SILANE, RUBBER MIXTURE CONTAINING THE SILANE AND VEHICLE TIRE INCLUDING THE RUBBER MIXTURE IN AT LEAST ONE COMPONENT, AS WELL AS A METHOD FOR PRODUCING THE SILANE

Description

[0001] The invention relates to a silane, a rubber mixture containing the silane and a vehicle tire which has the rubber mixture in at least one component, as well as to processes for producing the silane.

[0002] The subject matter of the invention is defined in the appended claims.

[0003] Silanes are known as additives for rubber compounds, particularly for vehicle tires, and specifically for rubber compounds containing at least one silica as a filler. Silanes known in the prior art are disclosed, for example, in DE 2536674 C3 and DE 2255577 C3. The silica is bonded to the polymer(s) by means of such silanes, which is why the silanes are also referred to as coupling agents. Bonding the silica by means of silane coupling agents results in advantages with regard to the rolling resistance behavior and the processability of the rubber compound. For this purpose, the silane typically contains at least one sulfur group, which is involved in the vulcanization of the rubber compound.

[0004] In principle, a distinction can be made between silanes that bind only to silica or comparable fillers and, for this purpose, in particular, have at least one silyl group, and silanes that, in addition to a silyl group, have a reactive sulfur group, such as, in particular, an S x group (where x is greater than or equal to 2) or a mercapto group SH or a blocked S-SG group, where SG stands for a protecting group, so that the silane can also bind to polymers by reaction of the S x or SH group or the S-SG group after removal of the protecting group during sulfur vulcanization. The presence of -H or -SG can also be expressed by a radical R.

[0005] In addition, there are approaches in the prior art involving known silanes that have multiple polymer attachment sites. Such silanes are disclosed, for example, in US Pat. No. 7,696,269 B2. The silica is bonded to the polymer(s) via more than one attachment site using such silanes. For this purpose, the silane typically contains at least two reactive sulfur groups described above, which are involved in the vulcanization of the rubber mixture.

[0006] EP 2944643 A1 relates to urea-containing mercaptosilanes, processes for their preparation and their use, wherein the urea-containing mercaptosilanes are applied to a carrier, for example silica.

[0007] The present invention is based on the object of providing a novel silane and a rubber mixture with the silane, whereby, compared to the prior art, a further improvement in the property profile comprising the rolling resistance behavior, the grip behavior ( English "grip"), especially wet grip, and the stiffness and thus in particular the handling predictors of the rubber compound, especially for application in vehicle tires, are achieved.

[0008] The object is achieved by the silane according to the invention according to claim 1, the silica modified with the silane according to the invention, the rubber mixture according to the invention containing the silane, and the vehicle tire according to the invention, which has the rubber mixture according to the invention in at least one component. Furthermore, the object is achieved by the process for producing the silane according to claim 12 or 13.

[0009] The silane according to the invention is derived from the silane of the following formula I disclosed below): I) (R 1< ) o Si-[R 2< -X] m -R 2< -Y(-R 2< -[XR 2< -] m SR 3< ) 2 , where o = 3 and the radicals R 1< can independently of one another be the same or different from one another and are selected from alkoxy groups having 1 to 10 carbon atoms, cycloalkoxy groups having 4 to 10 carbon atoms, phenoxy groups having 6 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, halides or alkylpolyether groups -O-(R 6< -O) r -R 5< where R 6< are the same or different and are branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic / aromatic bridging C 1 -C 30 hydrocarbon groups, preferably -CH 2 -CH 2 -, r is an integer from 1 to 30, preferably 3 to 10, and R 5< unsubstituted or substituted, branched or unbranched, terminal alkyl, alkenyl,aryl or aralkyl groups, preferably -C 13 H 27 alkyl group, or two R 1< form a cyclic dialkoxy group having 2 to 10 carbon atoms, or two or more silanes according to formula I) can be bridged via radicals R 1<; and where the radicals R 2< independently of one another can be the same or different and are selected from the group consisting of linear or branched alkylene groups having 1 to 20 carbon atoms or cycloalkylene groups having 4 to 12 carbon atoms or arylene groups having 6 to 20 carbon atoms or alkenylene groups having 2 to 20 carbon atoms, alkynylene groups having 2 to 20 carbon atoms or aralkylene groups having 7 to 20 carbon atoms; and wherein the group R 3< is a hydrogen atom or a -C(=O)-R 4< group or a -SiR 8< 3 group, wherein R 4< and R 8< are selected from C 1 -C 20 alkyl groups, C 4 -C 10 cycloalkyl groups, C 6 -C 20 aryl groups,C 2 -C 20 alkenyl groups and C 7 -C 20 aralkyl groups and R 8< is additionally selected from alkoxy groups having 1 to 10 carbon atoms, cycloalkoxy groups having 4 to 10 carbon atoms, phenoxy groups having 6 to 20 carbon atoms; and wherein Y represents a central at least trivalent unit selected from N, P, CH, SiH and B; and wherein the m can independently be the same or different and each m is an integer from 0 to 4; and wherein the groups X can independently be the same or different and are selected from the groups -HNC(=O)-, -C(=O)NH-, -C(=O)O-, -OC(=O)-, -OC(=O)NH-, -HNC(=O)O-, -HNC(=O)NH-, -R 7< NC(=O)NR 7< -, -R 7< NC(=NR 7< )NR 7< -, -R 7< NC(=S)NR 7< -,where the radicals R 7< within the group X can be the same or different and are selected from a hydrogen atom or are selected from the group consisting of linear or branched alkyl groups having 1 to 20 carbon atoms or cycloalkyl groups having 4 to 12 carbon atoms or aryl groups having 6 to 20 carbon atoms or alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms or aralkyl groups having 7 to 20 carbon atoms under the condition that at least one R 7< within the group X is a hydrogen atom, and where the silane can also be in the form of oligomers which are formed by hydrolysis and condensation of silanes of the formula I).

[0010] Compared to silanes known from the prior art, the silane with the group -Y(-R 2< -[XR 2< -] m SR 3< ) 2 has two groups that can bond to the polymer after removal of the protecting group R 3<. This provides a novel silane. A rubber compound containing the silane exhibits an optimized property profile, including rolling resistance behavior and stiffness. The rubber compound thus exhibits a certain improvement in the property profile, including handling predictors, and the vehicle tire exhibits, among other things, improved handling behavior.

[0011] The silane and its preferred embodiments are explained below. All aspects also apply to the silane in the rubber compound and in the vehicle tire, as well as to the manufacturing process, unless expressly stated otherwise.

[0012] The terms "residue" and "group" are used synonymously in the context of the present invention in connection with chemical formula components.

[0013] As shown in formula I), the silane is a blocked mercaptosilane with the grouping SR 3< , where R 3< represents a hydrogen atom or a protecting group due to its more precisely specified properties, so that the sulfur is then activated by removing the protecting group as described above in order to be able to participate in sulfur vulcanization.

[0014] The group R 3< is a hydrogen atom or a -C(=O)-R 4< group or a -SiR 8< 3 group, where R 4< and R 8< are selected from C 1 -C 20 alkyl groups, C 4 -C 10 cycloalkyl groups, C 6 -C 20 aryl groups, C 2 -C 20 alkenyl groups and C 7 -C 20 aralkyl groups and R 8< is additionally selected from alkoxy groups having 1 to 10 carbon atoms, cycloalkoxy groups having 4 to 10 carbon atoms, phenoxy groups having 6 to 20 carbon atoms.

