Rubber compositions

[0001] The invention relates to rubber mixtures, a method for their preparation and their use.

[0002] It is known that hydrolysable sulfur-containing organosilicon compounds are able to react with fillers containing hydroxyl groups, such as natural and synthetic silicates, carbonates, glass and metal oxides. At the same time, they are used to modify the surface and to increase adhesion. They are used in the rubber processing industry as adhesion promoters between the reinforcing filler and the polymer used (Angew. Chem. 98, (1986) 237253, DE2141159, DE2212239, DE19544469A1, US3978103, US4048206, EP784072A1). The best known representatives of this class of substances include polysulphides (alkyltrialkoxysilane) such as, for example, bis- (3-triethoxysilylpropyl) tetrasulfide or bis- (3-triethoxysilylpropyl) disulfide.

[0003] In addition, the use of mercaptic-functionalized organosilanes (US3350345, FR2.094.859) is known in rubber mixtures. Also known is the use of alkyl silanes to reduce the viscosity of rubber mixtures (EP795577A1, EP864605A2) and the combination of mercaptic functionalized silanes with long chain alkylsilanes (DE10015309A1).

[0004] The disadvantage of using trialkoxy functionalized silanes is the emission of volatile hydrocarbons, in practice mainly methanol and ethanol.

[0005] From patent claims US 6331605 and US 6140 393, rubber mixtures containing rubber, filler and one oligomerized mercaptoalkyl monodialkyl di / monoalkoxysilane are known. Furthermore, a rubber mixture containing rubber, filler and mercaptoalkyl mono / dialkyl di / monoalkoxysilane is known from patent claim WO 02/31040 A.

[0006] Dialkylmonoalkoxysilylpolysulphides are known from patent claims DE1043357A1 and EP1244676B1. Due to the dialkyl monoalkoxy group, the emission of volatile hydrocarbons is lower than in the case of trialkoxy compounds.

[0007] The disadvantages of dialkyl monoalkoxysilyl polysulphates are poor abrasion and resistance to further tearing.

[0008] The object of the present invention is to provide rubber mixtures, the production of which has low volatile hydrocarbon emissions and which show improved tear strength compared to rubber mixtures with known silanes.

The invention relates to rubber mixtures containing rubber, fillers, optionally further rubber auxiliaries and at least one organosilane of general formula I:

R¹R²R³SiR⁴-SH (I) wherein R¹ is methyl or ethyl

R² is -O- (YO) mX, where Y = is a branched or unbranched, saturated or unsaturated divalent hydrocarbon group, preferably CH2, CH2CH2, CH2CH (CH3) or CH (CH3) CH2, X is C1 to C9 alkyl, preferably methyl or ethyl, and m = 1-40, preferably 2-30, particularly preferably 3 to 25, very particularly preferably 4 to 20, extremely preferably 10 to 20,

R³ is methyl, ethyl, methoxy, ethoxy or R², and R⁴ means a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic / aromatic divalent C1-C12 hydrocarbon group.

Preferably at least one of the R groups² or R³ can be the group -O- (YO) mX.

[0011] R⁴ may be preferably CH2, CH2CH2, CH2CH2CH2, CH2CH2CH2CH2, CH (CH3), CH2CH (CH3), CH (CH3) CH2, C (CH3) 2, CH (C2H5), CH2CH2CH (CH3) or CH2CH (CH3) CH2. [0012] Compounds of formula I may be:

