ -(5-tert-butyl-4-hvdroxy-3-methylphenyl)propionic acid with mono- or poly- hydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6-hexanedi- ol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis- (hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethyl- olpropane, 4-hydroxymethyl-1
  • esters of ⁇ -(3,5-dicvclohexyl-4-hvdroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy- droxymethyl-1-phospha-2,6,7-triox
  • esters of 3,5-di-tert-butyl-4-hvdroxyphenyl acetic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy- droxymethyl-1-phospha-2,6,7-trioxabicyclo[
  • Aminic antioxidants for example N,N'-di-isopropyl-p-phenylenediamine, N,N'-di-sec-bu- tyl-p-phenylenediamine, N,N'-bis(1 ,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis(1-ethyl-3- methylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine, N,N'-dicy- clohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p- phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1 ,3-dimethylbutyl
  • 2-(2'-Hvdroxyphenyl)benzotriazoles for example 2-(2'-hydroxy-5'-methylphenyl)benzo- triazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphe- nyl)benzotriazole, 2-(2'-hydroxy-5'-(1 ,1 ,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di- tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphe- nyl)-5-chlorobenzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-sec-
  • azol-2-ylphenyl 2-[2'-hydroxy-3'-( ⁇ , ⁇ -dimethylbenzyl)-5'-(1 ,1 ,3,3-tetramethylbutyl)phenyl]- benzotriazole; 2-[2'-hydroxy-3'-(1 ,1 ,3,3-tetramethylbutyl)-5'-( ⁇ , ⁇ -dimethylbenzyl)phenyl]ben- zotriazole.
  • 2-Hvdroxybenzophenones for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyl- oxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.
  • Esters of substituted and unsubstituted benzoic acids for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylben- zoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzo- ate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxyben- zoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
  • Acrylates for example ethyl ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate, isooctyl ⁇ -cyano- ⁇ , ⁇ -diphe- nylacrylate, methyl ⁇ -carbomethoxycinnamate, methyl ⁇ -cyano- ⁇ -methyl-p-methoxycinna- mate, butyl ⁇ -cyano- ⁇ -methyl-p-methoxycinnamate, methyl ⁇ -carbomethoxy-p-methoxycin- namate and N-( ⁇ -carbomethoxy- ⁇ -cyanovinyl)-2-methylindoline.
  • Nickel compounds for example nickel complexes of 2,2'-thiobis[4-(1 ,1 ,3,3-tetramethyl- butyl)phenol], such as the 1 :1 or 1 :2 complex, with or without additional ligands such as n- butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert- butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphe- nylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.
  • additional ligands such as n- butylamine, triethanolamine or N-cyclohexyldiethanol
  • Sterically hindered amines for example bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1 ,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1 -octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1 ,2,2,6,6-pentamethyl-4-piperi- dyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2-hydroxyethyl)- 2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-
  • N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide N-(1 ,2,2,6,6- pentamethyl-4-piperidyl)-n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-di- aza-4-oxo-spiro[4,5]decane, a reaction product of 7,7,9, 9-tetramethyl-2-cycloundecyl-1 -oxa- 3,8-diaza-4-oxospiro-[4,5]decane and epichlorohydrin, 1 ,1-bis(1 ,2,2,6, 6-pentamethyl-4- piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene, N,N'-bis-formyl-N,N'-bis(2,2,2,
  • Oxamides for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy- 5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
  • Metal deactivators for example N,N'-diphenyloxamide, N-salicylal-N'-salicyloyl hydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1 ,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyl- oyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.
  • Phosphites and phosphonites for example triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-di- cumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphos
  • Hydroxylamines for example N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N, N- dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N, N- dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydrox- ylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
  • Nitrones for example N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone, N-octyl- alpha-heptylnitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnitrone, N- hexadecyl-alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-al- pha-heptadecylnitrone, N-ocatadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-hepta- decylnitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N
  • Thiosynergistic compounds for example thiodipropionic acid dilauryl ester or thiodipropio- nic acid distearyl ester or compounds of formula IV
  • Ri is hydrogen, d-C ⁇ alkyl, cyclohexyl, phenyl or benzyl,
  • R 2 is hydrogen or d-C 4 alkyl, and n is the number 0, 1 or 2.