[0015] According to particularly advantageous embodiments of the invention, R 3< is a -C(=O)-R 4< group or a -SiR 8< 3 group, whereby the silane in these advantageous embodiments is a blocked mercaptosilane. This has the advantage that the sulfur can only participate in chemical reactions after the aforementioned groups for R 3< have been removed, preventing undesirable side reactions from occurring beforehand. The silane is thus easier to process, in particular, easier to mix into a rubber mixture.

[0016] Particularly preferably, the group R 3< is a -C(=O)-R 4< group, where R 4< is selected from C 1 -C 20 alkyl groups.

[0017] R 4< is very particularly preferably selected from C 1 to C 7 alkyl groups, again preferably C 1 -C 3 alkyl groups, in particular, for example, a C 1 alkyl group, i.e. a methyl group.

[0018] The radicals R 1< of the silane according to the invention can be identical or different from one another within the silyl group (R 1< ) o Si-independently of one another and are selected from alkoxy groups having 1 to 10 carbon atoms, cycloalkoxy groups having 4 to 10 carbon atoms, phenoxy groups having 6 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, halides or alkyl polyether groups -O-(R 6< -O) r -R 5< where R 6< are identical or different and are branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic / aromatic bridging C 1 -C 30 hydrocarbon groups are, preferably -CH 2 -CH 2 -, r is an integer from 1 to 30, preferably 3 to 10, and R 5< unsubstituted or substituted, branched or unbranched,terminal alkyl, alkenyl, aryl, or aralkyl groups, preferably -C 13 H 27 alkyl groups, or two R 1< form a cyclic dialkoxy group having 2 to 10 carbon atoms, or two or more silanes according to formula I) can be bridged via R 1< radicals. All mentioned R 1< radicals and linkages can be combined with one another within a silyl group.

[0019] When two silanes according to formula I) are bridged together, they share a R 1< radical. In this way, more than two silanes can be linked together. Following the synthesis of the silane according to formula I), it is therefore conceivable that two silanes according to formula I) are bridged together via the R 1< radicals. In this way, more than two silanes can be linked together, for example, via dialkoxy groups.

[0020] The silane may also comprise oligomers formed by hydrolysis and condensation of the silanes of formula I). This includes, on the one hand, oligomers of two or more silanes according to formula I). Furthermore, oligomers formed by condensation of at least one silane according to formula I with at least one further silane that does not correspond to formula I) are also included. The "further silane" may, in particular, be silane coupling agents known to those skilled in the art.

[0021] According to an advantageous embodiment, in particular for use of the silane in a silicic acid-containing rubber mixture, the silane according to formula I) comprises in each silyl group (R 1< ) o Si- at least one radical R 1< which can serve as a leaving group, such as in particular alkoxy groups or all other of the groups mentioned which are bonded to the silicon atom by an oxygen atom, or halides.

[0022] It is preferred that the radicals R 1< comprise alkyl groups having 1 to 6 carbon atoms or alkoxy groups having 1 to 6 carbon atoms or halides, particularly preferred are alkoxy groups having 1 to 6 carbon atoms or halides.

[0023] According to a particularly advantageous embodiment of the invention, the radicals R 1< within a silyl group (R 1< ) o Si- are equal to and alkoxy groups having 1 or 2 carbon atoms, i.e. methoxy groups or ethoxy groups, very particularly preferably ethoxy groups, where o = 3.

[0024] But also in the case of oligomers or in the case where two R 1< form a dialkoxy group, the remaining radicals R 1< are preferably alkyl groups having 1 to 6 carbon atoms or halides or alkoxy groups having 1 to 6 carbon atoms, preferably 1 or 2 carbon atoms, i.e. methoxy groups or ethoxy groups, very particularly preferably ethoxy groups.

[0025] The radicals R 2< of the silane according to the invention can be independently identical or different from one another within a molecule and are selected from the group consisting of linear or branched alkylene groups having 1 to 20 carbon atoms or cycloalkylene groups having 4 to 12 carbon atoms or arylene groups having 6 to 20 carbon atoms or alkenylene groups having 2 to 20 carbon atoms, alkynylene groups having 2 to 20 carbon atoms or aralkylene groups having 7 to 20 carbon atoms.

[0026] It is preferred that the radicals R 2< are independently identical or different and are linear or branched alkylene radicals having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, particularly preferably 2 to 5 carbon atoms, in particular, for example, 2 or 3 carbon atoms.

[0027] The group Y represents a central at least trivalent unit which is selected from N, P, CH, SiH and B. N stands for nitrogen (trivalent nitrogen atom), P for phosphorus (trivalent phosphorus atom), CH for a carbon atom to which a hydrogen atom is bonded, so that three valences are still free, SiH stands analogously for silicon with one hydrogen atom and three free valences and B for boron, which is also trivalent.

[0028] According to the invention, Y is a trivalent nitrogen atom (N).

[0029] The groups X are, as stated for formula I), selected from the groups -HNC(=O)-, -C(=O)NH-, -C(=O)O-, -OC(=O)-, -OC(=O)NH-, -HNC(=O)O-, -HNC(=O)NH-, -R 7< NC(=O)NR 7< -, -R 7< NC(=NR 7< )NR 7< -, -R 7< NC(=S)NR 7< -, where the radicals R 7< within the group X can be the same or different and are selected from a hydrogen atom or are selected from the group consisting of linear or branched alkyl groups having 1 to 20 carbon atoms or cycloalkyl groups having 4 to 12 carbon atoms or aryl groups having 6 to 20 carbon atoms or alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms or aralkyl groups having 7 to 20 carbon atoms, provided that at least one R 7< within the group X is a hydrogen atom.

[0030] The groups -HNC(=O)- and -C(=O)NH- are carboxamide groups, whereby the two different notations are intended to express the possible connectivities with regard to the respective residues R 2< within the molecule.

[0031] The groups -C(=O)O- and -OC(=O)- are ester groups, whereby here too the two notations, analogous to the acid amide groups, refer to the different connectivities with regard to the respective residues R 2<.

[0032] The groups -OC(=O)NH- and -HNC(=O)O- are urethane groups, whereby here too the two notations, analogous to the acid amide groups, refer to the different connectivities with regard to the respective residues R 2<.

[0033] According to advantageous embodiments of the invention, X is a -OC(=O)NH- or -HNC(=O)O- group or a -C(=O)O- or -OC(=O)- group.

[0034] In embodiments of the invention, the silane according to the invention has the following formula II): II) (R 1< ) o Si-R 2< -XR 2< -Y(-R 2< -SR 3< ) 2 .

[0035] The silane according to formula II) represents a possible structure according to the invention.

[0036] It is preferred that in formula II) X is a -OC(=O)NH- or -HNC(=O)O- group. According to the invention, Y in formula II) is a trivalent nitrogen atom (N).

[0037] A particularly preferred embodiment of the formula II) is the silane of the formula II)-a): II)-a) (R 1< ) o Si-R 2< -(H)NC(=O)OR 2< -N(R 2< -SR 3< ) 2 .

[0038] In embodiments of the invention, the silane according to the invention alternatively has the following formula III): III) (R 1< ) o Si-R 2< -Y(-R 2< -XR 2< -SR 3< ) 2 .