[(C4H9O- (CH2-CH2O) 2] (Me) 2Si (CH2) 3SH, [(C4H9O- (CH2-CH2O) 3] (Me) 2Si (CH2) 3SH, [(C4H9O- (CH2-CH2O) 4 ] (Me) 2Si (CH2) 3SH, [(C4H9O- (CH2-CH2O) 5] (Me) 2Si (CH2) 3SH, [(C4H9O- (CH2-CH2O) 6] (Me) 2Si (CH2) 3SH, [(C5H11O- (CH2-CH2O) 2] (Me) 2Si (CH2) 3SH, [(C5H11O- (CH2-CH2O) 3] (Me) 2Si (CH2) 3SH, [(C5H11O- (CH2-CH2O) 4 ] (Me) 2Si (CH2) 3SH, [(C5H11O- (CH2-CH2O) 5] (Me) 2Si (CH2) 3SH, [(C5H11O- (CH2-CH2O) 6] (Me) 2Si (CH2) 3SH, [(C6H13O- (CH2-CH2O) 2] (Me) 2Si (CH2) 3SH, [(C6H13O- (CH2-CH2O) 3] (Me) 2Si (CH2) 3SH, [(C6H13O- (CH2-CH2O) 4] (Me) 2Si (CH2) 3SH, [(C6H13O- (CH2-CH2O) 5] (Me) 2Si (CH2) 3SH, [(C6H13O- (CH2-CH2O) 6 ] (Me) 2Si (CH2) 3SH, [(C7H15O- (CH2-CH2O) 2] (Me) 2Si (CH2) 3SH, [(C7H15O- (CH2-CH2O) 3] (Me) 2Si (CH2) 3SH, [(C7H15O- (CH2-CH2O) 4] (Me) 2Si (CH2) 3SH, [(C7H15O- (CH2-CH2O) 5] (Me) 2Si (CH2) 3SH, [(C7H15O- (CH2-CH2O) 6 ] (Me) 2Si (CH2) 3SH, [(C8H17O- (CH2-CH2O) 2] (Me) 2Si (CH2) 3SH, [(C8H17O- (CH2-CH2O) 3] (Me) 2Si (CH2) 3SH, [(C8H17O- (CH2-CH2O) 4] (Me) 2Si (CH2) 3SH, [(C8H17O- (CH2-CH2O) 5] (Me) 2Si (CH2) 3SH, [(C8H17O- (CH2-CH2O) 6] (Me) 2Si (CH2) 3SH, [(C9H19O- (CH2-CH2O) 2] (Me) 2Si (CH) 3SH, [(C9H19O- (CH2-CH2O) 3 ] (Me) 2Si (CH2) 3SH, [(C9H19O- (CH2-CH2O) 4] (Me) 2Si (CH) 3SH, [(C9H19O- (CH2-CH2O) 5] (Me) 2Si (CH2) 3SH, [(C9H19O- (CH2-CH2O) 6] (Me) 2Si (CH) 3SH, [(C4H9O- (CH2-CH2O) 2] 2 (Me) Si (CH2) 3SH, [(C4H9O- (CH2-CH2O) 3] 2 (Me) Si (CH2) 3SH, [(C4H9O- (CH2-CH2) 4] 2 (Me) Si (CH2) 3SH, [(C9H9O- (CH2-CH2O) 5] 2 (Me) Si ( CH2) 3SH, [(C4H9O- (CH2-CH2O) 6] 2 (Me) Si (CH2) 3SH, [(C5H11O- (CH2-CH2O) 2] 2 (Me) Si (CH2) 3SH, [(C5H11O- (CH 2 CH 2 O) 3] 2 (Me) Si (CH2) 3SH. [(C5H11O- (CH2-CH2O) 4] 2 (Me) Si (CH2) 3SH, [(C5H11O- (CH2-CH2O) 5] 2 (Me) Si (CH2) 3SH, [(C5H11O- (CH2-CH2O ) 6] 2 (Me) Si (CH2) 3SH, [(C6H13O- (CH2-CH2O) 2] 2 (Me) Si (CH2) 3SH, [(C6H13O- (CH2-CH2O) 3] 2 (Me) Si (CH2) 3SH, [(C6H13O- (CH2-CH2O) 4] 2 (Me) Si (CH2) 3SH, [(C6H13O- (CH2-CH2O) 5] 2 (Me) Si (CH2) 3SH, [(C6H13O - (CH2-CH2O) 6] 2 (Me) Si (CH2) 3SH, [(C7H15O- (CH2-CH2O) 2] 2 (Me) Si (CH2) 3SH, [(C7H15O- (CH2-CH2O) 3] 2 (Me) Si (CH2) 3SH, [(C7H15O- (CH2-CH2O) 4] 2 (Me) Si (CH2) 3SH, [(C7H15O- (CH2-CH2O) 5] 2 (Me) Si (CH2) 3SH, [(C7H15O- (CH2-CH2O) 6] 2 (Me) Si (CH2) 3SH, [(C8H17O- (CH2-CH2O) 2] 2 (Me) Si (CH2) 3SH, [(C8H17O- (CH2-CH2O) 3] 2 (Me) Si (CH2) 3SH, [(C8H17O- (CH2-CH2O ) 4] 2 (Me) Si (CH2) 3SH, [(C8H17O- (CH2-CH2O) 5] 2 (Me) Si (CH2) 3SH, [(C8H17O- (CH2-CH2O) 6] 2 (Me) Si (CH2) 3SH, [(C9H19O- (CH2-CH2O) 2] 2 (Me) Si (CH2) 3SH, [(C9H19O- (CH2-CH2O) 3] 2 (Me) Si (CH2) 3SH, [(C9H19O - (CH2-CH2O) 4] 2 (Me) Si (CH2) 3SH, [(C9H19O- (CH2-CH2O) 5] 2 (Me) Si (CH2) 3SH, [(C9H19O- (CH2-CH2O) 6] 2 (Me) Si (CH2) 3SH, [(C4H9O- (CH2-CH2O) 2] (Me) (EtO) Si (CH2) 3SH, [(C4H9O- (CH2-CH2O) 3] (Me) (EtO) Si (CH2) 3SH. [(C4H9O- (CH2-CH2O) 4] (Me) (EtO) Si (CH2) 3SH, [(C4H9O- (CH2-CH2O) 5] (Me) (EtO) Si (CH2) 3SH, [(C4H9O- (CH2-CH2O) 6] (Me) (EtO) Si (CH2) 3SH, [(C5H11O- (CH2-CH2O) 2] (Me) (EtO) Si (CH2) 3SH, [(C5H11O- (CH2-CH2O ) 3] (Me) (EtO) Si (CH2) 3SH, [(C5H11O- (CH2-CH2O) 4] (Me) (EtO) Si (CH2) 3SH, [(C5H11O- (CH2-CH2O) 5] ( Me) (EtO) Si (CH2) 3SH, [(C5H11O- (CH2-CH2O) 6] (Me) (EtO) Si (CH2) 3SH, [(C9H13O- (CH2-CH2O) 2] (Me) (EtO ) Si (CH2) 3SH, [(C6H13O- (CH2-CH2O) 3] (Me) (EtO) Si (CH2) 3SH, [(C6H13O- (CH2-CH2O) 4] (Me) (EtO) Si (CH2 ) 3SH, [(C6H13O- (CH2-CH2O) 5] (Me) (EtO) Si (CH2) 3SH, [(C5H13O- (CH2-CH2O) 6] (Me) (EtO) Si (CH2) 3SH, [(C7H15O- (CH2-CH2O) 2] (Me) (EtO) Si (CH2) 3SH, [(C7H15O- (CH2-CH2O) 3] (Me) (EtO) Si (CH2) 3SH, [(C7H15O- (CH2-CH2O) 4] (Me) (EtO) Si (CH2) 3SH, [(C7H15O- (CH2-CH2O ) 5] (Me) (EtO) Si (CH2) 3SH, [(C7H15O- (CH2-CH2O) 6] (Me) (EtO) Si (CH2) 3SH, [(C8H17O- (CH2-CH2O) 2] ( Me) (EtO) Si (CH2) 3SH, [(C8H17O- (CH2-CH2O) 3] (Me) (EtO) Si (CH2) 3SH, [(C8H17O- (CH2-CH2O) 4] (Me) (EtO ) Si (CH2) 3SH, [(C8H17O- (CH2-CH2O) 5] (Me) (EtO) Si (CH2) 3SH, [(C8H17O- (CH2-CH2O) 6] (Me) (EtO) Si (CH2 ) 3SH, [(C9H19O- (CH2-CH2O) 2] (Me) (EtO) Si (CH2) 3SH, [(C9H19O- (CH2-CH2O) 3] (Me) (EtO) Si (CH2) 3SH, [(C9H19O- (CH2-CH2O) 4] (Me) (EtO) Si (CH2) 3SH, [(C9H19O- (CH2CH2O) 5] (Me) (EtO) Si (CH2) 3SH, [(C9H19O- (CH2-CH2O) 6 ] (Me) (EtO) Si (CH2) 3SH, [(C4H9O- (CH2-CH2O) 2] (Me) (MeO) Si (CH2) 3SH, [(C4H9O- (CH2-CH2O) 3] (Me) (MeO) Si (CH2) 3SH, [(C4H9O- (CH2-CH2O) 4] (Me) (MeO) Si (CH2) 3SH, [(C4H9O- (CH2-CH2O) 5] (Me) (MeO) Si (CH2) 3SH, [(C4H9O- (CH2-CH2) 6] (Me) (MeO) Si (CH2) 3SH, [(C5H11O- (CH2-CH2O) 2] (Me) (MeO) Si (CH2) 3SH , [(C5H11O- (CH2-CH2O) 3] (Me) (MeO) Si (CH2) 3SH, [(C5H11O- (CH2-CH2O) 4] (Me) (MeO) Si (CH2) 3SH, [(C5H11O- (CH2-CH2O) 5] (Me) (MeO) Si (CH2) 3SH, [(C5H11O- (CH2-CH2O) 6] (Me) (MeO) Si (CH2) 3SH, [(C5H13O- (CH2-CH2O) 2] (Me) (MeO) Si (CH2) 3SH, [(C6H13O- (CH2-CH2O ) 3] (Me) (MeO) Si (CH2) 3SH, [(C6H13O- (CH2-CH2O) 4] (Me) (MeO) Si (CH2) 3SH, [(C6H13O- (CH2-CH2O) 5] ( Me) (MeO) Si (CH2) 3SH, [(C6H13O- (CH2-CH2O) 6] (Me) (MeO) Si (CH2) 3SH, [(C7H15O- (CH2-CH2O) 2] (Me) (MeO ) Si (CH2) 3SH, [(C7H15O- (CH2-CH2O) 3] (Me) (MeO) Si (CH2) 3SH, [(C7H15O- (CH2-CH2O) 4] (Me) (MeO) Si (CH2 ) 3SH, [(C7H15O- (CH2-CH2O) 5] (Me) (MeO) Si (CH2) 3SH, [(C7H15O- (CH2-CH2O) 6] (Me) (MeO) Si (CH2) 3SH, [(C8H17O- (CH2-CH2O) 2] (Me) (MeO) Si (CH2) 3SH, [(C8H17O- (CH2-CH2O) 3] (Me) (MeO) Si (CH2) 3SH, [(C8H17O- (CH2-CH2O ) 4] (Me) (MeO) Si (CH2) 3SH, [(C8H17O- (CH2-CH2O) 5] (Me) (MeO) Si (CH2) 3SH, [(C8H17O- (CH2-CH2O) 6] ( Me) (MeO) Si (CH2) 3SH, [(C9H19O- (CH2-CH2O) 2] (Me) (MeO) Si (CH2) 3SH, [(C9H19O- (CH2-CH2O) 3] (Me) (MeO ) Si (CH2) 3SH, [(C9H19O- (CH2-CH2O) 4] (Me) (MeO) Si (CH2) 3SH, [(C9H19O- (CH2-CH2O) 5] (Me) (MeO) Si (CH2) 3SH or [(C9H19O- (CH2-CH2O) 6] (Me) (MeO) Si (CH2) 3SH, with Me = CH3 and Et = CH2CH3.

