Stabilized compositions of sulfur-containing silanes with high mercapto content

Abstract

The present invention relates to a composition comprising one or more sulfur-containing silanes, one or more mercapto-functional organic compounds, and at least one acid selected from acids having a pKa of less than 3.75, determined in aqueous solution at a temperature of 25° C., and Lewis acids, as a stabilizer against the formation of hydrogen sulfide and disulfide by-products upon storage and aging of the composition.

Description

[Technical field]

[0001] The present invention relates to a composition comprising one or more sulfur-containing silanes, one or more mercapto-functional organic compounds, and at least one acid selected from acids having a pKa of less than 3.75, determined in aqueous solution at a temperature of 25° C., and Lewis acids, as a stabilizer, a method for preparing said composition, a method for reducing hydrogen sulfide emissions from sulfur-containing silane compositions, the use of said composition as an additive for silica-filled rubber compositions, and rubber compositions comprising the composition of the present invention and vulcanized articles made therefrom. The stabilized composition according to the present invention improves the wear characteristics of tire treads and dramatically reduces and / or prevents the formation of hydrogen sulfide and disulfide by-products during storage and aging of the composition. [Background technology]

[0002] Mercaptans are known to react with sulfur to form polysulfides and release hydrogen sulfide even at room temperature in the presence of small amounts of basic catalysts such as amines, e.g.: 2HS-R+S → RSS-R+H2S 2RSH+2S → RS3R+H2S (See, for example, Freeman H. MacMillan and J. A. King, "Studies on the Wilgerot reaction. VI. Mechanism of primary oxidation of thiols," J. Am. Chem. Soc. 1948, 70, 12, 4143-4150; US2237625; B. D. Vineyard, "Mercaptan-sulfur reactions. Alkyl trisulfides," J. Org. Chem. 1966, 31, 2, 601-602; and Liu L. F. et al., "Improvement of thiolate / disulfide mediated dye-sensitized solar cells by supramolecular lithium cation assemblies of crown ethers," Sci. Rep. 3, 2413; DOI:10. 1038 / srep02413(2013)).

[0003] The formation of H2S is also a known problem reported in the literature for sulfur-containing silanes and blends of sulfur-containing silanes with mercaptans. For example, Karen Raben and Hans-Detlef Luginsland, "Precipitated Silica, Optimal Blends of Silanes," Rubber & Plastics News, June 29, 2015; and Hans-Detlef Luginsland and Karen Raben, "Development of Sulfur-Functional Silanes as Coupling Agents in Silica-Reinforced Rubber Compounds, Their Historical Development Over Several Decades," GummiFasern Kunststoffe, 68, No.11, 2015, pp.734-737, report that polysulfides and mercaptans are known to form H2S at high temperatures when mixed in the liquid state. US 2021 / 0292520 A1 discloses improved processability of rubber mixtures containing a mixture of disulfide silanes or polysulfide silanes and at least one mercaptosilane, but no solution is provided for mitigating H2S emissions.

[0004] Although US6384256 and US6242618 provide examples of solutions that have been attempted to alleviate the H2S problem, there is no known method for inhibiting the mechanism of H2S formation in sulfur-containing silanes and blends thereof, particularly sulfur-containing silane blends with high mercapto concentrations.

[0005] Therefore, a solution is needed that can mitigate H2S emissions from such blends. Similarly, a solution remains necessary to address the problem of polysulfide formation, such as the formation of disulfide silane (bis-3-triethoxysilylpropyl disulfide, abbreviated as TESPD) in such blends, while at the same time changing the composition of the mixture to reduce mercaptosilanes (due to aging).

[0006] Therefore, the technical problem to be solved by this invention is to provide a storage stable composition of sulfur-containing silanes and mercaptans which when compounded with rubber will improve the performance of tire treads. Summary of the Invention

[0007] The inventors have surprisingly found that the technical problems of hydrogen sulfide formation and polysulfide by-product formation upon aging can be satisfactorily solved when at least one acid of a given pKa is added to a blend of sulfur-containing silanes without (free) mercapto functionality and organomercapto-functional compounds. Thus, according to the present invention: (a) one or more sulfur-containing silanes that are free of (free) mercapto (HS-) functionality; (b) one or more organic compounds with (free) mercapto (HS-) functionality; (c) at least one acid selected from (c1) an acid having a pKa, determined in aqueous solution at a temperature of 25° C., of less than 3.75, and (c2) a Lewis acid; A composition comprising: DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] Thus, the composition of the present invention comprises: (a) one or more sulfur-containing silanes that are free of (free) mercapto (HS-) functionality; (b) one or more organic compounds with (free) mercapto (HS-) functionality; (c) at least one acid selected from acids having a pKa, determined in aqueous solution at a temperature of 25° C., of less than 3.75, and Lewis acids; Contains:

[0009] The storage stable compositions of the present invention almost completely eliminate the formation of hydrogen sulfide and polysulfide by-products upon aging.

