RUBBER MIXTURE, VULCANIZATE OF THE RUBBER MIXTURE, AND VEHICLE TIRES

Abstract

A vulcanizate of a rubber mixture for a vehicle tire, the rubber mixture containing at least one filler and 10 to 100 phr of at least one polymer A of the following formula:
PSR.sup.1SR.sup.2).sub.n
where S is a sulfur atom, and P is a polymer chain which is obtainable by anionic polymerization of at least one conjugated diene and optionally one or more vinylaromatic compounds and which has optionally been chain end-modified, R.sup.1 is most preferably C.sub.1-C.sub.8-alkyl, R.sup.2 is preferably selected from H and SiR.sup.3R.sup.4R.sup.5 in which R.sup.3, R.sup.4 and R.sup.5 are independently selected from H, C.sub.1-C.sub.16-alkyl, C.sub.6-C.sub.16-aryl and C.sub.7-C.sub.16-aralkyl, and n is an integer selected from 1 to 200, where the SR.sup.1SR.sup.2 group(s) are bonded to the backbone of the polymer chain P.

Claims

1. A sulfur-crosslinkable rubber mixture comprising at least the following constituents: at least one filler; and, 10 to 100 phr of at least one polymer A of the following formula I):
PSR.sup.1SR.sup.2).sub.nI) wherein S is a sulfur atom, P is a polymer chain which is obtained by anionic polymerization of at least one conjugated diene and optionally one or more vinylaromatic compounds and which has optionally been chain end-modified, R.sup.1 is selected from C.sub.1-C.sub.8-alkyl, R.sup.2 is selected from SiR.sup.3R.sup.4R.sup.5 in which R.sup.3, R.sup.4 and R.sup.5 are selected from H, C.sub.1-C.sub.16-alkyl, C.sub.6-C.sub.16-aryl and C.sub.7-C.sub.16-aralkyl, and n is an integer selected from 1 to 200; and, wherein the SR.sup.1SR.sup.2 group(s) are bonded to the backbone of the polymer chain P.

2. The rubber mixture as claimed in claim 1, wherein the at least one conjugated diene is selected from the group consisting of 1,3-butadiene, 2-(C.sub.1-C.sub.5-alkyl)-1,3-butadiene, especially isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene, 1,3-hexadiene, 1,3-heptadiene, 1,3-octadiene, 2-methyl-2,4-pentadiene, cyclopentadiene and 1,3-cyclooctadiene.

3. The rubber mixture as claimed in claim 2, wherein the at least one conjugated diene is 1,3-butadiene.

4. The rubber mixture as claimed in claim 1, wherein the vinylaromatic compound is selected from the group consisting of styrene, C.sub.1-C.sub.4-alkyl-substituted styrene, especially 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,4,6-trimethylstyrene, -methylstyrene, 2,4-diisopropylstyrene and 4-tert-butylstyrene, stilbene, vinylbenzyldimethylamine, 4-vinylbenzyl dimethylaminoethyl ether, N,N-dimethylaminoethylstyrene, tert-butoxystyrene, vinylpyridine, 1,2-divinylbenzene, 1,3-divinylbenzene and 1,4-divinylbenzene, and any mixture of two or more of these.

5. The rubber mixture as claimed in claim 4, wherein the vinylaromatic compound is styrene.

6. The rubber mixture as claimed in claim 1, wherein the filler is at least one silica and/or at least one carbon black.

7. The rubber mixture as claimed in claim 1, wherein the rubber mixture contains 20 to 300 phr of said at least one filler.

8. The rubber mixture as claimed in claim 1, wherein it contains 40 to 90 phr of the at least one polymer A and 10 to 60 phr of at least one further rubber.

9. The rubber mixture as claimed in claim 8, wherein the at least one further rubber is a diene rubber selected from the group consisting of natural polyisoprene, synthetic polyisoprene, butadiene rubber and styrene-butadiene rubber.

10. A vulcanizate which is obtained by sulfur vulcanization of at least one rubber mixture as claimed in claim 1.

11. A vehicle tire comprising at least one vulcanizate of at least one rubber mixture as claimed in claim 10 in at least one component.

Description

(1) Selected examples of the SR.sup.1SR.sup.2 substructure in formula I) and formula II) are S(CH.sub.2).sub.2SSiMe.sub.3, S(CH.sub.2).sub.2SSiMe.sub.2Et, S(CH.sub.2).sub.2SSiMe.sub.2Pr, S(CH.sub.2).sub.2SSiMe.sub.2Bu, S(CH.sub.2).sub.2S-SiEt.sub.3, S(CH.sub.2).sub.3SSiMe.sub.3, S(CH.sub.2).sub.3SSiMe.sub.2Et, S(CH.sub.2).sub.3SSiMe.sub.2Pr, S(CH.sub.2).sub.3SSiMe.sub.2Bu, S(CH.sub.2).sub.3S-SiEt.sub.3, S(CH.sub.2).sub.6SSiMe.sub.3, S(CH.sub.2).sub.6SSiMe.sub.2Et, S(CH.sub.2).sub.6SSiMe.sub.2Pr, S(CH.sub.2).sub.6SSiMe.sub.2Bu and S(CH.sub.2).sub.6S-SiEt.sub.3.

(2) n is an integer selected from 1 to 200, preferably 1 to 100, more preferably 1 to 50.

(3) Step (i) of the process corresponds to the above-described preparation of the polymer chain P, and for details and conditions and preferred embodiments reference is made to the above-described preparation of the polymer chain P.

(4) The anionic polymerization of step (i) and hence the anionic living polymer chain obtained is terminated in a step (ii). This polymerization or chain termination can be effected in a conventionally known manner by means of a proton source or a functional reagent. An agent for chain termination contains at least one active hydrogen atom that can react with and protonates the anionic polymer chain end. A single chain terminator or two or more in combination may be used. Suitable chain terminators include water (water vapor), alcohols, amines, mercaptans and organic acids, preferably alcohols and more preferably C.sub.1-C.sub.4 alcohols, preferably methanol and ethanol and more preferably methanol. Rather than or together with the chain terminator, it is also possible to use one or more compounds that modify the chain end in order to modify the polymer chain at the chain ends. Corresponding compounds are known to the person skilled in the art from the prior art, and reference is made by way of example to the disclosure of the following documents already cited above: WO 2014/040640, WO 2014/040639, WO 2015/086039 and WO 2015/055252.