[0013] The compounds of formula I with X = C3H7, C4H9, C5H11, C6H13, C7H15, C8H17 or C9H19 may be:

[(XO- (CH2-CH (CH3) O-) 2] (Me) (MeO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 3] (Me) (MeO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 4] (Me) (MeO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 5] (Me) (MeO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 6] (Me) (MeO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3 ) O-) 7] (Me) (MeO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 8] (Me) (MeO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 9] (Me) (MeO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 10] (Me) (MeO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 11] (Me) (MeO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 12] (Me) ( MeO) Si (CH2) 3SH. [(XO- (CH2-CH (CH3) O-) 13] (Me) (MeO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 14] (Me) (MeO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 15] (Me) (MeO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 16] (Me) (MeO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 17] (Me) (MeO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3 ) O-) 18] (Me) (MeO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 19] (Me) (MeO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 20] (Me) (MeO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 2] (Me) (EtO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 3] (Me) (EtO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 4] (Me) ( EtO) Si (CH2) 3SH. [(XO- (CH2-CH (CH3) O-) 5] (Me) (EtO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 6] (Me) (EtO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 7] (Me) (EtO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 8] (Me) (EtO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 9] (Me) (EtO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3 ) O-) 10] (Me) (EtO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 11] (Me) (EtO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 12] (Me) (EtO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 13] (Me) (EtO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 14] (Me) (EtO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 15] (Me) (EtO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 16] (Me) (EtO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 17] (Me) (EtO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 18] (Me) (EtO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 19] (Me) (EtO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3 ) O-) 20] (Me) (EtO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 19] (Me) (EtO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 20] (Me) (EtO) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 2] 2 (Me) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 3] 2 (Me) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 4] 2 (Me) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 5] 2 (Me) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 6] 2 (Me) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 7] 2 (Me) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 8] 2 (Me) Si ( CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 9] 2 (Me) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 10] 2 (Me) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 11] 2 (Me) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 12] 2 ( Me) Si (CH) 3SH, [(XO- (CH2-CH (CH3) O-) 13] 2 (Me) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 14] 2 (Me) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 15] 2 (Me) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 16] 2 (Me) Si (CH2) 3SH. [(XO- (CH2-CH (CH3) O-) 17] 2 (Me) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 18] 2 (Me) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 19] 2 (Me) Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 20] 2 (Me) Si ( CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 2] (Me) 2Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 3] (Me) 2Si ( CH) 3SH, [(XO- (CH2-CH (CH3) O-) 4] (Me) 2Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 5] (Me) 2Si ( CH) 3SH, [(XO- (CH2-CH (CH3) O-) 6] (Me) 2Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 7] (Me) 2Si ( CH) 3SH, [(XO- (CH2-CH (CH3) O-) 8] (Me) 2Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 9] (Me) 2Si ( CH2) 3SH. [(XO- (CH2-CH (CH3) O-) 10] (Me) 2Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 11] (Me) 2Si (CH2) 3SH, [(XO- (CH2-CH (CH3) 0-) 12] (Me) 2Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 13] (Me) 2Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 14] (Me) 2Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 15] (Me) 2Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 16] (Me) 2Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 17] (Me) 2Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 18] (Me) 2Si (CH2) 3SH, [(XO- (CH2-CH (CH3) O-) 19] (Me) 2Si (CH2) 3SH or [(XO- (CH2-CH (CH3) O) 20] (Me) 2Si (CH2) 3SH.

[0014] The organosilane of general formula I may consist of a mixture of organosilane compounds of general formula I. These mixtures may contain organosilane compounds of the same or different m. These mixtures of organosilanes may contain compounds of the same or different Y groups. These mixtures contain organosilane compounds with the same or different R groups¹, R², R³ or R⁴.

[0015] From these organosilanes of general formula I, condensation products, ie oligo- and polysiloxanes, can be formed by the addition of water. Oligo- and polysiloxanes can be obtained by oligomerization or co-oligomerization of the corresponding alkoxysilane compounds of general formula I by the addition of water and the addition of additives and the procedure known to a person skilled in the art. The resulting oligoproducts, possibly polymerization products may be contained in organosilane compounds of general formula I.

[0016] The organosilane of general formula I may also be an oligoproduct or polymerization product of an organosilane compound of general formula I. The organosilane of general formula I may be a mixture of oligoproducts or polymerization products of an organosilane compound of general formula I and an unfused organosilane compound of general formula I.

[0017] The organosilane of general formula I can be added to the mixing process both in pure form and applied to an inert organic or inorganic carrier as well as previously reacted with an organic or inorganic carrier. Preferred support materials may be precipitated or pyrogenic silicas, waxes, thermoplastics, natural or synthetic silicates, natural or synthetic oxides, especially alumina or carbon black. In addition, organosilanes of the general formula I previously reacted with the filler used can also be added to the mixing process.