  • Peroxide scavengers for example esters of ⁇ -thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercapto- benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis( ⁇ - dodecylmercapto)propionate.
  • esters of ⁇ -thiodipropionic acid for example the lauryl, stearyl, myristyl or tridecyl esters
  • mercaptobenzimidazole or the zinc salt of 2-mercapto- benzimidazole zinc dibutyldithiocarbamate, dioctadecyl disul
  • Basic co-stabilisers for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.
  • Basic co-stabilisers for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ric
  • Nucleating agents for example inorganic substances, such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds, such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers (ionomers).
  • inorganic substances such as talcum
  • metal oxides such as titanium dioxide or magnesium oxide
  • phosphates carbonates or sulfates of, preferably, alkaline earth metals
  • organic compounds such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate
  • polymeric compounds such as ionic copolymers (
  • additives for example plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
  • compositions of the invention comprise, as other additives, one or more components selected from the group consisting of pigments, dyes, levelling assistants, dispersants, plasticizers, vulcanization activators, vulcanization accelerators, vulcanizers, charge control agents, adhesion promoters, light stabilizers or antioxidants, such as phenolic antioxidants (items 1.1 to 1.18 in the list) or aminic antioxidants (item 1.19 in the list), organic phosphites or phosphonites (item 4 in the list) and/or thiosynergists (item 7 in the list).
  • phenolic antioxidants items 1.1 to 1.18 in the list
  • aminic antioxidants item 1.19 in the list
  • organic phosphites or phosphonites item 4 in the list
  • thiosynergists thiosynergists
  • concentrations at which these other additives are added is from 0.01 to 10% by weight based on the total weight of the rubber.
  • Components (b), (c) and (d) and, if desired other additives may be in pure form or encapsulated in waxes, in oils or in polymers.
  • Components (c) and (d) can also be used in form of surface modified silica.
  • the composition of the present invention does not include paper, for example waste newspaper.
  • Also part of the invention is a process for the preparation of a filled rubber compound comprising the step of i) compounding the composition of the present invention.
  • the compounding step is usually performed at an elevated temperature, for example at a temperature in the range of 90 to 260 0 C, or at a temperature of 120 to 200 0 C or at a temperature of 140 to 180 0 C.
  • the composition of the present invention is usually mixed.
  • a Brabender mixer can be used for mixing.
  • the composition of the present invention can be heated up to 6 minutes at a temperature of 160 0 C.
  • volatile organic solvent which may be produced during the compounding step, are preferably removed. Also part of the invention is a filled rubber compound obtainable by above process.
  • Also part of the present invention is a process for the preparation of a filler-reinforced vulcanizate comprising the steps of i) compounding the composition of the present invention ii) homogenizing the rubber compound obtained in step i), iii) homogenizing the rubber compound obtained in step ii) in the presence of a vulcanization system, and iv) vulcanizing the rubber compound obtained in step iii).
  • Steps ii) and steps iii) can be performed at the same time.
  • Homogenization can be done by methods known in the art, for example using a two roll mill.
  • the temperature during homogenization is usually below 140 0 C, usually in the range of 60 to 120 0 C, or 80 to 100 0 C.
  • the vulcanization step is usually carried out at an elevated temperature, for example at a temperature in the range of 90 to 260 0 C, or at a temperature of 120 to 200 0 C or at a temperature of 140 to 180 0 C.
  • a filler-reinforced vulcanizate obtainable by a process comprising the steps of i) compounding the composition of the present invention, ii) homogenizing the rubber compound obtained in step i), iii) homogenizing the rubber compound obtained in step ii) in the presence of a vulcanization system, and iv) vulcanizing the rubber compound obtained in step iii).
  • Steps ii) and step iii) can be performed at the same time.