(5) After the chain termination in step (ii), the resultant polymer that has been deactivated at the chain ends is reacted with a compound of the formula II) in the presence of a free-radical initiator. The reaction leads to modification of the backbone of the polymer chain and hence to an elastomeric polymer of the formula I). The modification in step (iii) is typically conducted directly after step (ii). Optionally, however, after step (ii), the solvent can be removed and/or exchanged before the modification in step (iii) is conducted.

(6) The amount of the compound(s) of the formula II) added in step (iii) depends on the length of the polymer chain P and the desired index n in formula I). Typically, this amount is 0.01% to 10% by weight, based on the total amount of all monomers, preferably 0.025% to 7.5% by weight and more preferably 0.05% to 5% by weight.

(7) The free-radical initiator is typically added in an amount of 1 to 25 mol %, preferably 2 to 20 mol %, based on the amount of the compound(s) of the formula II) used. The reaction in step (iii) is generally conducted at a temperature of 50 to 180 C., preferably at 60 to 150 C.

(8) The free-radical initiator used in step (iii) may be selected, for example, from peroxides, azo initiators and photoinitiators, and two or more free-radical initiators may be used in combination. Preference is given to using a peroxide as free-radical initiator, for example lauroyl peroxide, dicumyl peroxide, benzoyl peroxide, tert-butyl peroxide or 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane. One example of an azo initiator is 2,2-azobis(2-methylpropionitrile).

(9) The reaction mixture obtained in step (iii) is typically worked up by conventional methods, giving the polymer A. Workup means the removal of solvents by distillation or vacuum evaporation. In this context, further polymers and customary constituents or products of side reactions of the desired polymerization as part of the polymer composition that are formed in the polymerization process may be present as part of the polymer A, but do not constitute an elastomeric polymer of formula I) of the invention.

(10) The statements of amount 10 to 100 phr of polymer A or the preferred embodimentsthus relate to the total amount of polymer A present including components that are present as customary impurities and are selected from (i) components that are obtained as a result of the polymerization to obtain the polymer chain P or are added to the polymerization, and (ii) components that remain after removal of the solvents from the polymerization.

(11) In an advantageous embodiment of the invention, the rubber mixture contains 100 phr of the polymer A, i.e. it does not contain any further rubber, and all other weight figures are based on 100% by weight of the polymer A, with the above-described exception that impurities may be present.

(12) In a further advantageous embodiment of the invention, the rubber mixture contains 10 to 90 phr, more preferably 40 to 90 phr, of the polymer A in combination with 10 to 90 phr or more preferably 10 to 60 phr of at least one further rubber.

(13) The at least one further rubber is preferably selected from the group consisting of natural polyisoprene and/or synthetic polyisoprene and/or butadiene rubber and/or solution-polymerized styrene-butadiene rubber and/or emulsion-polymerized styrene-butadiene rubber and/or liquid rubbers (having a molecular weight Mw by GPC of greater than 20 000 g/mol) and/or halobutyl rubber and/or polynorbornene and/or isoprene-isobutylene copolymer and/or ethylene-propylene-diene rubber and/or nitrile rubber and/or chloroprene rubber and/or acrylate rubber and/or fluoro rubber and/or silicone rubber and/or polysulfide rubber and/or epichlorohydrin rubber and/or styrene-isoprene-butadiene terpolymer and/or hydrogenated acrylonitrile-butadiene rubber and/or isoprene-butadiene copolymer and/or hydrogenated styrene-butadiene rubber.

(14) Nitrile rubber, hydrogenated acrylonitrile-butadiene rubber, chloroprene rubber, butyl rubber, halobutyl rubber or ethylene-propylene-diene rubber in particular are used in the production of technical rubber articles, such as belts, drive belts and hoses, and/or footwear soles.

(15) The further rubber is preferably at least one further diene rubber. The polymer A present is likewise a diene rubber.

(16) Diene rubbers refer to rubbers that result from polymerization or copolymerization of dienes and/or cycloalkenes and thus have CC double bonds either in the main chain or in the side groups.

(17) The at least one further diene rubber is preferably selected from the group consisting of synthetic polyisoprene (IR) and natural polyisoprene (NR) and styrene-butadiene rubber (SBR) and polybutadiene (BR).

(18) The natural and/or synthetic polyisoprene of all embodiments may be either cis-1,4-polyisoprene or 3,4-polyisoprene. However, the use of cis-1,4-polyisoprenes with a cis-1,4 content >90% by weight is preferred. Firstly, it is possible to obtain such a polyisoprene by stereospecific polymerization in solution with Ziegler-Natta catalysts or using finely divided lithium alkyls. Secondly, natural rubber (NR) is one such cis-1,4-polyisoprene; the cis-1,4 content in the natural rubber is greater than 99% by weight.

(19) In addition, a mixture of one or more natural polyisoprenes with one or more synthetic polyisoprenes is also conceivable.

(20) If the rubber mixture of the invention includes at least one butadiene rubber (BR, polybutadiene) as a further diene rubber in addition to the polymer A) present, the type of rubber in question may comprise any of the types known to the skilled person. These include so-called high-cis and low-cis types, wherein polybutadiene having a cis content of not less than 90% by weight is referred to as high-cis type and polybutadiene having a cis content of less than 90% by weight is referred to as low-cis type. An example of a low-cis polybutadiene is LiBR (lithium-catalyzed butadiene rubber) having a cis content of 20% to 50% by weight. A high-cis BR achieves particularly good abrasion properties and low hysteresis of the rubber mixture.

(21) The one or more polybutadienes used may have been end group-modified with modifications and functionalizations and/or functionalized along the polymer chains. The modification may be a modification having hydroxyl groups and/or ethoxy groups and/or epoxy groups and/or siloxane groups and/or amino groups and/or aminosiloxane and/or carboxyl groups and/or phthalocyanine groups and/or silane-sulfide groups. However, further modifications known to those skilled in the art, also known as functionalizations, are also suitable. Metal atoms may be a constituent of such functionalizations.