[0018] The following fillers can be used as fillers for the rubber mixtures according to the invention:

- carbon black: carbon black for use here is made using flame, furnace, gas or thermal soot and has a BET surface of 20 to 200 m²/ G. Carbon blacks can optionally also contain heteroatoms, such as Si.

- amorphous silicas, generated, for example, by precipitation from silicate solutions or by flame hydrolysis of silicon halides with specific surfaces from 5 to 1 000 m²/ g, preferably 20 to 400 m²/ g (BET surface) and primary particle sizes from 10 to 400 nm. Silicas can also optionally be present as mixed oxides with other metal oxides such as Al, Mg, Ca, Ba, Zn and titanium oxides.

- synthetic silicates, such as aluminum silicate, alkaline earth silicates, such as magnesium silicate or calcium silicate, with BET surfaces from 20 to 400 m²/ g and primary particle diameters from 10 to 400 nm.

- synthetic or natural aluminum oxides and hydroxides.

- natural silicates such as kaolin and other naturally occurring silicas.

- glass fibers and glass fiber products (mats, strands) or glass microspheres.

[0019] Amorphous silicas, produced by precipitation from silicate solutions, with BET surfaces of up to 20 to 400 m, may advantageously be used.²/ g in amounts of 5 to 150 parts by weight, each time referring to 100 parts of rubber.

[0020] Synthetic rubbers may be used in addition to natural rubber to produce the rubber mixtures of the invention. Preferred synthetic rubbers are described, for example, in W. Hofmann, Kautschuktechnologie, Genter Verlag, Stuttgart 1980. They include, among others:

- polybutadiene (BR),

- polyisoprene (IR),

- styrene / butadiene copolymers, for example emulsion SBR (E-SBR) or solution SBR (L-SBR), preferably with styrene contents from 1 to 60, particularly preferably 5 to 50% by weight (SBR),

- chloroprene (CR)

- isobutylene / isoprene (IIR) copolymers,

- butadiene / acrylonitrile copolymers with acrylonitrile contents from 5 to 60, preferably 10 to 50% by weight (NBR),

- partially hydrogenated or fully hydrogenated NBR rubber (HNBR),

- ethylene / propylene / diene copolymers (EPDM),

- the abovementioned rubbers, which additionally have functional groups, e.g. carboxy, silanol or epoxy groups, for example epoxidized NR, NBR functionalized with carboxy or SBR functionalized with silanol group (SiOH) or siloxy (-Si-OR), as well as mixtures these rubbers. Especially anionically polymerized L-SBR rubbers (SBR solution) with a glass transition temperature above -50 ° C as well as mixtures with diene rubbers can be used to produce tire treads for passenger cars.

[0021] The crude rubber mixtures according to the invention and the rubber vulcanizates according to the invention may contain further rubber auxiliaries, such as reaction accelerators, anti-aging agents, heat stabilizers, anti-light agents, antiozonants, processing aids, plasticizers, binders, blowing agents, dyes , pigments, waxes, extenders, organic acids, retarders, metal oxides or activators, such as triethanolamine or hexanotriol.

[0022] Further rubber excipients may be polyalkyl glycols.

The polyalkyl glycols can be polyethylene glycols, polypropylene glycols or / and polybutylene glycols.

[0023] Polyalkyl glycols may have a molecular weight of between 50 and 50,000 g / mol, preferably between 50 and 20,000 g / mol, particularly preferably between 200 and 10,000 g / mol, very particularly preferably between 400 and 6,000 g / mol, extremely preferably between

500 and 3,000 g / mol.

[0024] The polyethylene glycols may be an alk-O- (CH2-CH2-O) yI-H or alk- (CH2-CH2-O) yI-alk, hydrocarbon terminated polyethylene glycol.^AND = 2-25, preferably y^AND= 2-15, particularly preferably y^AND = 3-8 and 10-14, very particularly preferably y^AND = 3-6 and 1013, and alk equal to a branched or unbranched, substituted or unsubstituted, saturated or unsaturated hydrocarbon with 1 to 35, preferably 4 to 25, particularly preferably 6 to 20, very particularly preferably 10 to 20, extremely preferably 11 to 14, carbon atoms.

[0025] The polypropylene glycols may be a polypropylene glycol terminated with an alk-O- (CH2-CH (CH3) -O) yI-H or alk-O- (CH2-CH (CH3) -O) yI-hydrocarbon terminated s^AND and alk have the meanings given above.

[0026] Polybutylene glycols may be an alk-O- (CH2-CH2-CH2-CH2-O) yI-H hydrocarbon terminated polybutylene glycol, alk-O- (CH2-CH (CH3) -CH2-O) yI-H, alkO- (CH2-CH2-CH2-CH2-O) yI-alk or alk-O- (CH2-CH (CH3) -CH2-O) yI-alk, with y^AND and alk have the meanings given above.

[0027] The polyalkyl glycols may be neopentyl glycol HO-CH2-C (Me) 2-CH2-OH, pentaerythritol C (CH2-OH) 4 or trimethylolpropane CH3-CH2-C (CH2-OH) 3 etherified polyethylene glycol, polypropylene glycol , polybutylene glycol, or mixtures thereof, wherein the repeating units of ethylene glycol, polypropylene glycol or / and butylene glycol in etherified polyalcohols are between 2 and 100, preferably between 2 and 50, particularly preferably between 3 and 30, very particularly preferably 3 and 15.

[0028] The rubber excipients can be used in known amounts which are used inter alia according to the purpose of use. Typical amounts are, for example, amounts from 0.1 to 50% by weight, preferably 0.1 to 30% by weight, based on rubber. Sulfur or sulfur-releasing substances can be used as cross-linking agents. The rubber mixtures according to the invention may further contain vulcanization accelerators. For example, mercaptobenzothiazoles, sulfenamides, guanidines, thiurams, dithiocarbamates, thioureas and thiocarbonates may be used as suitable vulcanization accelerators. Vulcanization accelerators and sulfur can be used in amounts of from 0.1 to 10% by weight, preferably 0.1 to 5% by weight, based on rubber.

[0029] A further object of the invention is a method for producing the rubber mixture according to the invention, characterized in that the rubber, filler, optionally further rubber auxiliaries and at least one organosilane of general formula I are mixed.

[0030] The vulcanization of the rubber mixtures according to the invention can take place at temperatures from 100 to 200 ° C, preferably 130 to 180 ° C, optionally at a pressure from 10 to 200 bar. Mixing of rubbers with a filler, optionally with rubber excipients and with an organosilane of general formula I can be carried out in known mixing units, such as rollers, closed mixers and mixer-extruders.

[0031] The rubber mixtures according to the invention can be used for the production of shaped parts, for example for the production of pneumatic tires, tire treads, cable coatings, hoses, drive belts, conveyor belts, shaft coatings, tires, shoe soles, sealing rings and damping elements.