[0039] The silane according to formula III) represents a possible structure according to the invention. It is preferred that in formula III) X is a -C(=O)O- or -OC(=O)- group. According to the invention, Y in formula III) is a trivalent nitrogen atom (N).

[0040] A particularly preferred embodiment of the formula III) is the silane of the formula III)-a): III)-a) (R 1< ) o Si-R 2< -N(-C(H) 2 -C(H) 2 -C(=O)OC(H) 2 -C(H) 2 -C(H) 2 -SR 3< .

[0041] In a particularly preferred and exemplary embodiment of the invention, the silane according to the invention has the following formula IV):

[0042] The silane according to formula IV) is an example of structure III)-a), which is an example of the more general structure III), which is a possible structure of formula I).

[0043] In a further particularly preferred and exemplary embodiment of the invention, the silane according to the invention has the following formula V)

[0044] The silane according to formula V) is an example of structure II)-a), which is an example of the more general structure II), which is a possible structure of formula I).

[0045] The present invention further provides a process for preparing the silane according to the invention according to formula II)-a) as an example for II), where X in formula II) is an HNC(=O)O group and Y is a trivalent nitrogen atom. II)-a) (R 1< ) o Si-R 2< -(H)NC(=O)OR 2< -N(R 2< -SR 3< ) 2

[0046] The inventive method V1 according to this embodiment comprises at least the following method steps: a) Providing a substance (R l< ) o Si-R 2< -N=C=O ; b) Providing a substance (HO-R 2< ) 3 N ; c) Reacting the substance from step a) with the substance from step b) to give (R 1< ) o Si-R 2< -(H)NC(=O)OR 2< -N(R 2< -OH) 2 d) Providing a substance R 3< -SH ; e) Reacting one equivalent of the substance from step c) with two equivalents of the substance from step d) to give II)-a) (R 1< ) o Si-R 2< -(H)NC(=O)OR 2< -N(R 2< -SR 3< ) 2 f) Optionally purifying the silane obtained in step e).

[0047] The above statements apply to the radicals R 1< , R 2< , R 3< and the index o unless expressly stated otherwise.

[0048] For example, the silane according to formula V) can be prepared in the manner described according to process V1.

[0049] The substances according to steps a) and b) and d) can be purchased and supplied commercially.

[0050] The reaction according to step c) is preferably carried out in an organic solvent, such as tetrahydrofuran (THF), dimethylformamide (DMF) or dimethyl sulfoxide (DMSO), preferably THF.

[0051] Preferably, the reaction according to step c) takes place under a protective gas atmosphere, such as argon, and at room temperature (RT).

[0052] The reaction mixture is preferably stirred for several hours, for example 2 to 12 hours.

[0053] Preferably, the product according to step c) is purified before further reaction according to step e).

[0054] The reaction according to step e) is preferably carried out in an organic solvent, such as in particular tetrahydrofuran (THF) and is preferably carried out as a Mitsunobu reaction.

[0055] Here, the substance obtained in step c) is preferably first treated with triphenylphosphine (PPh 3 ) and diisopropyl azodicarboxylate (DIAD) or diethyl azodicarboxylate (DEAD) or tetramethylazodicarboxamide (TMAD) in THF at 0 °C under a protective gas atmosphere, followed by the addition of the substance according to step d). Only then is the mixture preferably warmed to room temperature.

[0056] The reaction mixture is preferably stirred for several hours, for example 2 to 12 hours.

[0057] The present invention further provides a process for preparing the silane according to the invention according to formula III)-a), where in formula III) X is a -C(=O)O- or -OC(=O)- group and Y is a trivalent nitrogen atom. III)-a) (R 1< ) o Si-R 2< -N(-C(H) 2 -C(H) 2 -C(=O)OC(H) 2 -C(H) 2 -C(H) 2 -SR 3<

[0058] The inventive method V2 according to this embodiment comprises at least the following method steps: aa) Providing a substance (R 1< ) o Si-R 2< -NH 2 ; bb) Providing a substance H 2 C=CC(=O)OC(H) 2 -C(H)=CH 2 ; cc) Reacting one equivalent of the substance from step aa) with two equivalents of the substance from step bb) to give (R 1< ) o Si-R 2< -N(-C(H) 2 -C(H) 2 -C(=O)OC(H) 2 -C(H)=CH 2 ) 2 ; dd) Providing a substance R 3< -SH ; ee) Reaction of one equivalent of the substance from step cc) with two equivalents of the substance from step dd) to III)-a) (R 1< ) o Si-R 2< -N(-C(H) 2 -C(H) 2 -C(=O)OC(H) 2 -C(H) 2 -C(H) 2 -SR 3< ; ff) Optionally purification of the silane obtained in step ee).

[0059] The above statements apply to the radicals R 1< , R 2< , R 3< and the index o unless expressly stated otherwise. By specifying the starting substances, some of the radicals R 2< in the prepared silane according to formula III) are already defined, resulting in the preferred embodiment according to formula III)-a).

[0060] For example, the silane according to formula IV) can be prepared in the manner described according to process V2.

[0061] The substances according to steps aa) and bb) and dd) can be purchased and made available commercially.

[0062] The reaction according to step cc) is preferably carried out in an organic solvent, such as ethanol, tetrahydrofuran (THF), dimethylformamide (DMF), dimethyl sulfoxide (DMSO) or 1,4-dioxane, preferably ethanol.

[0063] Preferably, the reaction according to step cc) takes place under a protective gas atmosphere, such as argon, and at RT.

[0064] The reaction mixture is preferably stirred for several hours, for example 2 to 12 hours.

[0065] Preferably, the product according to step cc) is purified before further reaction according to step ee).

[0066] The reaction according to step ee) is preferably carried out in an organic solvent, such as toluene or benzene and preferably in the presence of radical initiators such as azobis(isobutyronitrile (AIBN) or dibenzoyl peroxide (DBPO).

[0067] In this case, the substance obtained in step cc) is preferably first mixed with AIBN at 50 to 70 °C under a protective gas atmosphere, followed by the addition of the substance according to step dd). Only then is the mixture preferably heated to 80 to 95 °C.

[0068] The reaction mixture is preferably stirred for several hours, for example 2 to 12 hours.

[0069] According to process step f) or ff), the silane obtained in step e) or ee) is optionally purified, whereby the type of purification is determined by the state of aggregation in which the silane is obtained.

[0070] However, it is also conceivable to further use the produced silane without a purification step, for example by coating it on silica, as described below.

[0071] The present invention further provides a silica modified at least on its surface with at least one silane according to the invention. For example, the modification is carried out by at least the following process steps: gg) Optionally, dissolving the silane according to the invention from step e) or f) or ee) or ff) in an organic solvent; hh) contacting at least one silica with the silane from step e) or f) or ee) or ff) or the solution from step gg) and then stirring the resulting suspension, preferably for 30 minutes to 18 hours; ii) drying the resulting modified silica.

[0072] The silica may be any silica known to the person skilled in the art, in particular the types of silica listed in more detail below.

[0073] These further process steps represent a modification of silica with the silane prepared according to the invention and are a further aspect of the present invention.