(22) In the case where at least one styrene-butadiene rubber (styrene-butadiene copolymer) is present in the rubber mixture as a further diene rubber in addition to the polymer A, this may be either solution-polymerized styrene-butadiene rubber (SSBR) or emulsion-polymerized styrene-butadiene rubber (ESBR), and it is also possible to use a mixture of at least one SSBR and at least one ESBR. The terms styrene-butadiene rubber and styrene-butadiene copolymer are used synonymously in the context of the present invention. The styrene-butadiene copolymer used may be end group-modified and/or functionalized along the polymer chains with the modifications and functionalizations recited above for the polybutadiene.

(23) In the context of the present application, the styrene-butadiene rubber (styrene-butadiene copolymer) from the group of the further diene rubbers is a styrene-butadiene rubber known in the prior art.

(24) It is essential to the invention that the rubber mixture contains at least one filler. Preferably, the rubber mixture contains 20 bis 300 phr of at least one filler.

(25) The latter may be any of the fillers conceivable in the rubber industry, such as carbon black and/or silica or other fillers, for example aluminosilicates, kaolin, chalk, starch, magnesium oxide, titanium dioxide or rubber gels, and fibers (for example aramid fibers, glass fibers, carbon fibers, cellulose fibers).

(26) Further optionally reinforcing fillers are, for example, carbon nanotubes ((CNT), including discrete CNTs, what are called hollow carbon fibers (HCF) and modified CNTs containing one or more functional groups, such as hydroxyl, carboxyl and carbonyl groups), graphite and graphene, and so-called carbon-silica dual-phase fillers.

(27) In the context of the present invention, zinc oxide does not belong to the group of fillers.

(28) The filler is preferably at least one silica and/or at least one carbon black.

(29) Possible carbon blacks are all types of carbon black known to a person familiar with the technical field.

(30) In one embodiment, the carbon black has an iodine number in accordance with ASTM D 1510, which is also referred to as iodine adsorption number, between 30 g/kg and 250 g/kg, preferably 30 to 180 g/kg, more preferably 40 to 180 g/kg, and most preferably 40 to 130 g/kg, and a DBP number in accordance with ASTM D 2414 of 30 to 200 mL/100 g, preferably 70 to 200 mL/100 g, more preferably 90 to 200 mL/100 g.

(31) The DBP number in accordance with ASTM D 2414 determines the specific absorption volume of a carbon black or a light-colored filler by means of dibutyl phthalate.

(32) The use of such a type of carbon black in the rubber mixture, in particular for vehicle tires, ensures the best possible compromise between abrasion resistance and heat buildup, which in turn influences the ecologically relevant rolling resistance. Preference is given here to only one type of carbon black being used in the respective rubber mixture, but it is also possible to mix various types of carbon black into the rubber mixture. But the total amount of carbon blacks present corresponds to a maximum of 300 phr.

(33) The silica may be any of the types of silica known to those skilled in the art that are suitable as filler for tire rubber mixtures. However, particular preference is given to using a finely divided, precipitated silica which has a nitrogen surface area (BET surface area) (in accordance with DIN ISO 9277 and DIN 66132) of 35 to 400 m.sup.2/g, preferably 35 to 350 m.sup.2/g, more preferably 100 to 320 m.sup.2/g and most preferably 120 to 235 m.sup.2/g, and a CTAB surface area (in accordance with ASTM D 3765) of 30 to 400 m.sup.2/g, preferably 50 to 330 m.sup.2/g, more preferably 100 to 300 m.sup.2/g and most preferably 110 to 230 m.sup.2/g. Such silicas lead, for example in rubber mixtures for tire treads, to particularly good physical properties of the vulcanizates. In addition, advantages can arise in processing of the mixture as a result of a reduction in the mixing time while maintaining the same product properties that lead to improved productivity. Silicas used may thus, for example, be either those of the Ultrasil VN3 type (trade name) from Evonik or highly dispersible silicas known as HD silicas (e.g. Zeosil 1165 MP from Solvay).

(34) The filler is more preferably at least one silica.

(35) In a preferred embodiment of the invention, the rubber mixture comprises at least one silica as filler, where one or more different silicas having the abovementioned features are conceivable, where the total amount of silicas present is not more than 300 phr.

(36) In this embodiment, the rubber mixture of the invention contains 20 to 300 phr, preferably 20 to 250 phr, more preferably 20 to 150 phr and most preferably 80 to 110 phr of at least one silica.

(37) In an advantageous development of this embodiment of the invention, the rubber mixture does not contain any further filler apart from one or more silica(s).

(38) In a further advantageous development of this embodiment of the invention, the rubber mixture contains exclusively at least one carbon black as a further filler apart from one or more silica(s). The amount of carbon black here is 0.1 to 20 phr, preferably 0.1 to 10 phr, where the total amount of carbon black and silica is not more than 300 phr.

(39) In a preferred embodiment of the invention, the rubber mixture comprises at least one carbon black as filler, where one or more different carbon blacks (carbon black types) having the abovementioned features are conceivable.

(40) In this embodiment, the rubber mixture of the invention contains 20 to 300 phr of at least one carbon black, preferably 20 to 150 phr, more preferably 40 to 150 phr, most preferably 40 to 100 phr.

(41) To improve processability and to attach the silica and any other polar fillers present to the diene rubber, silane coupling agents may be used in rubber mixtures. It is possible here to use one or more different silane coupling agents in combination with one another. The rubber mixture may thus comprise a mixture of different silanes.

(42) The silane coupling agents react with the surface silanol groups of the silica or other polar groups during the mixing of the rubber or of the rubber mixture (in situ) or in the manner of a pretreatment (premodification) even before addition of the filler to the rubber. Silane coupling agents used may be any silane coupling agents known to those skilled in the art for use in rubber mixtures. Such coupling agents known from the prior art are bifunctional organosilanes which have at least one alkoxy, cycloalkoxy or phenoxy group as leaving group on the silicon atom and have, as other functionality, a group which can, optionally after dissociation, undergo a chemical reaction with the double bonds of the polymer. The latter group may, for example, be the following chemical groups:

(43) SCN, SH, NH.sub.2 or S.sub.x (with x=2 to 8).