[0032] The rubber mixtures according to the invention show improved resistance to further tearing.

Examples:

Comparative Example 1: 3-mercaptopropyl (dimethylethoxysilane) (MPDMES) [0033] In a double-jacket autoclave with Hastelloy C22 + fitting (Buechi AG), 37.5 g of dehydrated NaSH and 600 ml of dehydrated ethanol are placed at room temperature. The suspension is heated and stirred 20 min at 50 ° C. A mixture consisting of 100 g 3-chloropropyl (dimethylethoxysilane) and 5 g 3-chloropropyl (dimethylchlorosilane) is added to the suspension with a pressure burette. A further 200 ml of ethanol is added to the mixture and it is heated to 93-96 ° C with stirring. The temperature is maintained for 180 min. The mixture is then cooled to room temperature.

[0034] The resulting suspension is filtered and the filter cake is washed with toluene. The filtrate is freed of solvent on a rotary evaporator. The suspension obtained is filtered, the filter cake is washed with toluene and the filtrate is again free of rotary evaporation from toluene.

[0035] 88.3 g of a liquid, colorless product are obtained.

Comparative Example 2: [(EtO) Me2Si-CH2-CH2-CH2-] 2S.66 [0036] In a 2000 ml four-necked flask, 700 ml of ethanol is weighed with 337 g of dehydrated Na2S4 (1.94 mol) and 700 g 3-chloropropyl (dimethylethoxysilane) (3.88 mol) and brought to boiling with stirring. The reaction mixture is refluxed for 270 min. 3 g of 3-chloropropyl (dimethylethoxysilane) are added to the suspension and heated to reflux for another 30 min.

[0037] The resulting suspension is cooled, filtered and the residue is washed with ethanol. The filtrate is freed on a rotary evaporator from solvent at 20-400 mbar and 6090 ° C and filtered again. 769.2 g of an orange liquid are isolated.

Analytics:

[0038]

1. ¹H-NMR

<td rowspan="2">Content 3-chloropropyl (dimethylethoxysilane)</td><td colspan="3">Content [(EtO) Me₂Si-CH2-CH2-CH2-] 2SX</td>

<td>x = 2</td><td>x = 3</td><td>x = 4</td>

<td>mol%</td><td>mol%</td><td>mol%</td><td>mol%</td>

<td> 2,8</td><td> 17,1</td><td> 28,0</td><td> 25,2</td>

The average chain length -Sx-, based on NMR data (S1-S10), is 3, 66.

2. ²⁹Si-NMR

Comparative Example 2 contains 1.6 mole% dimerized [(EtO) Me2Si-CH2-CH2CH2-] 2Sx.

[0039] For analyzing comparative products, a Bruker DRX 500 NMR device is used according to the rules and instructions for use known to the skilled person. The measurement frequencies are 99.35 MHz for the nucleus²⁹Si and 500.13 MHz for the kernel ¹H. Tetramethylsilane (TMS) serves as a reference.

[0040] The analysis of bis (alkoxysilyl organganyl) polysulphides and mercaptoorganyl (alkoxysilanes) and mixtures thereof is described, for example, in U. Gorl, J. Mϋnzenberg, D. Luginsland, A. Muller Kautschuk Gummi Kunststoffe 1999, 52 (9), 588ff, D. Luginsland Kautschuk Gummi Kunststoffe 2000, 53 (1-2), 10ff or MW Backer et al, Polymer Preprints 2003, 44 (1), 245ff. Example 2: Technical rubber testing.

[0041] The recipe used for the rubber mixtures is given in Table 1 below. The unit phr means here the weight shares, referring to 100 parts of the raw rubber used. The silanes according to the invention are dosed identically by weight. A general method of producing rubber mixtures and their vulcanizates is described in the book Rubber Technology Handbook, W. Hofmann, Hanser Verlag 1994.

[0042] Si 69 coupling reagents, bis- (triethoxy-silylpropyl) tetrasulfide (TESPT), and VP Si 263, 3-mercaptopropyl (triethoxysilane) (MPTES) are commercial products of Degussa AG. Coupling reagent VP Si 208, octyl silyltriethoxysilane, is a processing aid as alkyl silane and is a commercial product of Degussa AG.

Table 1

<td>Substance</td><td>Mixture 1 Reference [Phr]</td><td>Mixture 2 Reference [Phr]</td><td>Mixture 3 Reference [Phr]</td><td>Mixture 4 Reference [Phr]</td>

<td>1st degree</td><td></td><td></td><td></td><td></td>

<td>Buna VSL 5025-1</td><td> 96</td><td> 96</td><td> 96</td><td> 96</td>

<td>Buna CB 24</td><td> 30</td><td> 30</td><td> 30</td><td> 30</td>

<td>Ultrasil 7000 GR</td><td> 80</td><td> 80</td><td> 80</td><td> 80</td>

<td>Si 69 (TESPT)</td><td> 2</td><td> -</td><td> -</td><td> -</td>

<td>VP Si 263 (MPTES)</td><td> -</td><td> 2</td><td> -</td><td> -</td>

<td>Silane from comparative example 2 (DMESPT)</td><td></td><td></td><td> 2</td><td></td>

<td>Silane from comparative example 1 (MPDMES)</td><td></td><td></td><td></td><td> 2</td>

<td>VP Si 208</td><td> 2,5</td><td> 2,5</td><td> 2,5</td><td> 2,5</td>

<td>ZnO</td><td> 3</td><td> 3</td><td> 3</td><td> 3</td>

<td>Stearic acid</td><td> 2</td><td> 2</td><td> 2</td><td> 2</td>

<td>Naftol en ZD</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td>

<td>Vulkanox 4020</td><td> 1,5</td><td> 1,5</td><td> 1,5</td><td> 1,5</td>

<td>Protector G 3108</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td>

<td colspan="5">2nd degree</td>

<td colspan="5">Entry grade 1</td>

<td colspan="5">3rd degree</td>

<td colspan="5">Entry grade 2</td>

<td>Vulkacit D</td><td> 2</td><td> 2</td><td> 2</td><td> 2</td>

<td>Vulkacit CZ</td><td> 1,5</td><td> 1,5</td><td> 1,5</td><td> 1,5</td>

<td>Percacit TBzTD</td><td> 0,2</td><td> 0,2</td><td> 0,2</td><td> 0,2</td>

<td>Sulfur</td><td> 1,5</td><td> 1,5</td><td> 1,5</td><td> 1,5</td>

[0043] The polymer VSL 5025-1 is a solution polymerized SBR copolymer from Bayer AG with a styrene content of 25% by weight and a content of butadiene of 75% by weight. The copolymer contains 37.5 phr oil and has a Mooney viscosity (ML 1 + 4/100 ° C) 50.