  • a coupling agent selected from the group consisting of organofunctionalized silanes, polysulfide silanes, blocked mercaptosilanes, thio substituted silanes, sulfoxide or sulfone substituted silane coupling agents, and oligomeric hydrolysis product thereof
  • a coupling agent regulator selected from the group consisting of cyclic or acyclic 1 ,2- disubstituted alkenes bearing two electron-withdrawing groups, cyclic or acyclic 1 ,2- disubstituted alkenes bearing one electron-withdrawing group and one electron- donating group, cyclic or acyclic 1 ,1-disubstituted alkenes bearing two electron-withdrawing groups, cyclic or acyclic 1 ,1-disubstituted alkenes bearing two electron-withdrawing groups, cyclic or
  • Also part of the invention is the use of above mixture as a coupling agent mixture in the preparation of filled rubber compounds and filler-reinforced vulcanizates.
  • the present invention provides also a process for the manufacture of a filled rubber compound with improved processability which comprises mixing in one-step a) a rubber, b) a white reinforcing filler, c) a coupling agent selected from the group consisting of organofunctionalized silanes, polysulfide silanes, blocked mercaptosilanes, thio substituted silanes, sulfoxide or sulfone substituted silane coupling agents, and oligomeric hydrolysis product thereof, and d) a coupling agent regulator selected from the group consisting of cyclic or acyclic 1 ,2- disubstituted alkenes bearing two electron-withdrawing groups, cyclic or acyclic 1 ,2- disubstituted alkenes bearing one electron-withdrawing group and one electron- donating group, cyclic or acyclic 1 ,1-disubstituted alkenes bearing two electron-withdrawing groups, cyclic or acycl
  • Components (b), (c) and (d), and also, if desired, other additives are incorporated into the rubber by known methods, especially in one-step, for example during mixing in internal mixers with rams (Branbury), on mixing rolls or in mixing extruders, prior to vulcanization, or else by applying dissolved or dispersed components (b), (c) and (d) to the rubber, if desired with subsequent removal of the solvent by evaporation.
  • components (b), (c) and (d) and, if desired, other additives may also be in the form of a masterbatch comprising these, for example at a concentration of from 2.5 to 25% by weight.
  • Components (b), (c) and (d) and, if desired, other additives may also be added prior to or during the polymerization and/or coagulation of the rubbers, i.e. advantageously, if desired, as a first-level mixture in the raw rubber, which may also comprise other components, such as carbon black as filler and/or extender oils.
  • Components (b), (c) and (d) and, if desired, other additives may also be sprayed onto the rubber to be treated.
  • Also part of the invention is a process for ensuring the coupling of a white reinforcing filler to rubber compositions reinforced by a white filler solely or with a white filler/carbon black blend, which comprises incorporating into the rubber a component (c) and a component (d) and then vulcanizing the composition.
  • Also part of the invention is the use of a mixture of a component (c) and a component (d) as coupling agent for ensuring the coupling of a white reinforcing filler with a rubber.
  • the resultant rubber compounds may be used in a wide variety of forms, e.g. ribbons, moulding compositions, profiles, conveyor belts or tires (pneumatic).
  • the composition of the present invention is particularly useful for tread application in vehicle tires.
  • the advantage of the process for the preparation of filled rubber compounds of the present invention using a mixture of a coupling agent and a coupling agent regulator in the compounding step is that the compounding step does not suffer from the disadvantages of the state-of-the-art processes, namely high sensitivity towards prolonged exposure to elevated temperatures resulting in a high control-intensity of this step, and at the same time the other steps of the process and/or of the physical properties of the vulcanized filler- reinforced rubber compound are not negatively influenced.
  • the process of the present invention provides a rubber compound of lower Mooney viscosity and increased scorch resistance (longer t S2 )-
  • a low Mooney viscosity of the rubber compound allows an easier handling of the rubber compound when loading the rubber compound in a molding form, and a long t S2 value in the curing step allows a longer time to load and distribute the rubber compound in the molding form.
  • the process of the present invention can provide further improvements in the other steps of the process and/or of the physical properties of the rubber compound intermediates and/or of the filler-reinforced vulcanizates.
  • it is possible to add the curing system in the first homogenization step instead of adding the curing system in an additional step after the first homogenization step.
  • a high tan ⁇ max value of the filler-reinforced vulcanizates for example of a vehicle tire, relates to good ice traction and to good wet traction.
  • Example 1 Preparation of silica filled styrene-butadiene/butadiene rubber compound - two- step homogenization process.
  • the dump temperature of the "first basic rubber compound” is 170 to 190 0 C.
  • the torque required to operate the rotors during mixing as well as the stock temperatures are recorded continuously.