(44) For example, silane coupling agents used may be 3-mercaptopropyltriethoxysilane, 3-thiocyanatopropyltrimethoxysilane or 3,3-bis(triethoxysilylpropyl) polysulfides having 2 to 8 sulfur atoms, e.g. 3,3-bis(triethoxysilylpropyl) tetrasulfide (TESPT), the corresponding disulfide (TESPD), or else mixtures of the sulfides having 1 to 8 sulfur atoms and different contents of the various sulfides. TESPT can, for example, also be added as a mixture with industrial carbon black (X50S trade name from Evonik). Preference is given to using a silane mixture which contains 40% to 100% by weight of disulfides, more preferably 55% to 85% by weight of disulfides and most preferably 60% to 80% by weight of disulfides.

(45) Blocked mercaptosilanes, as are known, for example, from WO 99/09036, can also be used as silane coupling agent. It is also possible to use silanes as described in WO 2008/083241 A1, WO 2008/083242 A1, WO 2008/083243 A1 and WO 2008/083244 A1. It is possible to use, for example, silanes which are marketed under the NXT name in a number of variants from Momentive, USA, or those that are marketed under the VP Si 363 name by Evonik Industries.

(46) In a preferred embodiment of the invention, the rubber mixture contains a 3,3-bis(triethoxysilylpropyl) polysulfide having 2 to 8 sulfur atoms as silane, preferably a mixture comprising 70% to 80% by weight of 3,3-bis(triethoxysilylpropyl) disulfide.

(47) In a further preferred embodiment of the invention, the rubber mixture comprises at least one blocked and/or unblocked mercaptosilane.

(48) What are meant by unblocked mercaptosilanes are silanes which have an SH group, i.e. a hydrogen atom on the sulfur atom. What are meant by blocked mercaptosilanes are silanes which have an S-PG group, where PG is the abbreviation for a protecting group on the sulfur atom. Preferred protecting groups, as set out below, are acyl groups.

(49) The expression blocked and/or unblocked mercaptosilane means that the rubber mixture of the invention may comprise a blocked silane, an unblocked silane, or a mixture of blocked and unblocked silane.

(50) To the skilled person, it is clear that this detail relates to the initial state of the constituents of the sulfur-crosslinkable rubber mixture, and that the protecting groups are eliminated during the mixing process and/or during vulcanization, and the respective sulfur atoms react chemically.

(51) The blocked and/or unblocked mercaptosilane preferably has the general empirical formula X):

(52) where the R.sup.7 radicals within a molecule may be the same or different and are alkoxy groups having 1 to 10 carbon atoms and/or alkyl polyether groups of the O((CH.sub.2).sub.xO).sub.zR.sup.9 form with z=2 to 9 and x=2 to 9, where the R.sup.9 radicals within a molecule may be the same or different and are alkyl groups having 10 to 25 carbon atoms, and
where R.sup.8 is an acyl group having 1 to 20 carbon atoms or is a hydrogen atom (H), and where Z is an alkyl group having 1 to 10 carbon atoms.

(53) S is the abbreviation for sulfur, Si for silicon, and O for oxygen atom.

(54) A preferred embodiment of the invention concerns at least one blocked mercaptosilane. In a preferred development of this embodiment of the invention, the rubber mixture of the invention does not contain any, i.e. contains 0 phf of, unblocked mercaptosilane, i.e. in this embodiment is free of unblocked mercaptosilane.

(55) Blocked mercaptosilanes bear a protecting group on the sulfur atom, in the present case the R.sup.8 group in formula I), and hence are also called protected mercaptosilanes.

(56) In a preferred embodiment of the blocked mercaptosilane, all the R.sup.7 groups are alkoxy groups. More preferably, at least one of the three R.sup.7 groups is an ethoxy group. Most preferably, each of the three R.sup.7 groups is an ethoxy group (abbreviated to OEt).

(57) In one preferred embodiment of the invention, the blocked mercaptosilane is 3-octanoylthio-1-propyltriethoxysilane, meaning that, in formula I) stated above, all R.sup.4 radicals are ethoxy (OEt) and Z is a propyl group and R.sup.8 is an octanoyl group. Surprisingly, the combination of the above-described polymer A with a blocked mercaptosilane, especially 3-octanoylthio-1-propyltriethoxysilane, results in a particularly good improvement in the rolling resistance indicators.

(58) The amount of coupling agent is preferably 0.1 to 20 phf, more preferably 1 to 15 phf. The expression phf (parts per hundred parts of filler by weight) used in this text is the conventional unit of amount for coupling agents for fillers in the rubber industry. In the context of the present application, phf relates to the silica present, meaning that any other fillers present, such as carbon black, are not included in the calculation of the amount of silane.

(59) In addition, the rubber mixture may contain further activators and/or agents for the binding of fillers, in particular carbon black. The latter may, for example, be the compound S-(3-aminopropyl)thiosulfuric acid as disclosed, for example, in EP 2589619 A1, and/or metal salts thereof, which gives rise to very good physical properties of the rubber mixture especially in combination with at least one carbon black as filler.

(60) The silanes and activators mentioned are added in the production of the rubber mixture preferably in at least one masterbatch mixing stage.

(61) The rubber mixture of the invention may contain 0 to 150 phr of at least one plasticizer. In a preferred embodiment, the rubber mixture of the invention contains at least one plasticizer, where the total amount of plasticizers is preferably 0.1 to 150 phr. Especially in combination with the abovementioned constituents, this results in particularly good processibility of the rubber mixture, especially of the extrudates prior to crosslinking, with simultaneously good rolling resistance indicators and good (and hence low) heat buildup. In a preferred embodiment of the invention, the rubber mixture comprises, more particularly and by way of example for inner tire components, 1 to 25 phr of at least one plasticizer.

(62) In a further preferred embodiment of the invention, the rubber mixture comprises, more particularly and by way of example for treads, preferably of winter tires, 30 to 80 phr of at least one plasticizer.