[0074] The rubber mixture according to the invention contains at least one silane according to the invention. It is conceivable in principle for the rubber mixture to contain a plurality of silanes according to the invention of different embodiments, i.e. with optionally different groups X, as well as R 1< , R 2< and R 3< in the mixture. In particular, the rubber mixture can also contain a mixture of two or more silanes I) or II) or II)-a) or III) or III)-a) or IV) or V). The rubber mixture can also contain the silane according to the invention according to the formulas II) or II)-a) or III) or III)-a) or IV) or V) shown in combination with other silanes known in the prior art, optionally as oligomers, as described above.

[0075] Such coupling agents known from the prior art are, in particular and for example, bifunctional organosilanes which have at least one alkoxy, cycloalkoxy, or phenoxy group as a leaving group on the silicon atom and which have, as another functionality, a group which, optionally after cleavage, can enter into a chemical reaction with the double bonds of the polymer. The latter group can be, for example, the following chemical groups: -SCN, -SH, -NH 2 , or -Sx- (where x = 2 to 8).

[0076] For example, 3-mercaptopropyltriethoxysilane, 3-thiocyanatopropyltrimethoxysilane, or 3,3'-bis(triethoxysilylpropyl)polysulfides with 2 to 8 sulfur atoms, such as 3,3'-bis(triethoxysilylpropyl)tetrasulfide (TESPT), the corresponding disulfide (TESPD), or mixtures of sulfides with 1 to 8 sulfur atoms with varying contents of the various sulfides, can be used as silane coupling agents. TESPT can also be added, for example, as a mixture with carbon black (trade name X50S ®< from Evonik).

[0077] Also known in the prior art is a silane mixture containing 40 to 100 wt.% disulfides, particularly preferably 55 to 85 wt.% disulfides, and most preferably 60 to 80 wt.% disulfides. Such a mixture is available, for example, under the trade name Si 266 ®< from Evonik, which is described, for example, in DE 102006004062 A1.

[0078] Blocked mercaptosilanes, such as those known from WO 99 / 09036, can also be used as silane coupling agents. Silanes such as those described in WO 2008 / 083241 A1, WO 2008 / 083242 A1, WO 2008 / 083243 A1, and WO 2008 / 083244 A1 can also be used. Examples of suitable silanes include those sold under the name NXT (e.g., 3-(octanoylthio)-1-propyltriethoxysilane) in various variants by Momentive, USA, or those sold under the name VP Si 363 ® by Evonik Industries.

[0079] According to a particularly advantageous embodiment of the invention, the rubber mixture contains the silane according to formula II).

[0080] According to a particularly advantageous embodiment of the invention, the rubber mixture contains the silane according to formula II)-a).

[0081] According to a particularly advantageous embodiment of the invention, the rubber mixture contains the silane according to formula III).

[0082] According to a particularly advantageous embodiment of the invention, the rubber mixture contains the silane according to formula III)-a).

[0083] According to a particularly advantageous embodiment of the invention, the rubber mixture contains the silane according to formula IV).

[0084] According to a particularly advantageous embodiment of the invention, the rubber mixture contains the silane according to formula V).

[0085] The rubber mixture according to the invention is preferably a rubber mixture which is suitable for use in vehicle tires and for this purpose preferably contains at least one diene rubber.

[0086] Diene rubbers are rubbers that are produced by polymerization or copolymerization of dienes and / or cycloalkenes and thus have C=C double bonds either in the main chain or in the side groups.

[0087] The diene rubber is selected from the group consisting of natural polyisoprene and / or synthetic polyisoprene and / or epoxidized polyisoprene and / or butadiene rubber and / or butadiene-isoprene rubber and / or solution-polymerized styrene-butadiene rubber and / or emulsion-polymerized styrene-butadiene rubber and / or styrene-isoprene rubber and / or liquid rubbers with a molecular weight M w 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 fluororubber 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 hydrogenated styrene-butadiene rubber.

[0088] In particular, nitrile rubber, hydrogenated acrylonitrile butadiene rubber, chloroprene rubber, butyl rubber, halobutyl rubber or ethylene-propylene-diene rubber are used in the production of technical rubber articles, such as belts, straps and hoses, and / or shoe soles.

[0089] Preferably, the diene rubber is 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.

[0090] According to a preferred development of the invention, at least two different diene rubber types are used in the rubber mixture.

[0091] The rubber mixture according to the invention preferably contains at least one silica as a filler, which particularly emphasizes the advantages of the silane according to the invention. If the at least one silane according to the invention is added to the rubber mixture according to the invention in a form coated on a silica, the rubber mixture can contain additional silicas.

[0092] The terms "silicic acid" and "silica" are used synonymously in the present invention.

[0093] The silicas may be those known to the person skilled in the art that are suitable as fillers for tire rubber compounds. However, it is particularly preferred to use a finely divided, precipitated silica which has a nitrogen surface area (BET surface area) (according to DIN ISO 9277 and DIN 66132) of 35 to 400 m 2 / g, preferably of 35 to 350 m 2 / g, particularly preferably of 100 to 320 m 2 / g and very particularly preferably of 100 to 235 m 2 / g, and a CTAB surface area (according to ASTM D 3765) of 30 to 400 m 2 / g, preferably of 30 to 330 m 2 / g, particularly preferably of 95 to 300 m 2 / g and very particularly preferably of 95 to 200 m 2 / g. Such silicas lead, for example, to particularly good physical properties of the vulcanizates in rubber mixtures for inner tire components.Furthermore, this can result in advantages in compound processing due to a reduction in mixing time while maintaining consistent product properties, leading to improved productivity. Suitable silicas include, for example, Ultrasil®< VN3 (trade name) from Evonik, silicas with a comparatively low BET surface area (such as Zeosil®< 1115 or Zeosil®< 1085 from Solvay), and highly dispersible silicas, so-called HD silicas (such as Zeosil®< 1165 MP from Solvay).

[0094] The amount of at least one silica is preferably 5 to 300 phr, particularly preferably 10 to 200 phr, most preferably 20 to 180 phr. In the case of different silicas, the stated amounts refer to the total amount of silicas present.

[0095] The term phr (parts per hundred parts of rubber by weight) used in this document is the standard quantity used in the rubber industry for compound formulations. The dosage of the parts by weight of the individual substances in this document is based on 100 parts by weight of the total mass of all high-molecular-weight (Mw greater than 20,000 g / mol) and therefore solid rubbers present in the compound.

[0096] The term phf (parts per hundred parts of filler by weight) used in this document is the quantity commonly used in the rubber industry to specify coupling agents for fillers. In the context of this application, phf refers to the silica present, meaning that other fillers that may be present, such as carbon black, are not included in the calculation of the silane quantity.

[0097] The rubber mixture according to the invention preferably contains at least one silane of the formula I), namely at least the silane according to formula II) or III) or III)-a) or IV) or V), in an amount of 1 to 25 phr and, in the preferred case with silica as filler, preferably 2 to 20 phf.

[0098] The silane(s) according to the invention are preferably added in at least one basic mixing stage during the production of the rubber mixture according to the invention, which preferably contains at least one diene rubber and preferably at least one silica as filler.

[0099] A further subject of the present invention is thus a process for producing the rubber mixture according to the invention, wherein at least one silane according to the invention is preferably added in at least one basic mixing stage as described above.

[0100] According to an advantageous embodiment of the invention, the at least one silane according to the invention is previously applied to silica and mixed in this form into the rubber mixture.

[0101] In the process according to the invention for producing the rubber mixture according to the invention, it is therefore preferred if the at least one silane according to the invention is previously applied to silica and mixed into the rubber mixture in this form.