  • the "first basic rubber compound” is homogenized on a two roll mill at 90 0 C for 6 minutes to yield a "second basic rubber compound”.
  • a curing system (1.4 phr sulphur, 2.0 phr N-cyclohexyl- 2-benzothiazolesulfenamide [Vulkacit® CZ/C from Lanxess] and 2.0 phr 1 ,3-diphenyl- guanidine [Vulkacit® D/C from Lanxess]) is added to the "second basic rubber compound" on the two roll mill at 90 0 C during 6 minutes and homogenization is continued for 6 minutes after start of the addition of the vulcanization system to yield a "rubber compound comprising the vulcanization system".
  • the Mooney viscosity of the "rubber compound comprising the vulcanization system” is measured according to ASTM Method D 1646 with a Mooney viscometer. In the viscometer, the rubber compound is subjected to shearing forces while the torque required to rotate the rotor is registered. The greater the resistance of the rubber compound to shear, the higher the Mooney viscosity value is.
  • the viscosity value is obtained by using either a small rotor (S) or a large rotor (L).
  • MS (1 +4) (100 0 C) indicates a Mooney viscosity number obtained by using a small rotor after 1 min of pre-heating followed by 4 min of heating at 100 0 C.
  • the Mooney value gives indication about the behaviour of the rubber compound under high shearing, this value relates to the high shear rate of the processing.
  • the "rubber compounds comprising the vulcanization system" of the present invention have low Mooney viscosities resulting in a good flowability for the form filling step prior to the on-set of the curing process.
  • the low Mooney viscosities indicate that less un-wanted side reactions have occurred during the compounding step.
  • Table 1 Mooney viscosity of the "rubber compounds comprising the vulcanization system". Explanation of footnotes see end of Table 1 1.
  • the curing isotherms of the "rubber compounds comprising the vulcanization system” are measured at 160 0 C with an Oscillating Disc Rheometer (ODR).
  • ODR Oscillating Disc Rheometer
  • the "rubber compounds comprising the vulcanization system” are compression molded to t 95 of the curing isotherm at 160 0 C.
  • the curing kinetics are also showing beneficial improvements in terms of scorch time of the "rubber compounds comprising the vulcanization system".
  • the t S2 value of the curing isotherm (ASTM Method D 2084) is the time to 2 units above minimum torque and indicates the scorch resistance of a rubber compound.
  • S' max is the maximum torque.
  • Cure time (t 95 ) is the time to 95% of delta torque above minimum with a curing time of 30 minutes.
  • the mixtures of coupling agent and coupling agent regulator of the present invention fulfill the high criteria as coupling agents with superior scorch resistance (longer t S2 ) for silica filled styrene-butadiene/butadiene rubber compounds. The results are summarized in Table 2.
  • the coupling of the filler network to the rubber matrix influences the physical properties of the vulcanizates.
  • the tensile strength, the modulus 100, the compression set and the abrasion values give indications about the level of coupling efficiency.
  • Efficient coupling agents afford vulcanizates with good abrasion resistance characterized by low compression set values.
  • the mixture of coupling agent and coupling agent regulator of the present invention fulfill the high criteria as coupling agents for silica in a styrene-butadiene/butadiene rubber compound. The results are summarized in Table 3.
  • Table 3 Physical properties of vulcanizates. Explanation of footnotes see end of Table 1 1.
  • Example 2 Preparation of silica filled styrene-butadiene/butadiene rubber compound - one- step homogenization process.
  • the dump temperature of the "first basic rubber compound” is 170 to 190 0 C.
  • the torque required to operate the rotors during mixing as well as the stock temperatures are recorded continuously.
  • the "first basic rubber compound” is homogenized on a two roll mill at 90 0 C for 6 minutes while a curing system (1.4 phr sulphur, 2.0 phr N-cyclohexyl ⁇ -benzothiazolesulfenamide [Vulkacit® CZ/C from Lanxess] and 2.2 phr 1 ,3-diphenylguanidine [Vulkacit® D/C from Lanxess]) is added on the two roll mill at 90 0 C during the time of homogenization to yield a "rubber compound comprising the vulcanization system".
  • the Mooney viscosity of the "rubber compound comprising the curing system” is measured according to ASTM Method D 1646 with a Mooney viscometer as described in example 1.