(63) The plasticizers used in the context of the present invention include all the plasticizers that are known to those skilled in the art, such as aromatic, naphthenic or paraffinic mineral oil plasticizers, for example MES (mild extraction solvate) or RAE (residual aromatic extract) or TDAE (treated distillate aromatic extract), or rubber-to-liquid oils (RTL) or biomass-to-liquid oils (BTL) preferably having a content of polycyclic aromatics of less than 3% by weight according to method IP 346 or rapeseed oil or factices or plasticizer resins or liquid polymers having a mean molecular weight (determination by GPC=gel permeation chromatography, in accordance with BS ISO 11344:2004) between 500 and 20 000 g/mol. If additional liquid polymers are used as plasticizers in the rubber mixture of the invention, these are not counted as rubber in the calculation of the composition of the polymer matrix. The plasticizer is preferably selected from the group consisting of the abovementioned plasticizers.

(64) Mineral oils are particularly preferred as plasticizer oils.

(65) When mineral oil is used, it is preferably selected from the group consisting of DAE (distilled aromatic extracts) and/or RAE (residual aromatic extracts) and/or TDAE (treated distilled aromatic extracts) and/or MES (mild extracted solvents) and/or naphthenic oils.

(66) The plasticizer(s) is/are preferably added in at least one masterbatch-mixing stage in the production of the rubber mixture of the invention.

(67) Furthermore, the rubber mixture of the invention may comprise standard additives in customary proportions by weight. These additives include

(68) a) aging stabilizers, for example N-phenyl-N-(1,3-dimethylbutyl)-p-phenylenediamine (6PPD), N,N-diphenyl-p-phenylenediamine (DPPD), N,N-ditolyl-p-phenylenediamine (DTPD), N-isopropyl-N-phenyl-p-phenylenediamine (IPPD), 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ), N,N-bis-(1,4-dimethylpentyl)-p-phenylenediamine (77PD),
b) activators, for example zinc oxide and fatty acids (e.g. stearic acid),
c) waxes,
d) resins, especially tackifying resins,
e) masticating aids, for example 2,2-dibenzamidodiphenyl disulfide (DBD), and
f) processing aids, for example fatty acid salts, for example zinc soaps, and fatty acid esters and derivatives thereof.

(69) Particularly when the rubber mixture of the invention is used for the internal components of a tire or an industrial rubber article which come into direct contact with strengthening elements present, a suitable bonding system, often in the form of tackifying resins, is generally also added to the rubber mixture.

(70) The proportion of the total amount of further additives is 3 to 150 phr, preferably 3 to 100 phr and more preferably 5 to 80 phr.

(71) The total proportion of the further additives includes 0.1 to 10 phr, preferably 0.2 to 8 phr, more preferably 0.2 to 4 phr, of zinc oxide (ZnO).

(72) This may be any type of zinc oxide known to those skilled in the art, for example ZnO pellets or powder. The conventionally used zinc oxide generally has a BET surface area of less than 10 m.sup.2/g. However, it is also possible to use what is called nano-zinc oxide having a BET surface area of 10 to 60 m.sup.2/g.

(73) The vulcanization is optionally carried out in the presence of sulfur and/or sulfur donors and with the aid of vulcanization accelerators, with some vulcanization accelerators simultaneously being able to act as sulfur donors.

(74) Bonded within polymer A of formula I) are network-forming groups that are involved in the vulcanization and crosslink during the vulcanization. However, the polymer A of formula I), in the context of the present invention, is not one of the sulfur donors.

(75) Sulfur and/or further sulfur donors and also one or more accelerators are added to the rubber mixture in the last mixing step. The accelerator is selected from the group consisting of thiazole accelerators and/or mercapto accelerators and/or sulfenamide accelerators and/or thiocarbamate accelerators and/or thiuram accelerators and/or thiophosphate accelerators and/or thiourea accelerators and/or xanthogenate accelerators and/or guanidine accelerators.

(76) Preference is given to using at least one sulfenamide accelerator selected from the group consisting of N-cyclohexyl-2-benzothiazolesulfenamide (CBS) and/or N,N-dicyclohexylbenzothiazole-2-sulfenamide (DCBS) and/or benzothiazyl-2-sulfenomorpholide (MBS) and/or N-tert-butyl-2-benzothiazylsulfenamide (TBBS).

(77) Sulfur donor substances used may be any sulfur donor substances known to those skilled in the art. If the rubber mixture comprises a sulfur-donating substance, it is preferably selected from the group comprising, for example, thiuram disulfides, for example tetrabenzylthiuram disulfide (TBzTD) and/or tetramethylthiuram disulfide (TMTD) and/or tetraethylthiuram disulfide (TETD), and/or thiuram tetrasulfides, for example dipentamethylenethiuram tetrasulfide (DPTT), and/or dithiophosphates, for example DipDis (bis(diisopropyl)thiophosphoryl disulfide) and/or bis(O,O-2-ethylhexylthiophosphoryl) polysulfide (e.g. Rhenocure SDT 50, Rheinchemie GmbH) and/or zinc dichloryldithiophosphate (e.g. Rhenocure ZDT/S, Rheinchemie GmbH) and/or zinc alkyldithiophosphate, and/or 1,6-bis(N,N-dibenzylthiocarbamoyldithio)hexane and/or diaryl polysulfides and/or dialkyl polysulfides.

(78) Further network-forming systems as obtainable, for example, under the Vulkuren, Duralink or Perkalink trade names or network-forming systems as described in WO 2010/049216 A2 can also be used in the rubber mixture. This system contains a vulcanizing agent which crosslinks with a functionality of greater than four and at least one vulcanization accelerator. The vulcanizing agent which crosslinks with a functionality of greater than four has, for example, the general formula D):
G[C.sub.aH.sub.2aCH.sub.2S.sub.bY].sub.cD)
where G is a polyvalent cyclic hydrocarbon group and/or a polyvalent heterohydrocarbon group and/or a polyvalent siloxane group containing 1 to 100 atoms; where each Y is selected independently from a rubber-active group containing sulfur-containing functionalities; and where a, b and c are integers where, independently, a=0 to 6; b=0 to 8; and c=3 to 5.

(79) The rubber-active group is preferably selected from a thiosulfonate group, a dithiocarbamate group, a thiocarbonyl group, a mercapto group, a hydrocarbon group and a sodium thiosulfonate group (Bunte salt group).