[0102] The rubber base mixture containing at least one silane according to the invention and / or one silica according to the invention is then processed into a finished rubber mixture by adding vulcanization chemicals, see below in particular a sulfur vulcanization system, and then vulcanized, whereby a vulcanizate according to the invention of the rubber mixture according to the invention is obtained.

[0103] Further aspects of the present invention are the production of a rubber base mixture containing at least one silane according to the invention and / or one silica according to the invention, as well as the production of a finished rubber mixture containing at least one silane according to the invention and / or one silica according to the invention, as well as the production of a vulcanizate according to the invention of the rubber mixture according to the invention.

[0104] The rubber mixture according to the invention may contain carbon black as a further filler, preferably in amounts of 2 to 200 phr, particularly preferably 2 to 70 phr.

[0105] The rubber mixture according to the invention may contain further fillers, preferably in the smallest possible amounts, i.e., preferably 0 to 3 phr. Other (non-reinforcing) fillers within the scope of the present invention include aluminosilicates, kaolin, chalk, starch, magnesium oxide, titanium dioxide, or rubber gels, as well as fibers (such as aramid fibers, glass fibers, carbon fibers, and cellulose fibers).

[0106] Other potentially reinforcing fillers include carbon nanotubes (CNTs) including discrete CNTs, so-called hollow carbon fibers (HCFs) and modified CNTs containing one or more functional groups, such as hydroxyl, carboxy and carbonyl groups), graphite and graphene and so-called "carbon-silica dual-phase fillers".

[0107] Zinc oxide is not considered a filler in the context of the present invention.

[0108] Furthermore, the rubber mixture may contain conventional additives in the usual parts by weight, which are preferably added in at least one basic mixing stage during its production. These additives include a) ageing inhibitors, such as 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), b) activators, such as zinc oxide and fatty acids (e.g. stearic acid) and / or other activators, such as zinc complexes such as zinc ethylhexanoate, c) ozone protection waxes, d) resins, in particular adhesive resins for internal tire components, e) mastication aids, such as B. 2,2'-Dibenzamidodiphenyl disulfide (DBD) and f) processing aids, such as in particular fatty acid esters and metal soaps, such as zinc soaps and / or calcium soaps g) plasticizers, such as in particular aromatic, naphthenic or paraffinic mineral oil plasticizers, such asMES (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 with a polycyclic aromatics content of less than 3% by weight according to method IP 346, or triglycerides, such as rapeseed oil, or factices or hydrocarbon resins or liquid polymers whose average molecular weight (determined by GPC = gel permeation chromatography, based on BS ISO 11344:2004) is between 500 and 20,000 g / mol, with mineral oils being particularly preferred as plasticizers.

[0109] When using mineral oil, this is preferably selected from the group consisting of DAE (Distilled Aromatic Extracts) and / or RAE (Residual Aromatic Extract) and / or TDAE (Treated Distilled Aromatic Extracts) and / or MES (Mild Extracted Solvents) and / or naphthenic oils.

[0110] The proportion of the total amount of further additives is preferably 3 to 150 phr, particularly preferably 3 to 100 phr and most preferably 5 to 80 phr.

[0111] The total amount of other additives may contain zinc oxide (ZnO) in the amounts stated above.

[0112] This can be any type of zinc oxide known to those skilled in the art, such as ZnO granules or powder. The conventionally used zinc oxide generally has a BET surface area of less than 10 m 2 / g. However, a zinc oxide with a BET surface area of 10 to 100 m 2 / g, such as so-called "nano-zinc oxides," can also be used.

[0113] The vulcanization of the rubber mixture according to the invention is preferably carried out in the presence of sulfur and / or sulfur donors with the aid of vulcanization accelerators, whereby some vulcanization accelerators can also act as sulfur donors. 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 xanthate accelerators and / or guanidine accelerators.

[0114] Preference is given to using a sulfenamide accelerator selected from the group consisting of N-cyclohexyl-2-benzothiazolesufenamide (CBS) and / or N,N-dicyclohexylbenzothiazole-2-sulfenamide (DCBS) and / or benzothiazyl-2-sulfenemorpholide (MBS) and / or N-tert-butyl-2-benzothiazylsulfenamide (TBBS) or a guanidine accelerator such as diphenylguanidine (DPG).

[0115] All sulfur-donating substances known to the person skilled in the art can be used as the sulfur-donating substance. If the rubber mixture contains a sulfur-donating substance, this is preferably selected from the group comprising, for example, thiuram disulfides, such as tetrabenzylthiuram disulfide (TBzTD) and / or tetramethylthiuram disulfide (TMTD) and / or tetraethylthiuram disulfide (TETD), and / or thiuram tetrasulfides, such as dipentamethylenethiuram tetrasulfide (DPTT), and / or dithiophosphates, such as

[0116] DipDis (bis-(diisopropyl)thiophosphoryl disulfide) and / or bis(O,O-2-ethylhexyl-thiophosphoryl)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 diarylpolysulfides and / or dialkylpolysulfides.

[0117] Other network-forming systems, such as those available under the trade names Vulkuren®, Duralink®, or Perkalink®, or network-forming systems as described in WO 2010 / 049216 A2, can also be used in the rubber compound. This system contains a vulcanizing agent that crosslinks with a functionality greater than four and at least one vulcanization accelerator.

[0118] The use of the accelerators TBBS and / or CBS and / or diphenylguanidine (DPG) is particularly preferred.

[0119] In addition, vulcanization retarders may be present in the rubber compound.

[0120] The terms "vulcanized" and "crosslinked" are used synonymously in the context of the present invention.

[0121] According to a preferred development of the invention, several accelerators are added in the final mixing stage during the production of the sulfur-crosslinkable rubber mixture.

[0122] The sulfur-crosslinkable rubber mixture according to the invention is produced according to the process customary in the rubber industry, in which a base mixture containing all components except the vulcanization system (sulfur and vulcanization-influencing substances) is first prepared in one or more mixing stages. The finished mixture is created by adding the vulcanization system in a final mixing stage. The finished mixture is further processed, for example, by an extrusion process or calendering, and formed into the appropriate shape. Further processing then takes place by vulcanization, whereby sulfur crosslinking occurs due to the vulcanization system added within the scope of the present invention.

[0123] The above-described inventive rubber mixture is particularly suitable for use in vehicle tires, especially pneumatic vehicle tires. Application is conceivable in principle in all tire components, especially in a tread, especially in the cap of a tread with a cap / base construction. The cap is the part of the tread of the vehicle tire that comes into contact with the road surface, while the base is the radially underlying inner part of the tread that does not come into contact with the road surface.

[0124] For use in vehicle tires, the mixture is preferably formed into a tread shape as a ready-mix before vulcanization and applied as usual during the production of the green vehicle tire.

[0125] The rubber mixture according to the invention for use as a sidewall or other body mixture in vehicle tires is produced as already described. The difference lies in the shaping after the extrusion process or calendering of the mixture. The resulting shapes of the still unvulcanized rubber mixture for one or more different body mixtures are then used to construct a green tire.

[0126] The body compound refers to the rubber compounds for the inner components of a tire, such as the squeegee, inner liner (inner layer), apex, belt, shoulder, belt tread, carcass, bead reinforcement, bead tread, flange tread, and bandage. The unvulcanized green tire is then vulcanized.