  • the "rubber compound comprising the vulcanization system” of the present invention show again low Mooney viscosities resulting in a good flowability for the form filling step prior to the on-set of the curing process. The results are summarized in Table 4.
  • Table 4 Mooney viscosity and Payne effect of the "rubber compounds comprising the vulcanization system". Explanation of footnotes see end of Table 1 1.
  • the curing isotherms of the "rubber compounds comprising the vulcanization system” are measured at 160 0 C with an Oscillating Disc Rheometer (ODR).
  • ODR Oscillating Disc Rheometer
  • the "rubber compounds comprising the vulcanization system” are compression molded to t 95 of the curing isotherm at 160 0 C.
  • the curing kinetics of the "rubber compound comprising the vulcanization system” are also analysed in analogy to example 1.
  • the mixtures of the coupling agent and the coupling agent regulator of the present invention fulfill again the high criteria as coupling agents with superior scorch resistance (longer t S2 ) for silica filled styrene-butadiene/butadiene rubber compounds.
  • the results are summarized in Table 5.
  • the dynamic mechanical properties of the vulcanizates are measured with a TA Instrument ARES under torsion strain at a frequency of 1 Hz, at 0.5% dynamic amplitude and over a temperature range of -70 to 60 0 C with a heating rate of 1 °C/minute.
  • a high tangent delta at -20 0C to 0 0 C is related to good ice traction and at slightly higher temperatures to good wet traction.
  • a low tangent delta at 50 to 80 0 C is indicative of a compound that will have low rolling resistance.
  • the mixtures of a coupling agent and a coupling agent regulator of the present invention show an increased tangent delta value and thus a significantly improved ice-wet traction. The results are summarized in Table 7.
  • Table 7 Dynamic mechanical properties of the vulcanizates. Explanation of footnotes see end of Table 11.
  • Example 3 Preparation of a silica filled styrene-butadiene/butadiene rubber compound - two-step homogenization process.
  • Rubber compounds comprising the curing system are prepared in analogy to example 1 , except that a mixture of a coupling agent and a coupling agent regulator as indicated in tables 8 to 11 and as vulcanization system (1.4 phr sulphur, 2.0 phr N-cyclohexyl-2-benzo- thiazolesulfenamide [Vulkacit® CZ/C from Lanxess] and 2.2 phr 1 ,3-diphenylguanidine [Vulkacit® D/C from Lanxess]) is used.
  • the Mooney viscosity of the "rubber compounds comprising the vulcanization system” is measured according to ASTM Method D 1646 with a Mooney viscometer as described in example 1.
  • the "rubber compound comprising the vulcanization system” of the invention show again a low Mooney viscosity resulting in a good flowability for the form filling step prior to the on-set of the curing process. The results are summarized in Table 8.
  • the determination of the filler-filler interaction in the "rubber compounds comprising the vulcanization system” is carried out via amplitude sweep measurement in an Oscillating Disk Rheometer (ODR) at 80 0 C at a frequency of 1.67 Hz with an amplitude range increasing from 0.04° to 14.34°.
  • ODR Oscillating Disk Rheometer
  • the good hydrophobation effect provided by the mixtures of a coupling agent and a coupling agent regulator of the present invention leading to a weaker filler-filler interaction is proved by the better incorporation of the filler particles into the rubber matrix.
  • the lower values of the G * ma ⁇ modulus show the better hydrophobation effect of the mixtures of coupling agent and coupling agent regulator the present invention.
  • the end values of the modulus at higher amplitudes show that the coupling efficiency is as good as the comparison examples.
  • Table 8 The results are summarized in Table 8.
  • Table 8 Mooney viscosities and "G * m a ⁇ -G * m ⁇ n " of the "rubber compounds comprising the vulcanization system". Explanation of footnotes see end of Table 1 1.
  • the curing isotherms of the "rubber compounds comprising the vulcanization system” are measured at 160 0 C with an Oscillating Disc Rheometer (ODR).
  • ODR Oscillating Disc Rheometer
  • the "rubber compounds comprising the vulcanization system” are compression molded to t 95 of the curing isotherm at 160 0 C.