(80) Very good abrasion and tensile properties of the rubber mixture according to the invention are achieved in this way.

(81) The required amount of further sulfur in the form of elemental sulfur and/or further sulfur donors depends on the field of use of the respective rubber mixture. The respective amounts to be added are known to those skilled in the art. When elemental sulfur is added, the amounts in the case of a rubber mixture for the bead of vehicle tires are, for example, 0 to 5 phr. In the case of treads of vehicle tires, which generally have a lower sulfur content than the bead, the amount of elemental sulfur to be added is preferably 0 to 4 phr.

(82) In an advantageous development of the invention, a plurality of accelerators are used. Preference is given to using a sulfenamide accelerator, more preferably CBS, in combination with the guanidine accelerator DPG (diphenylguanidine). The amount of DPG is 0 to 5 phr, preferably 0.1 to 3 phr, more preferably 0.5 to 2.5 phr, most preferably 1 to 2.5 phr.

(83) In addition, vulcanization retarders may be present in the rubber mixture.

(84) The present invention further provides a process for producing a sulfur-crosslinkable rubber mixture. The process of the invention comprises a) the mixing of 10 to 100 phr of at least one modified polymer A which has been prepared as described above with 0 to 90 phr of at least one further rubber and 20 to 300 phr of at least one filler for production of a rubber base mixture, and b) the subsequent mixing with at least one sulfur donor and/or elemental sulfur and/or at least one vulcanization accelerator for production of a finished rubber mixture, as detailed above. This is preferably followed by a vulcanization.

(85) All the statements made above relating to polymer A and the other constituents of the rubber mixture of the invention are analogously applicable to the process of the invention.

(86) Such a process provides a rubber mixture which, by comparison with prior art rubber mixtures, has an improvement in the trade-off between rolling resistance and wet grip, with abrasion characteristics remaining at a comparable level or likewise being improved.

(87) It is essential to the invention that the polymer, as already set out above for the rubber mixture of the invention, is modified along the polymer chains P before being mixed into the rubber mixture.

(88) The mere mixing of a polymer with a modifier and subsequent further processing to form or in a rubber mixture, as disclosed in WO2008/076875A1, does not lead to such a surprising improvement in the trade-off between rolling resistance and wet grip; see tab. 4.

(89) The rubber mixture is otherwise produced by the process which is customary in the rubber industry and in which a base mixture comprising all constituents apart from the vulcanization system (sulfur and vulcanization-influencing substances) is firstly produced in one or more mixing stages. The final mixture is produced by adding the vulcanization system in a final mixing stage. The finished mixture is processed further, for example, by an extrusion operation and converted to the appropriate shape.

(90) The present invention further provides a vulcanizate which is obtained by sulfur vulcanization of at least one rubber mixture of the invention comprising the polymer A and at least one filler. What is provided by the invention here is thus the vulcanized rubber mixture.

(91) All the statements made above relating to polymer A and the other constituents of the rubber mixture of the invention are analogously applicable to the vulcanizate of the invention.

(92) For use in vehicle tires, the mixture is preferably brought into the shape of a tread and applied in a known manner in the production of the vehicle tire blank. However, the tread can also be rolled up in the form of a narrow strip of rubber mixture onto a tire blank. In the case of two-part treads (upper part: cap and lower part: base), the rubber mixture of the invention can be used both for the cap and for the base.

(93) The rubber mixture of the invention for use as body mixture in vehicle tires is produced as described above for the tread. The difference lies in the shaping after the extrusion operation. The resulting shapes of the rubber mixture of the invention for one or more different body mixtures then serve for construction of a tire blank.

(94) The invention will now be illustrated in detail with the aid of comparative examples and working examples which are summarized in tables 1 to 3.

(95) Room temperature (RT) as used herein refers to a temperature of about 20-25 C. or, in the case of measurement of a specific parameter, of 20 C.

(96) Synthesis of the Polymer Backbone Modifier BM1

(97) Hexane-1,6-dithiol (12.7 g, 84.2 mmol) was dissolved in 300 mL of tert-butyl methyl ether, and n-BuLi (30.0 g mL, 92.5 mmol, 20% by weight in cyclohexane) was added dropwise. The mixture was stirred at room temperature for 2 h, and tert-butyldimethylchlorosilane was added (12.6 g, 83.7 mmol). After the mixture had been refluxed overnight, water was added. The organic phase was removed and washed twice with water. The collected aqueous phases were combined and washed with diethyl ether. The collected and combined organic phases were dried with sodium sulfate, and the volatile constituents were removed under reduced pressure. The residue was fractionally distilled to obtain a yield of 64% of BM1, boiling point 105 C. at 0.2 mbar.

(98) .sup.1H NMR (400 Hz, C.sub.6D.sub.6, 298 K): =0.21 (s, 6H, Si(CH.sub.3).sub.2); 0.99 (s, 9H, C(CH.sub.3).sub.3); 1.15-1.05 (m, 3H, CH.sub.2/SH); 1.23-1.15 (m, 2H, CH.sub.2); 1.29 (qu, 2H, CH.sub.2); 1.50 (qu, 2H, CH.sub.2); 2.12 (q, 2H, CH.sub.2SH); 2.40 (t, 2H, CH.sub.2SSi); .sup.13C NMR (101 Hz, C.sub.6D.sub.6, 298 K): =3.09 (CH.sub.3), 19.50 (CH.sub.2), 24.90 (CH.sub.2), 26.91 (CH.sub.3), 27.04 (CH.sub.2), 28.43 (CH.sub.2), 28.67 (CH.sub.2), 33.63 (CH.sub.2), 34.53 (CH.sub.2).