[0127] For use of the rubber mixture according to the invention in belts and straps, particularly conveyor belts, the extruded, still unvulcanized mixture is molded into the appropriate shape and, during or afterward, often provided with reinforcements, e.g., synthetic fibers or steel cords. This usually results in a multi-layer structure consisting of one or more layers of rubber mixture, one or more layers of the same and / or different reinforcements, and one or more additional layers of the same and / or a different rubber mixture.

[0128] A further subject of the present invention is a vehicle tire which comprises the rubber mixture according to the invention containing at least one silane according to the invention in at least one component.

[0129] The vulcanized vehicle tire comprises, in at least one component, a vulcanizate of at least one rubber mixture according to the invention. It is known to those skilled in the art that most substances, such as the rubbers and silanes contained therein, in particular the silane according to the invention, are present in a chemically altered form either immediately after mixing or only after vulcanization.

[0130] For the purposes of the present invention, vehicle tires are understood to mean pneumatic vehicle tires and solid rubber tires, including tires for industrial and construction vehicles, truck, car and two-wheel tires.

[0131] The vehicle tire according to the invention preferably comprises the rubber mixture according to the invention at least in the tread.

[0132] The vehicle tire according to the invention preferably has the rubber mixture according to the invention at least in the sidewall.

[0133] The rubber mixture according to the invention is also suitable for other components of vehicle tires, such as, in particular, the horn profile, as well as inner tire components. The rubber mixture according to the invention is also suitable for other technical rubber articles, such as bellows, conveyor belts, air springs, belts, straps, or hoses, as well as shoe soles.

[0134] In the following, the invention will be explained in more detail using exemplary embodiments.

[0135] The silane according to formula IV) as an example according to the invention was prepared in the following way: 1. Preparation of diallyl-3,3'-((3-(triethoxysilyl)propyl)azanediyl)-dipropionate according to the synthesis scheme according to formula VI)

[0136]

[0137] (3-Aminopropyl)triethoxysilane (10.8 mL, 10.00 g, 45.2 mmol, 1.0 eq.) was added dropwise over 10 min to a solution of allyl acrylate (16.0 mL, 15.20 g, 136.0 mmol, 3.0 eq.) in ethanol (50 mL) at RT under an argon atmosphere. The reaction mixture was then stirred at reflux overnight, and the solvent was removed under reduced pressure.

[0138] After column chromatographic purification on silica gel (120 g, DCM / MeOH 0 % → 2 %), the target compound was isolated as a colorless liquid (13.81 g, 31.0 mmol, 69 %).

[0139] 1< H-NMR ( English "nuclear magnetic resonance") (500 MHz, DMSO d 6 ) δ 5.90 (ddt, J = 17.3, 10.7, 5.4 Hz, 2 H, -OCH 2 C H =CH 2 ), 5.29 (dq, J = 17.3, 1.6 Hz, 2 H, -OCH 2 CH=C H 2 ), 5.19 (dq, J = 10.5, 1.4 Hz, 2 H, -OCH 2 CH=C H 2 ), 4.52 (German, J = 5.4, 1.5 Hz, 4 H, -OC H 2 CH=CH 2 ), 3.73 (q, J =7.0 Hz, 6 H, -SiOC H 2 CH 3 ), 2.66 (t, J = 7.0 Hz, 4 H, -NCH 2 C H 2 C(O)O-), 2.42 (t, J = 6.9 Hz, 4 H, -NCH 2 C H 2 C(O)O-), 2.38 - 2.31 (m, 2 H, -SiCH 2 CH 2 C H 2 -), 1.39 (tt, J = 8.2, 6.4 Hz, 2 H, -SiCH 2 C H 2 CH 2 -), 1.14 (t, J = 7.0 Hz, 9 H, -SiOCH 2 C H 3 ), 0.54 - 0.46 (m, 2H, -SiC H 2 CH 2 CH 2 -).

[0140] ESI-MS (electrospray ionization mass spectrometry) m / z (%): 446.2 [M+H] +< (100). 2. Preparation of the silane according to formula IV) (bis-(3-(thioacetyl)propyl)-3,3'-((3-(triethoxysilyl)propyl)azanediyl)-dipropionate) according to the synthesis scheme according to formula VII)

[0141]

[0142] Azobis(isobutyronitrile) (AIBN) (7.37 g, 44.9 mmol, 4.0 eq.) was added to a solution of diallyl 3,3'-((3-(triethoxysilyl)propyl)azanediyl)-dipropionate (5.00 g, 11.2 mmol, 1.0 eq.) in toluene (60 mL) at 60 °C under an argon atmosphere and stirred for 10 min. Thioacetic acid (3.2 mL, 3.42 g, 44.9 mmol, 4.0 eq.) was then added dropwise to the reaction mixture over a period of 10 min at 85 °C. The reaction mixture was stirred overnight at 85 °C, and the solvent was removed under reduced pressure.

[0143] After purification by column chromatography on silica gel (80 g, DCM / MeOH 0% → 10%), the target compound was isolated as a brown oil (2.28 g, 3.8 mmol, 34%). According to NMR and MS, approximately 20% of the byproduct (NP) with a remaining double bond is present.

[0144] 1< H-NMR (500 MHz, DMSO- d 6 ) δ 4.02 (t, J = 6.4 Hz, 4 H, -C H 2 OC(O)-), 3.73 (q, J = 7.0 Hz, 6 H, -SiOC H2 CH 3 ), 2.88 (t, J = 7.1 Hz, 4 H, -C H 2 SC(O)CH 3 ), 2.66 (t, J = 7.0 Hz, 4 H, -NCH 2 C H 2 C(O)O-), 2.41 - 2.34 (m, 6 H, -NC H 2 CH 2 C(O)O-, -SiCH 2 CH 2 C H 2 -), 2.32 (s, 6 H, -SC(O)CH 3 ), 1.86 - 1.76 (m, 4 H, -CH 2 CH 2 SC(O)CH 3 ), 1.43 - 1.34 (m, 2 H, -SiCH 2 CH 2 C H 2 -), 1.14 (t, J = 7.0 Hz, 9 H, -SiOCH 2 C H 3 ), 0.54 - 0.45 (m, 2H, -SiC H 2 CH 2 CH 2 -).

[0145] 13< C-NMR (126 MHz, DMSO- d 6 ) δ 195.48, 172.38, 133.14, 117.97, 62.72, 58.00, 49.17, 32.53, 30.96, 28.83, 25.51, 18.58, 8.84.

[0146] ESI-MS m / z (%): 522.26 [NP+H] +< (65), 598.26 [M+Na] +< (100).

[0147] The silane according to formula V) as an example according to the invention was prepared in the following way: 3. Preparation of 2-(bis-(2-hydroxyethyl)amino)-ethyl-(3-(triethoxysilyl)propyl)-carbamate according to the synthesis scheme according to formula VIII)

[0148]

[0149] Triethoxypropyl isocyanate (0.8 mL, 0.83 g, 3.4 mmol, 1.0 eq.) was added dropwise over 30 min to a solution of triethanolamine (2.50 g, 16.8 mmol, 5.0 eq.) in THF (20 mL) at RT under an argon atmosphere. The reaction mixture was then stirred overnight at RT, and the solvent was removed under reduced pressure. After purification by column chromatography on silica gel (40 g, DCM / MeOH 20%), the target compound was isolated as a colorless liquid (0.84 g, 2.1 mmol, 63%).