[0044] The Buna CB 24 polymer is cis-1,4-polybutadiene (Neodym type) from Bayer AG, with a cis-1,4 content of at least 96% and a Mooney viscosity of 44 ± 5.

[0045] Ultrasil 7000 GR is easily dispersible silicic acid from Degussa AG with a BET surface of 170 m²/ G.

[0046] As aromatic oil, Naftolen ZD from Chemetall is used, in the case

Vulkanox 4020 is PPD from Bayer AG, and Protektor G3l08 is a protective ozone wax from Paramelt BV Vulkacit D (DPG) and Vulkacit CZ (CBS) are the company's commercial products

Bayer AG. Percacit TBzTD (tetrabenzylthiuramodisulfide) is a product of the company

Flexsys NV

[0047] The rubber mixtures will be made in a closed mixer in accordance with the mixing instructions in Table 2.

Table 2

<td>1st degree</td><td></td>

<td>Set values</td><td></td>

<td>Mixing assembly</td><td>Werner &amp; Pfleiderer type E</td>

<td>Number of revolutions</td><td>60 min^-1</td>

<td>Punch pressure</td><td>5.5 bar</td>

<td>Empty volume</td><td>1.58 L.</td>

<td>Degree of filling</td><td> 0,56</td>

<td>Temp. flow</td><td>70 ° C</td>

<td>Mixing process</td><td></td>

<td>0 to 1 min</td><td>Buna VSL 5025-1 + Buna CB 24</td>

<td>1 to 2 minutes</td><td>1/2 silicic acid, ZnO, stearic acid, Naphtholene ZD, silane</td>

<td>2 to 4 minutes</td><td>1/2 silicic acid, Vulkanox, Protector</td>

<td>4 min</td><td>Cleansing</td>

<td>4 to 5 min</td><td>Mixing</td>

<td>5 min</td><td>Airing</td>

<td>5 to 6 min</td><td>Mixing and output</td>

<td>Temp. the charge</td><td>145-155 ° C</td>

<td>storage</td><td>24 h at room temperature</td>

<td>2nd degree</td><td></td>

<td>Set values</td><td></td>

<td>Mixing assembly</td><td>As in grade 1 up to:</td>

<td>Number of revolutions</td><td>70 min^-1</td>

<td>Temp. flow</td><td>80 ° C</td>

<td>Degree of filling</td><td> 0,54</td>

<td>Mixing process</td><td></td>

<td>0 to 2 min</td><td>Break out stage 1 load</td>

<td>2 to 5 min</td><td>Maintain the batch temperature of 150 ° C by changing the speed of rotation</td>

<td>5 min</td><td>Output</td>

<td>Temp. the charge</td><td>145-155 ° C</td>

<td>storage</td><td>4 h at room temperature</td>

<td colspan="2">3rd degree</td>

<td>Set values</td><td></td>

<td>Mixing assembly</td><td>As in grade 1 up to:</td>

<td>Number of revolutions</td><td>40 min^-1</td>

<td>Degree of filling</td><td> 0,52</td>

<td>Temp. flow</td><td>50 ° C</td>

<td>Mixing process</td><td></td>

<td>0 to 2 min</td><td>Batch grade 2, accelerator, sulfur</td>

<td>2 min</td><td>Lead out and create a "skin" on a laboratory roller mixer (diameter 200 mm, length 450 mm, flow temperature 50 ° C)</td>

<td></td><td>homogenization: 5 * on the left, 5 * on the right, cut and 6 * for the wide roller gap (6 mm) and 3 * for the narrow roller gap (3 mm) Peel off the skin.</td>

<td>Temp. the charge</td><td>&lt;110 ° C</td>

[0048] Table 3 lists the rubber testing methods. Table 3

<td>Physical examination</td><td>Standard / conditions</td>

<td>Tensile test on rim, 23 ° C</td><td>DIN 53504, ISO 37</td>

<td>Tensile strength (MPa)</td><td></td>

<td>Stress values ​​(MPa) Elongation at break (%)</td><td></td>

<td>Attempt to further tear according to</td><td>DIN 53 515</td>

<td colspan="2">Graves</td>

<td>DIN abrasion, force 10 N (mm³)</td><td>DIN 53 516</td>

<td>Ball-Rebound test, 60 ° C (%)</td><td>ASTM D 5308</td>

[0049] Table 4 shows the results of a technical rubber test. Table 4

<td>Vulcanizate data</td><td>Unit</td><td>Mixture 1 (Ref.)</td><td>Mixture 2 (Ref.)</td><td>Mixture 3 (Ref.)</td><td>Mixture 4 (Ref.)</td>

<td>Resistance to stretching</td><td>[MPa]</td><td> 12,8</td><td> 15,2</td><td> 12,2</td><td> 15,2</td>

<td>100% stress value</td><td>[MPa]</td><td> 1,2</td><td> 1,2</td><td> 1,3</td><td> 1,2</td>

<td>Stress value 300%</td><td>[MPa]</td><td> 5,8</td><td> 6,2</td><td> 6,1</td><td> 6,7</td>

<td>Tension value 300% / 100%</td><td> [-]</td><td> 4,8</td><td> 5,2</td><td> 4,7</td><td> 5,6</td>

<td>Elongation at break</td><td> [%]</td><td> 480</td><td> 480</td><td> 480</td><td> 480</td>

<td>Resistance to further tearing</td><td>[N / mm]</td><td> 53</td><td> 63</td><td> 45</td><td> 74</td>

<td>Ball-Rebound (60 ° C)</td><td> [%]</td><td> 65,5</td><td> 69,5</td><td> 65,1</td><td> 69,1</td>

<td>DIN abrasion</td><td>[mm³]</td><td> 88</td><td> 66</td><td> 82</td><td> 59</td>

[0050] It is known from the patent claim DE10015309A1 that mercaptosilanes have a higher coupling efficiency and in this case a reinforcement as polysulfide. This is confirmed in the comparison of Mix 2 with Mix 1 through a higher gain factor (300% / 100% stress value), a higher value in the Ball-Rebound test and through improved (lower) DIN abrasion.

[0051] Patent claim EP 1043357 A1 shows for triethoxysilylpropyl disulfide (Example 1) that by substituting two ethoxy groups per silicon atom with methyl groups (Example 2) no deterioration of the technical properties of the rubber, such as static data such as tensile strength and stress values, and dynamic data such as Ball-Rebound, dynamic modules and tan δ, relative to the triethoxy variant.

[0052] Contrary to the above-mentioned observations in the case of the polysulphides of claim EP 1043357, the dimethyl mercaptosilane variant (Mixture 4) shows a significant improvement in important properties. Thus, the stress value at 300% elongation, reinforcement factor (stress value 300% / 100%), further tear strength and abrasion according to DIN are clearly better than the corresponding triethoxy (MPTES) variant (Mixture 2). They are also clearly better than for TESPT (Mixture 1) and the corresponding DMESPT dimethyl variant (Mixture 3).