(99) ##STR00001##
Copolymerization of 1,3-Butadiene with Styrene (Comparative Polymer V)

(100) The copolymerization was conducted in a jacketed 40 L steel reactor that was purged with nitrogen prior to the addition of the organic solvent, the monomers, the polar coordinator compound, the initiator compound and other components. The following components were added in the sequence specified: cyclohexane solvent (18 560 g); butadiene monomer (1777 g), styrene monomer (448 g) and tetramethylethylenediamine (TMEDA, 1.0 g), and the mixture was heated to 40 C., followed by titration with n-butyllithium to remove traces of moisture or other impurities. n-BuLi (17.6 mmol) was added to the polymerization reactor to initiate the polymerization reaction. The polymerization was conducted for 20 minutes, in the course of which the polymerization temperature was not allowed to rise to more than 70 C. Then butadiene (1202 g) and styrene (91 g) as monomers were added over the course of 55 min. The polymerization was conducted for a further 20 minutes, followed by the addition of 63 g of butadiene monomer. After 20 minutes, the polymerization was terminated by addition of methanol (one equivalent based on the initiator). 0.25% by weight of IRGANOX 1520, based on the total monomer weight, was added to the polymer solution as stabilizer. This mixture was stirred for 10 minutes. The resulting polymer solution was then stripped with steam for one hour in order to remove solvents and other volatile substances, and dried in an oven at 70 C. for 30 minutes and then additionally at room temperature for three days.

(101) Preparation of Backbone-Modified Polymer A

(102) First of all, the copolymerization of 1,3-butadiene and styrene was conducted analogously to the preparation of the comparative polymer V. The backbone modification was conducted in a jacketed 10 L steel reactor that had first been purged with nitrogen before the comparative polymer V (4000 g) was added, followed by the addition of cyclohexane (2000 g) and the backbone modifier BM1 (7.7 g, 29.1 mmol). The mixture was heated to 95 C., and lauroyl peroxide solution in cyclohexane was added in 4 portions every 30 minutes (1.13/0.86/0.57/0.28 mmol, total of 2.84 mmol). The polymer solution was cooled down to room temperature, and 1.2 g of IRGANOX 1520 were added. A GC analysis of the unconverted backbone modifier BM1 showed a graft yield of 60%. The modified polymer solution was then stripped with steam for one hour in order to remove solvents and other volatile substances, and dried in an oven at 70 C. for 30 minutes and then additionally at room temperature for three days.

(103) Preparation of Polymer A by Extraction of the Unconverted Backbone Modifier BM1 from Polymer A

(104) Polymer A (94 g) was comminuted in a granulator, and the rubber crumbs obtained were suspended in isopropanol (800 g). The suspension was refluxed for 8 hours, and the rubber crumbs were removed and dried. A GC analysis showed that 90% of the backbone modifier BM1 present had been removed.

(105) TABLE-US-00001 TABLE 1 Analytical data for the comparative polymer V and polymer A Mw Mn Mooney Vinyl content Styrene content Tg [g/mol] [g/mol] viscosity [% by wt.] [% by wt.] [ C.] Comparative 334417 303967 35.3 29.2 15.1 60.6 polymer V Polymer A 476469 358682 66.2 29.6 14.7 60.7
Production of Rubber Mixtures and Comparative Tests

(106) The mixtures marked I are here mixtures of the invention, while the mixtures marked C are comparative mixtures. In all the examples of mixtures in tables 2 to 4, the stated amounts are in parts by weight based on 100 parts by weight of total rubber (phr) or on 100 parts by weight of silica (phf).

(107) The mixture was produced under standard conditions in two stages in a laboratory tangential mixer.

(108) The inventive rubber mixtures I1, I2 and I4 contain 90 phr of polymer A (formula I). In the rubber mixtures C1, C3 and C4, rather than a polymer of formula I), the comparative polymer V having a comparable molecular weight, a comparable vinyl content and a comparable styrene content to polymer A was used. The comparative polymer is unmodified and is not a coupled polymer. Rubber mixture C2 has been adjusted with a greater amount of vulcanizing agents (accelerator and sulfur) to the same hardness at 70 C. as I1 and is thus the reference of equal hardness. The inventive rubber mixture I3 contains the polymer A which has been obtained after completion of modification from the polymer A by purification, i.e. removal of any residual modifier BM1.

(109) All mixtures were used to produce test specimens by vulcanization, and these test specimens were used to determine material properties typical for the rubber industry. For the above-described tests on test specimens, the following test methods were employed: Shore A hardness (unit: Shore A, abbreviated to ShA) at room temperature (RT) and at 70 C. in accordance with DIN 53 505 Rebound resilience (resilience) at room temperature (RT) and 70 C. in accordance with DIN 53 512 Stress values at 50%, 100%, 200%, 300% elongation (50 modulus, 100 modulus, 200 modulus and 300 modulus respectively) at room temperature (RT) in accordance with DIN 53 504 with the ring test specimens: C1, C2, I1, C3, I2, I3, C5, C6, C7 and S3 specimen from 2 mm frame: C4, I4, C8, C9, C10 Tensile strength and elongation at break at room temperature in accordance with DIN 53 504 Abrasion at room temperature in accordance with DIN 53 516 or DIN/ISO 4649 Maximum loss factor tan (max) from dynamic-mechanical measurement in accordance with DIN 53 513 (temperature sweep)
Substances Used
.sup.a) Aging stabilizers: antiozonant wax and 6PPD
.sup.b) Silica: VN3, from Evonik
.sup.c) Silane: S2 silane, 75% by weight of disulfides, for example Si 266 from Evonik Industries AG
.sup.d) Blocked mercaptosilane: NXT, 3-(octanoylthio)-1-propyltriethoxysilane, from Momentive
.sup.e) Modifier: hexane-1,6-dithiol
.sup.f) Modifier: double-protected hexane-1,6-dithiol:

(110) ##STR00002##

(111) TABLE-US-00002 TABLE 2 Unit C1 C2 I1 Constituents NR TSR phr 10 10 10 Comparative polymer V phr 90 90 Polymer A phr 90 N339 carbon black phr 85 85 85 TDAE oil phr 45 45 45 Aging stabilizer.sup.a) phr 4 4 4 Stearic acid phr 2.5 2.5 2.5 Zinc oxide phr 2.5 2.5 2.5 CBS accelerator phr 6.4 9.6 6.4 Sulfur phr 0.64 0.96 0.64 Physical properties Shore hardness at RT Shore A 65 68 66 Shore hardness at 70 C. Shore A 60.4 64 64 Rebound resilience at RT % 31 31.8 37.8 Rebound resilience at 70 C. % 45.8 49.1 55.3 Diff. rebound (70 C. - RT) 14.8 17.3 17.5 50 modulus MPa 1.4 1.7 1.8 100 modulus MPa 2.5 3.5 4.2 Tensile strength MPa 11.7 11.7 11.3 Elongation at break % 342 265 206 Tan (max) 0.259 0.243 0.188 Abrasion mm.sup.3 94 129 92