[0150] 1< H-NMR (500 MHz, DMSO- d 6 ) δ 7.07 (t, J = 5.8 Hz, 1 H, -OC(O)NH-), 4.29 (t, J = 5.5 Hz, 2 H, -OH), 3.95 (t, J = 6.4 Hz, 2 H, -C H 2 OC(O)NH-), 3.73 (q, J = 7.0 Hz, 6 H, -SiOC H 2 CH 3 ), 3.40 (q, J = 6.0 Hz, 4 H, -C H 2 OH), 2.92 (td, J = 7.2, 5.9 Hz, 2 H, -OC(O)NHC H 2 -), 2.68 (t, J = 6.4 Hz, 2 H, -NC H2 CH 2 OC(O)NH-), 2.56 (t, J = 6.3 Hz, 4 H, -NC H 2 CH 2 OH), 1.43 (tt, J = 8.1, 6.3 Hz, 2 H, -SiCH 2 CH 2 C H 2 -), 1.14 (t, J = 7.0 Hz, 9 H, -SiOC H 2 CH 3 ), 0.57 - 0.47 (m, 2 H, -SiC H 2 CH 2 CH 2 -).

[0151] ESI-MS m / z (%): 397.2 [M+H] +< (100), 419.1 [M+Na] +< (15). 4. Preparation of the silane according to formula V) ((Bis-(2-thioacetyl)ethyl)amino)-ethyl-(3-(triethoxysilyl)propyl)-carbamate) according to the synthesis scheme according to formula IX)

[0152]

[0153] Triphenylphosphine (2.91 g, 11.1 mmol, 2.2 eq.) and diisopropyl azodicarboxylate (DIAD) (2.2 mL, 2.24 g, 11.1 mmol, 2.2 eq.) were added to a solution of 2-(bis-(2-hydroxyethyl)amino)ethyl-(3-(triethoxysilyl)propyl)carbamate (2.00 g, 5.0 mmol, 1.0 eq.) in THF (20 mL) at 0 °C under an argon atmosphere. Thioacetic acid (0.8 mL, 0.85 g, 11.1 mmol, 2.2 eq.) was then added dropwise to the reaction mixture over a period of 10 min at 0 °C. The reaction mixture was warmed to RT and stirred at RT overnight. The solvent was then removed under reduced pressure, and the residue was dissolved in cyclohexane (20 mL), forming a white precipitate. The resulting crystalline solid was collected by filtration, and the solvent from the filtrate was removed under reduced pressure.

[0154] After column chromatographic purification on silica gel (120 g, cyclohexane / ethyl acetate 0 % → 60 %), the target compound was isolated as a yellow oil (1.82 g, 3.6 mmol, 70 %).

[0155] 1< H-NMR (500 MHz, DMSO- d 6 ) δ 7.07 (t, J = 5.8 Hz, 1 H, -OC(O)NH-), 3.95 (t, J = 6.1 Hz, 2 H, -C H 2 OC(O)NH-), 3.74 (q, J = 7.0 Hz, 6 H, -SiOC H 2 CH 3 ), 2.97 - 2.91 (m, 2 H, -OC(O)NHC H 2 -), 2.92 - 2.85 (m, 4 H, -C H 2 SC(O)CH 3 ), 2.70 (t, J = 6.2 Hz, 2 H, -NC H 2 CH 2 OC(O)NH-), 2.64 (dd, J = 8.2, 6.2 Hz, 4 H, -NC H 2 CH 2 S-), 2.32 (s, 6 H, -SC(O)CH 3 ), 1.44 (tt, J = 8.0, 6.2 Hz, 2 H, -SiCH 2 C H 2 CH 2 -), 1.15 (t, J = 7.0 Hz, 9 H, -SiOCH 2 C H 3 ), 0.56 - 0.48 (m, 2H, -SiC H 2 CH 2 CH 2 -).

[0156] 13< C-NMR (126 MHz, DMSO- d6 ) δ 195.42, 156.07, 61.77, 57.65, 53.11, 51.95, 42.94, 30.52, 26.64, 22.97, 18.17, 7.14.

[0157] Elemental analysis (%) (calculated): C, 46.59 (46.85); H, 7.82 (7.86); N, 6.16 (5.46); S, 11.36 (12.51).

[0158] ESI-MS m / z (%): 513.5 [M+H] +< (100), 535.4 [M+Na] +< (20).

[0159] The silane prepared according to formula IV) and / or V) is mixed into a rubber mixture according to the invention containing at least one diene rubber and at least one silica as a filler. For this purpose, the silane according to formula IV) and / or V) is preferably first coated onto a silica and then added in this form to the rubber mixture.

[0160] The process of applying the silane to silica is carried out as follows: A solution of the silane according to formula IV) and / or V) in the desired ratio of silica to silane dissolved in DMF is added to a suspension of silica, e.g., granulated silica, at room temperature in DMF. For example, silica (VN3, Evonik) can be used with up to 16.8 phf of the silane according to formula IV) or up to 14.4 phf of the silane according to formula V).

[0161] The resulting suspension is stirred overnight at 120 °C, for example, and then the solvent is removed under reduced pressure. After drying for one day under high vacuum at 40 °C, the resulting modified silica is ground using a mortar and pestle, if necessary, depending on the desired fineness. It is then dried for another day at 40 °C under high vacuum.

[0162] The rubber mixture according to the invention is applied, for example, in the form of a preformed tread of a vehicle tire (as described above) to a green tire and then vulcanized with it.

[0163] The invention will be further explained in more detail using comparative and exemplary embodiments of rubber mixtures, which are summarized in Table 1. The comparative mixtures are marked V, and the mixtures according to the invention are marked E. The quantity of silanes in phf refers to the respective amount of silica.

[0164] The compounds were produced under standard conditions in several stages in a twin-screw extrusion mixer. Test specimens were produced from all compounds by vulcanization, and these specimens were used to determine material properties typical for the rubber industry.

[0165] The following test procedures were used for the described tests on test specimens: Standard: ISO 6502, ASTM D5289; Minimum torque at the lowest point of the vulcanization curve measured using an MDR (moving die rheometer). Standard: ISO 868, DIN 53 505; Shore A hardness at room temperature and 70 °C. Standard: ISO 4662, DIN 53 512; Rebound resilience at room temperature. Standard: ISO 37, ASTM D 412, DIN 53 504; Elongation at break at room temperature and fracture energy density at room temperature determined in a tensile test, where fracture energy density is the work required until fracture, relative to the sample volume. Standard: DIN 53 513; Dynamic storage modulus at 0.15% elongation (E'(0.15%)) from dynamic mechanical measurement at 55 °C.