Example 3: HS-CH2-CH2CH2Si (Me) (OMe) [(O-CH (CH3) -CH2) 5-O-C4H9] [0053] 86.64 g HS-CH2-CH2-CH2 are mixed in a spherical flask. -Si (Me) (OMe) 2,163.29 g polypropylene glycol monobutyl ether (CAS 9003-13-8, Aldrich, Mw = 340 g / mol) and 0.23 g p-toluenesulfonic acid. The mixture is treated on a rotary evaporator at an oil bath temperature of 150-155 ° C and 100-400 mbar for 6.5 hours. The volatile alcohol released is distilled off. The extracted product mass is 236 g.

Example 4: HS-CH2-CH2-CH2-Si (Me) (OMe) [(O-CH (CH3) -CH2) 16-O-C4H9] [0054] 86.64 g HS-CH2 is mixed in a spherical flask. -CH2-CH2-Si (Me) (OMe) 2, 480.03 g polypropylene glycol monobutyl ether (CAS 9003-13-8, Aldrich, Mw = 1,000 g / mol) and 0.23 g p-toluenesulfonic acid . The mixture is treated on a rotary evaporator at an oil bath temperature of 145-155 ° C and 100-400 mbar for 4.5 hours. The volatile alcohol released is distilled off. The extracted product mass is 552 g.

Example 5: HS-CH2-CH2-CH2-Si (Me) (OMe) [(O-CH2-CH2) 4-O-CH2-CH (Et) -C9H9] [0055] 86.62 are mixed in a spherical flask. g HS-CH2-CH2-CH2-Si (Me) (OMe) 2, 147 g polyethylene glycol mono-2-ethylhexyl ether (Aduxol HEX-04, CAS 26468-86-0, company Scharer &amp; Schlapfer AG) and 0, 5 g Ti (OBu)₄. The mixture is treated on a rotary evaporator at an oil bath temperature of 125-135 ° C and 150-300 mbar for 4.5 hours. The volatile alcohol released is distilled off. The extracted product mass is 214 g.

Example 6: HS-CH2-CH2-CH2-Si (Me) (OEt) [(O-CH2-CH2) 2-O-C6H13] [0056] 50 g of HS-CH2-CH2-CH2- are mixed in a spherical flask. Si (Me) (OEt) 2, 45.7 g diethylene glycol monohexyl ether (CAS 112-59-4, purchased through Merck / VWR International) and 0.23 g Ti (OBu) 4. The mixture is treated on a rotary evaporator at an oil bath temperature of 130-135 ° C and 100-300 mbar for 6 hours. The volatile alcohol released is distilled off. The amount of isolated product is 80 g.

Example 7: HS-CH2-CH2-CH2-Si (Me) (OEt) [(O-CH (CH3) -CH2) 16-O-C4H9] [0057] 80 g of HS-CH2-CH2 are mixed in a spherical flask. -CH2-Si (Me) (OEt) 2,384.07 g polypropylene glycol monobutyl ether (CAS 9003-13-8, Aldrich, Mw = 1,000 g / mol) and 0.2 g p-toluenesulfonic acid. The mixture is treated on a rotary evaporator at an oil bath temperature of 145-155 ° C and 100-300 mbar for 6 hours. The volatile alcohol released is distilled off. The weight of the product obtained is 448 g.

Example 8: HS-CH2-CH2-CH2-Si (Me) (OEt) [(O-CH2-CH2) 4-O-CH2-CH (Et) -C4H9] [0058] 50 g HS are mixed in a spherical flask. -CH2-CH2-CH2-Si (Me) (OEt) 2,73.5 g polyethylene glycol mono-2-ethylhexyl ether - (Aduxol HEX-04, CAS 26468-86-0, company Scharer &amp; Schlapfer AG) and 0.3 g Ti (OBu)₄. The mixture is treated on a rotary evaporator at an oil bath temperature of 125-135 ° C and 150-300 mbar for 4.5 hours. The volatile alcohol released is distilled off. The product obtained is 108 g.

Comparative Example 3: Production of HS-CH2-CH2-CH2-SiMe (OEt) 2 [0059] HS-CH2-CH2-CH2-SiMe (OEt) 2 is prepared based on EP 1 538 152 A1 Example 4. As input materials Cl-CH2-CH2-CH2-SiMe (OEt) 2, Cl-CH2-CH2-CH2-SiMeCl2, NaSH (dehydrated) and ethanol are used. The resulting suspension is filtered, freed from the solvent and the silane is purified by distillation.

Example 10: Technical rubber testing.

[0060] The formulation used for the rubber mixtures is given in Table 5 below. The mixtures differ in the added coupling agent as given in Table 6, the mixing instructions are given in Table 2.

Table 5

<td>Substance</td><td>Mixtures 5 to 13 [Phr]</td>

<td colspan="2">1st degree</td>

<td>Buna VSL 5025-1</td><td> 96</td>

<td>Buna CB 24</td><td> 30</td>

<td>Ultrasil 7000 GR</td><td> 80</td>

<td>Silanes from Table 6</td><td> 2</td>

<td>ZnO</td><td> 3</td>

<td>Stearic acid</td><td> 2</td>

<td>Naftolen ZD</td><td> 10</td>

<td>Vulkanox 4020</td><td> 1,5</td>

<td>Protector G 3108</td><td> 1</td>

<td colspan="2">2nd degree</td>

<td colspan="2">Entry grade 1</td>

<td colspan="2">3rd degree</td>

Entry grade 2

<td>Vulkacit D</td><td> 2</td>

<td>Vulkacit CZ</td><td> 1,5</td>

<td>Percacit TBzTD</td><td> 0,2</td>

<td>Sulfur</td><td> 1,5</td>

Table 6

<td>Mix No.</td><td>silane</td>

<td>5 (reference)</td><td>VP Si 263</td>

<td>6 (reference)</td><td>Silane from comparative example 1</td>

<td>7 (reference)</td><td>Silane from comparative example 3</td>

<td> 8</td><td>Silane from Example 3</td>

<td> 9</td><td>Silane from Example 4</td>

<td> 10</td><td>Silane from Example 5</td>

<td> 11</td><td>Silane from Example 6</td>

<td> 12</td><td>Silane from Example 7</td>

<td> 13</td><td>Silane from Example 8</td>

[0061] Table 7 summarizes the rubber testing methods. Table 7

<td>Physical examination</td><td>Standard / conditions</td>

<td>Curing properties, 130 ° C</td><td>DIN 53523/4, ISO 667</td>

<td>Vulcanization time t₅</td><td></td>

<td>Vulcanization time t₃₅</td><td></td>

<td>Trying to tear DIE A further</td><td>ASTM D 624</td>

<td>Trying to tear DIE B further</td><td>ASTM D 624</td>

[0062] Table 8 shows the results of a technical rubber test. Table 8

<td>Vulcanizate data</td><td>Unit</td><td>Mixture 5 (reference)</td><td>Mixture 6 (reference)</td><td>Mixture 7 (reference)</td>