(112) TABLE-US-00003 TABLE 3 Constituents Unit C3 I2 I3 C4 I4 NR TSR phr 10 10 10 10 10 Comparative polymer V phr 90 90 Polymer A phr 90 90 Polymer A phr 90 Silica .sup.b) phr 95 95 95 95 95 Silane .sup.d) phf 7.2 7.2 7.2 Silane .sup.d) phf 8.1 8.1 TDAE oil phr 35 35 35 35 35 Ag. st. .sup.a) phr 4 4 4 4 4 Stearic acid phr 2.5 2.5 2.5 2.5 2.5 Zinc oxide phr 2.5 2.5 2.5 2.5 2.5 DPG phr 2.0 2.0 2.0 2.0 2.0 CBS phr 6.4 6.4 6.4 6.4 6.4 Sulfur phr 0.64 0.64 0.64 0.64 0.64 Physical properties Hardness RT Shore A 74.2 73.9 76 72.7 70.2 Hardness 70 C. Shore A 69.6 70.6 72.2 68.7 68.3 Rebound RT % 36.9 41 40.5 37.0 45.6 Rebound 70 C. % 47.4 55.9 54.6 48.8 62.8 Diff. rebound 10.5 14.9 14.1 11.8 17.2 50 modulus MPa 1.8 2.1 2.1 100 modulus MPa 2.9 4.2 4 2.9 3.3 200 modulus MPa 5.6 10 10.1 5.5 8.1 Tensile strength MPa 16.4 15 18 14.9 14.6 Elongation at break % 506 296 329 472 308 Tan (max) 0.212 0.167 0.174 0.189 0.127 Abrasion mm.sup.3 61 77 58 69 95

(113) TABLE-US-00004 TABLE 4 Constituents Unit C5 C6 C7 C8 C9 C10 NR TSR phr 10 10 10 10 10 10 Comparative polymer V phr 90 90 90 90 90 90 Modifier .sup.e) phr 0.85 3.0 3.0 Modifier .sup.f) phr 7.75 N339 carbon black phr 85 85 85 Silica .sup.b) phr 95 95 95 Silane .sup.c) phf 7.2 7.2 7.2 TDAE oil phr 35 35 35 45 45 45 Ag. st. .sup.a) phr 4 4 4 4 4 4 Stearic acid phr 2.5 2.5 2.5 2.5 2.5 2.5 Zinc oxide phr 2.5 2.5 2.5 2.5 2.5 2.5 DPG phr 2.0 2.0 2.0 CBS phr 6.4 6.4 6.4 6.4 6.4 6.4 Sulfur phr 0.64 0.64 0.64 0.64 0.64 0.64 Physical properties Hardness RT Shore A 74.1 75.8 73.4 64 60 56 Hardness 70 C. Shore A 69.6 71.0 68.2 59 55 49 Rebound RT % 18.0 17.8 18.5 18 19 20 Rebound 70 C. % 46.5 48.0 47.6 37 40 35 Diff. rebound 28.5 30.2 29.1 19 21 15 50 modulus MPa 2.0 2.2 1.8 100 modulus MPa 3.7 3.9 3.1 2.09 1.90 1.24 200 modulus MPa 7.3 7.7 6.1 5.63 5.17 2.79 Tensile strength MPa 12 11 12 14.4 14.3 12.9 Elongation at break % 318 288 368 412 459 627 Tan (max) 0.196 0.195 0.206 0.272 0.268 0.299 Abrasion mm.sup.3 175 135 146 181 211 312

(114) As apparent from table 1, the inventive rubber mixture I1 comprising carbon black as filler, compared to the comparative mixture C1, shows an improvement in the trade-off between rolling resistance and wet grip, which is apparent from the greater difference in the two indicators of rebound resilience at 70 C. (rolling resistance) and room temperature (wet grip). Moreover, the improved rolling resistance of I1 is apparent from the lower value for maximum loss factor (tan max.). In addition, the inventive rubber mixture I1 compared to C1 shows comparable abrasion characteristics and comparable tensile strength. Compared with the equal-hardness reference C2, the inventive rubber mixture I1 shows a distinct improvement in abrasion characteristics.

(115) As can be seen from table 2, the inventive rubber mixtures I2, I3 and I4 comprising silica as filler, compared to the respective comparative mixtures C3 and C4, show an improvement in the trade-off between rolling resistance and wet grip, which is apparent from the greater differences in the two indicators of rebound resilience at 70 C. (rolling resistance) and room temperature (wet grip). It appears here that the purification of the polymer on completion of modification (I3 with purified modified polymer A vs. I2 with modified polymer A) does not have any significant effect on the improvement in the trade-off between rolling resistance and wet grip. The abrasion characteristics of I2 and I4, by comparison with the respective comparative mixtures, are at an acceptable level, whereas I3 comprising the purified polymer A surprisingly exhibits good abrasion characteristics. It is thus possible with the rubber mixture of the invention, especially through the use in the tread, to further improve the trade-off between rolling resistance and wet grip characteristics on the basis of the prior art without any deterioration in abrasion resistance. As can be seen from table 3, the improvements are not observed either with hexane-1,6-dithiol (C6 or C7 versus C5 and C9 versus C8) or with the double-protected hexane-1,6-dithiol (C10 versus C8), which are added as modifiers to the comparative polymer V in the mixing of the rubber mixture and have not been linked to the polymer beforehand. Here there is either a deterioration in the differences in the rebound resiliences and tangent delta, or they remain at a similar level with a deterioration in the abrasion characteristics.

(116) It is thus essential to the invention that polymer A has already been modified as per formula I) before it is mixed into the rubber mixture together with the other mixture constituents, and there is no separate addition of unmodified polymer and modifier to the rubber mixture.