  • Table 10 Physical properties of the vulcanizates. Explanation of footnotes see end of Table 11.
  • Table 1 1 Dynamic mechanical properties of the vulcanizates.

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Abstract

L’invention concerne une composition qui comprend a) un caoutchouc naturel ou synthétique sensible à la dégradation oxydative, thermique, dynamique, induite par la lumière et/ou induite par l’ozone, b) des charges blanches renforçantes, c) un agent de couplage choisi dans le groupe constitué des silanes organofonctionnalisés, des polysulfure silanes, des mercaptosilanes bloqués, des silanes à substitution thio, des agents de couplage silanes à substitution sulfone ou sulfoxyde, et son produit d’hydrolyse oligomère, et d) un régulateur d’agent de couplage choisi dans le groupe constitué des alcènes 1,2-disubstitués cycliques ou acycliques portant deux groupes accepteurs d’électrons, des alcènes 1,2-disubstitués cycliques ou acycliques portant un groupe accepteur d’électrons et un groupe donneur d’électrons, des alcènes 1,1-disubstitués cycliques ou acycliques portant deux groupes accepteurs d’électrons, des alcènes 1,1-disubstitués cycliques ou acycliques portant un groupe accepteur d’électrons et un groupe donneur d’électrons, et des alcènes trisubstitués cycliques ou acycliques portant au moins deux groupes accepteurs d’électrons.
PCT/EP2009/057753 2008-07-18 2009-06-23 Agents de couplage pour caoutchoucs chargés WO2010006889A2 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130030097A1 (en) * 2009-12-22 2013-01-31 Michelin Recherche Et Technique S.A. Article, in particular a pneumatic tyre, having an external rubber mixture comprising a lanthanide salt
US8975316B2 (en) 2010-09-03 2015-03-10 Cabot Corporation Modified fillers and elastomeric composites comprising same
US9175150B2 (en) 2012-03-02 2015-11-03 Cabot Corporation Modified carbon blacks having low PAH amounts and elastomers containing the same
US10640630B2 (en) 2012-03-02 2020-05-05 Cabot Corporation Elastomeric composites containing modified fillers and functionalized elastomers

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1176167A2 (fr) * 2000-07-26 2002-01-30 Sumitomo Rubber Industries Ltd. Composition de caoutchouc pour pneu et pneumatique
WO2004000932A1 (fr) * 2002-06-21 2003-12-31 Lanxess Deutschland Gmbh Melanges de caoutchouc contenant des copolymeres pour produire des pneus
EP1535961A1 (fr) * 2002-09-03 2005-06-01 Bridgestone Corporation Pneu
EP1803769A2 (fr) * 2005-12-30 2007-07-04 The Goodyear Tire & Rubber Company Composition pour couche de ceinture renforcée

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1176167A2 (fr) * 2000-07-26 2002-01-30 Sumitomo Rubber Industries Ltd. Composition de caoutchouc pour pneu et pneumatique
WO2004000932A1 (fr) * 2002-06-21 2003-12-31 Lanxess Deutschland Gmbh Melanges de caoutchouc contenant des copolymeres pour produire des pneus
EP1535961A1 (fr) * 2002-09-03 2005-06-01 Bridgestone Corporation Pneu
EP1803769A2 (fr) * 2005-12-30 2007-07-04 The Goodyear Tire & Rubber Company Composition pour couche de ceinture renforcée

Non-Patent Citations (1)

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Title
DATABASE WPI Week 200678 Thomson Scientific, London, GB; AN 2006-758662 & IN KOL200500462 (NICCO CORP LTD) 15 September 2006 (2006-09-15) XP002507567 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130030097A1 (en) * 2009-12-22 2013-01-31 Michelin Recherche Et Technique S.A. Article, in particular a pneumatic tyre, having an external rubber mixture comprising a lanthanide salt
US8975316B2 (en) 2010-09-03 2015-03-10 Cabot Corporation Modified fillers and elastomeric composites comprising same
US9175150B2 (en) 2012-03-02 2015-11-03 Cabot Corporation Modified carbon blacks having low PAH amounts and elastomers containing the same
US10640630B2 (en) 2012-03-02 2020-05-05 Cabot Corporation Elastomeric composites containing modified fillers and functionalized elastomers

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