<td>Vulcanization time t₅</td><td>[Min]</td><td> 14,0</td><td> 10,2</td><td> 13,0</td>

<td>Vulcanization time t₃₅</td><td>[Min]</td><td> 18,4</td><td> 13,2</td><td> 16,8</td>

<td>Tear strength further A</td><td>[N / mm]</td><td> 30,3</td><td> 33,6</td><td> 34,2</td>

<td>Strength for further</td><td>[N / mm]</td><td> 23,6</td><td> 29</td><td> 24,6</td>

<td>tearing B</td><td></td><td></td><td></td><td></td>

<td>Vulcanizate data</td><td>Unit</td><td>Mixture 8</td><td>Mixture 9</td><td>Mixture 10</td>

<td>Vulcanization time t₅</td><td>[Min]</td><td> 20,5</td><td> 27,6</td><td> 21,2</td>

<td>Vulcanization time t₃₅</td><td>[Min]</td><td> 24,1</td><td> 31,7</td><td> 24,9</td>

<td>Tear strength further A</td><td>[N / mm]</td><td> 39,9</td><td> 47,5</td><td> 40,0</td>

<td>Tear strength B</td><td>[N / mm]</td><td> 33</td><td> 42,6</td><td> 34,8</td>

<td>Vulcanizate data</td><td>Unit</td><td>Mixture 11</td><td>Mixture 12</td><td>Mixture 13</td>

<td>Vulcanization time t₅</td><td>[Min]</td><td> 19,9</td><td> 26,1</td><td> 19,2</td>

<td>Vulcanization time t₃₅</td><td>[Min]</td><td> 24,3</td><td> 30,1</td><td> 22,7</td>

<td>Tear strength further A</td><td>[N / mm]</td><td> 39,5</td><td> 44,3</td><td> 47,9</td>

<td>Tear strength B</td><td>[N / mm]</td><td> 31,3</td><td> 41,5</td><td> 33,5</td>

[0063] The tear resistance of Mixtures 8 to 13 are clearly better than Mixtures 5, 6, 7, as can be deduced from the results of vulcanizates. Mixtures of silanes with long-chain alcohol as substituent show improved tear behavior relative to other mixtures. This applies to both unsubstituted mercaptosilane from Mixture 5 (VP Si 263) as well as to mercaptosilanes with one methyl group (Mixture 7) and with two methyl groups (Mixture 9). Mixtures 8 to 13 also show improved Mooney-Scorch data. This is combined with improved machining security, e.g. when extruding tire treads or die casting.

Example 11: Technical rubber testing.

[0064] The formulation used for the rubber mixtures is given in Table 9. The mixtures differ in terms of the added coupling agent on the basis of equimolar dosing as given in Table 10, the mixing instructions are given in Table 2.

Table 9

<td>Substance</td><td>Mixtures 14 to 21</td>

<td colspan="2">[Phr]</td>

<td colspan="2">1st degree</td>

<td>Buna VSL 5025-1</td><td> 96</td>

<td>Buna CB 24</td><td> 30</td>

<td>Ultrasil 7000 GR</td><td> 80</td>

<td>Silanes from Table 10</td><td>equimolar</td>

<td>ZnO</td><td> 3</td>

<td>Stearic acid</td><td> 2</td>

<td>Naftolen ZD</td><td> 10</td>

<td>Vulkanox 4020</td><td> 1,5</td>

<td>Protector G 3108</td><td> 1</td>

<td colspan="2">2nd degree</td>

<td colspan="2">Entry grade 1</td>

<td colspan="2">3rd degree</td>

<td>Entry grade 2</td><td></td>

<td>Vulkacit D</td><td> 2</td>

<td>Vulkacit CZ</td><td> 1,5</td>

<td>Percacit TBzTD</td><td> 0,2</td>

<td>Sulfur</td><td> 1,5</td>

Table 10

<td>Mix No.</td><td>silane</td><td>phr</td>

<td>14 (reference)</td><td>VP Si 263</td><td> 2,00</td>

<td>15 (reference)</td><td>Silan from the example comparative 3</td><td> 1,75</td>

<td> 16</td><td>Silane from Example 3</td><td> 4,31</td>

<td> 17</td><td>Silane from Example 4</td><td> 9,68</td>

<td> 18</td><td>Silane from Example 5</td><td> 3,82</td>

<td> 19</td><td>Silane from Example 6</td><td> 2,97</td>

<td> 20</td><td>Silane from Example 7</td><td> 9,80</td>

<td> 21</td><td>Silane from Example 8</td><td> 3,94</td>

[0065] The tests carried out are listed in Table 7. Table 11 shows the results of a technical rubber test.

Table 11

<td>Vulcanizate data</td><td>Unit</td><td>Mixture 14 (reference)</td><td>Mixture 15 (reference)</td><td>Mixture 16</td><td>Mixture 17</td>

<td>Time scorching^t5</td><td>[Min]</td><td> 12,2</td><td> 13,2</td><td> 16,3</td><td> 14,6</td>

<td>Time scorching^t35</td><td>[Min]</td><td> 16,1</td><td> 17,2</td><td> 20,9</td><td> 19,7</td>

<td>Strength for further tearing A</td><td>[N / mm]</td><td> 28,3</td><td> 30,1</td><td> 32,9</td><td> 37,6</td>

<td>Strength for further tearing B</td><td>[N / mm]</td><td> 24,0</td><td> 25,2</td><td> 29,9</td><td> 31,4</td>

<td>Vulcanizate data</td><td>Unit</td><td>Mixture 18</td><td>Mixture 19</td><td>Mixture twenty</td><td>Mixture 21</td>

<td>Time scorching^t5</td><td>[Min]</td><td> 20,1</td><td> 15,2</td><td> 17,0</td><td> 14,6</td>

<td>Time scorching^t35</td><td>[Min]</td><td> 25,1</td><td> 19,6</td><td> 23,0</td><td> 19,2</td>

<td>Strength for further tearing A</td><td>[N / mm]</td><td> 35,9</td><td> 33,4</td><td> 37,4</td><td> 32,6</td>

<td>Strength for further tearing B</td><td>[N / mm]</td><td> 30,1</td><td> 26,8</td><td> 31,1</td><td> 25,8</td>

[0066] Also with equimolar dosing of the mixture with the silanes of Examples 3 to 8, they show advantages in both tear behavior as well as in behavior

Scorcha relative to unsubstituted mercaptosilane and mercaptosilane with one methyl group and two ethoxy groups.

Prepared and verified by dr Aleksandra Twardowska Patent Attorney