[0166] The inventive formulations E1 and E2 (containing the inventive silane according to formula V)) exhibit a reduced rebound resilience RT compared to the reference mixture V1 with the same dynamic storage modulus E' (0.15%). These properties indicate to the person skilled in the art an improvement in grip behavior in tire applications. For E1 and E2, a reduction in Shore A hardness at RT and 70°C is observed compared to V1. Furthermore, the increased elongation at break and fracture energy density indicate improved durability and tear strength. In addition, improved processability is expected for E1 and E2 due to a reduced S' for ML. These properties clearly demonstrate the advantage of the inventive silanes over the prior art. Table 1 Components Unit V1 E1 E2 NR TSR a) phr 10 10 10 BR b) phr 18 18 18 SSBR c) phr 72 72 72 Silica d) phr 85 85 85 Silane NXT e) phf 10.2 - - Silane according to formula V) e) phf - 14.4 7.2 TDAE phr 35 35 35 ZnO phr 2.5 2.5 2.5 Other additives f) phr 6.5 6.5 6.5 DPG phr 2 2 2 CBS phr 2 2 2 sulfur phr 2 2 2 Physical measurements Unit ML dNm 4.9 1.7 2.1 Shore A hardness RT ShA 63.4 57.7 61.4 Shore A hardness 70 °C ShA 62.2 55.5 57.2 Rebound resilience RT % 36.3 30.2 29.3 Elongation at break RT (S3) % 244 564 624 Fracture energy density (S3) J / cm3 13 35 40 Dynamic storage modulus (E'(0.15%)) 55 °C MPa 10.5 9.6 10.8 a) NR TSR: Natural rubber. b) BR: Polybutadiene: Europrene Neocis BR 40, Polimeri. c) SSBR: State-of-the-art solution-polymerized styrene-butadiene copolymer with hydroxy groups, Nipol®< NS 612, Zeon Corporation. d) Silica: VN3, Evonik. e) Silane was pre-silanized / reacted with the specified silica in a separate step in the appropriate amount (50% and 100% equimolar replacement to the reference NXT, 3-(octanoylthio)-1-propyltriethoxysilane, Momentive). Silica and silane were added together as modified fillers to the mixing process. f) Other additives: Anti-aging agent / antiozonant / stearic acid.

Claims

1. Silane according to formula II) or III):         II)     (R1)oSi-R2-X-R2-Y(-R2-S-R3)2         III)     (R1)oSi-R2-Y(-R2-X-R2-S-R3)2 wherein o = 3 and the radicals R1 may independently of one another be identical or different and are selected from alkoxy groups having 1 to 10 carbon atoms, cycloalkoxy groups having 4 to 10 carbon atoms, phenoxy groups having 6 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, halides or alkyl polyether groups -O-(R6-O)r-R5, wherein R6 are identical or different and are branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic / aromatic bridging C1-C30 hydrocarbon groups, r are an integer from 1 to 30 and R5 are unsubstituted or substituted, branched or unbranched, terminal alkyl, alkenyl, aryl or aralkyl groups or two R1 form a cyclic dialkoxy group having 2 to 10 carbon atoms or two or more silanes according to formula II) or III) may be bridged via radicals R1 ; and wherein the radicals R2 may independently of one another be identical or different and are selected from the group consisting of linear or branched alkylene groups having 1 to 20 carbon atoms or cycloalkylene groups having 4 to 12 carbon atoms or arylene groups having 6 to 20 carbon atoms or alkenylene groups having 2 to 20 carbon atoms, alkynylene groups having 2 to 20 carbon atoms or aralkylene groups having 7 to 20 carbon atoms; and wherein the group R3 is a hydrogen atom or a -C(=O)-R4 group or an -SiR83 group, wherein R4 and R8 are selected from C1-C20-alkyl groups, C4-C10-cycloalkyl groups, C6-C20-aryl groups, C2-C20-alkenyl groups, and C7-C20-aralkyl groups and R8 is additionally selected from alkoxy groups having 1 to 10 carbon atoms, cycloalkoxy groups having 4 to 10 carbon atoms, phenoxy groups having 6 to 20 carbon atoms; and wherein Y is a trivalent nitrogen atom (N); and wherein the groups X may independently of one another be identical or different and are selected from the groups -HNC(=O)-, -C(=O)NH-, -C(=O)O-, -OC(=O)-, -OC(=O)NH-, -HNC(=O)O-,-HNC(=O)NH-, -R7NC(=O)NR7-, -R7NC(=NR7)NR7-, -R7NC(=S)NR7-, wherein the radicals R7 within the group X may be identical or different and are selected from a hydrogen atom or are selected from the group consisting of linear or branched alkyl groups having 1 to 20 carbon atoms or cycloalkyl groups having 4 to 12 carbon atoms or aryl groups having 6 to 20 carbon atoms or alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms or aralkyl groups having 7 to 20 carbon atoms with the proviso that at least one R7 within the group X is a hydrogen atom, and wherein the silane may also be in the form of oligomers formed by hydrolysis and condensation of silanes of formula II) or III).

2. Silane according to the preceding claim, characterized in that the radicals R2 are linear alkylene radicals having 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms, particularly preferably 2 to 5 carbon atoms.

3. Silane according to either of the preceding claims, characterized in that the group R3 is a -C(=O)-R4 group, wherein R4 is selected from C1-C20-alkyl groups, preferably C1-C7-alkyl groups.

4. Silane according to any of the preceding claims, characterized in that the radicals R1 within a silyl group (R1)oSi- are identical and are alkoxy groups having 1 or 2 carbon atoms, i.e. methoxy groups or ethoxy groups, very particularly preferably ethoxy groups.

5. Silane according to Claim 1, characterized in that X in formula II) is an - OC(=O)NH- or -HNC(=O)O- group.

6. Silane according to Claim 1, characterized in that X in formula III) is a - C(=O)O- or -OC(=O)- group.

7. Silane according to Claim 1, characterized in that it has the following formula IV):

8. Silane according to Claim 1, characterized in that it has the following formula V):

9. Silica modified with at least one silane according to any of Claims 1 to 8 at least at its surface.

10. Rubber mixture containing at least one silane according to any of Claims 1 to 8 and / or at least one silica according to Claim 9.

11. Vehicle tyre comprising the rubber mixture according to Claim 10 in at least one component.

12. Process V1 for producing a silane according to formula II)-a),         II)-a)     (R1)oSi-R2-(H)NC(=O)O-R2-N(R2-S-R3)2, wherein the process V1 comprises at least the following process steps a) providing a substance (R1)oSi-R2-N=C=O; b) providing a substance (HO-R2)3N; c) reacting the substance from step a) with the substance from step b) to afford (R1)oSi-R2-(H)NC(=O)O-R2-N(R2-OH)2; d) providing a substance R3-SH; e) reacting one equivalent of the substance from step c) with two equivalents of the substance from step d) to afford         II)-a)     (R1)oSi-R2-(H)NC(=O)O-R2-N(R2-S-R3)2; f) optionally purifying the silane obtained in step e), wherein R1, R2 and R3 and also o are as defined for Claim 1.

13. Process V2 for producing a silane according to formula III)-a),         III)-a)     (R1)oSi-R2-N(-C(H)2-C(H)2-C(=O)O-C(H)2-C(H)2-C(H)2-S-R3, wherein the process V2 comprises at least the following process steps aa) providing a substance (R1)oSi-R2-NH2; bb) providing a substance H2C=C-C(=O)O-C(H)2-C(H)=CH2; cc) reacting one equivalent of the substance from step aa) with two equivalents of the substance from step bb) to afford         (R1)oSi-R2-N(-C(H)2-C(H)2-C(=O)O-C(H)2-C(H)=CH2)2; dd) providing a substance R3-SH; ee) reacting one equivalent of the substance from step cc) with two equivalents of the substance from step dd) to afford         III)-a)     (R1)oSi-R2-N(-C(H)2-C(H)2-C(=O)O-C(H)2-C(H)2-C(H)2-S-R3; ff) optionally purifying the silane obtained in step ee), wherein R1, R2 and R3 and also o are as defined for Claim 1.