[0010] Sulfur-containing silanes (component (a)) that do not have (free) mercapto (HS-) functionality The compositions of the present invention contain one or more sulfur-containing silanes (a), preferably one or two, more preferably one sulfur-containing silane (a).

[0011] The sulfur-containing silanes (a) do not have free mercapto (HS-) functionality, i.e. they do not have the functional group HS- (i.e. mercapto group) in their structure, which distinguishes them from the organic compounds (b) with (free) mercapto (HS-) functionality described in particular below.

[0012] Preferably, the sulfur-containing silanes (a) without mercapto (HS-) functionality are selected from the group consisting of blocked mercaptosilanes, organosilane polysulfides, and mixtures thereof, more preferably from blocked mercaptosilanes. Even more preferably, they are selected from the group consisting of blocked mercaptosilanes having both blocked thiol and alkoxysilane functionality, and even more preferably, they are selected from blocked mercapto-functional alkylalkoxysilanes, i.e., (mercaptoalkyl)(alkoxy)silanes.

[0013] In some embodiments of the composition according to the invention, the sulfur-containing silane (a) having no mercapto (HS-) functionality is selected from the group consisting of blocked mercaptosilanes of the formula: [ka] R in the formula 1 independently a straight chain alkylene group of 1 to 6 carbon atoms or a branched chain alkylene group of 3 to 6 carbon atoms; R 2 each of which is a straight chain alkylene group of from 2 to 8 carbon atoms or a branched chain alkylene group of from 3 to 8 carbon atoms; R 3 each independently is a straight chain alkylene group of 1 to 6 carbon atoms or a branched chain alkylene group of 3 to 6 carbon atoms; X 1 -OR 4 Group, where R 4 is an alkyl group of 1 to 4 carbon atoms, -OR 5 OH group, where R 5is a straight chain alkylene group having 2 to 8 carbon atoms or a branched chain alkylene group having 3 to 8 carbon atoms, or X 1 -OR 6 (OR 7 )cOR 8 , where R 6 is a linear alkylene group having 2 to 6 carbon atoms or a branched alkylene group having 3 to 6 carbon atoms, preferably 3 carbon atoms; R 7 each independently represents an alkylene group of 2 to 4 carbon atoms, and R 8 is a straight chain alkyl group of 1 to 16 carbon atoms or a branched chain alkyl group of 3 to 16 carbon atoms, and c is an integer from 1 to 20; X 2 and X 3 is independent of X 1 or methyl; X 4 Each of X is independent. 1 or methyl; Y 1 Each of these is -C(=O)R 9 , -C(=S)OR 9 or -CN, where R 9 each is independently a straight chain alkylene group of 1 to 16 carbon atoms, more preferably 5 to 11 carbon atoms, and even more preferably 6 to 9 carbon atoms, or a branched chain alkylene group of 3 to 16 carbon atoms, more preferably 5 to 11 carbon atoms, and even more preferably 6 to 9 carbon atoms; and a is an integer from 0 to 8, with the proviso that (iii) X 1 and X 2 -OR 4 In the case of two -OR 4 are bonded to each other via covalent bonds to form a ring structure containing two oxygen atoms and a silicon atom bonded to the same silicon atom, -OR 4 -R 4 may form O-groups; (iv) a is 1 to 8 and X 3 and X 4 -OR 4 If so, then two -OR 4The groups are bonded to each other through covalent bonds to form a ring structure that is bonded to the same silicon atom and contains 2 to 8 carbon atoms, 2 oxygen atoms, and a silicon atom, -OR 4 -R 4 An O-group may be formed.

[0014] In some embodiments of the composition according to the invention, the sulfur-containing silane (a) having no mercapto (HS-) functionality is selected from the group consisting of blocked mercaptosilanes of formula (XI), where R 1 is a linear alkylene group having 1 to 6 carbon atoms or a branched alkylene group having 3 to 6 carbon atoms; Y 1 is -C(=O)R 9 , -C(=S)OR 9 or -CN, where R 9 each independently represents a straight chain alkylene group of 1 to 16 carbon atoms, more preferably 5 to 11 carbon atoms, and even more preferably 6 to 9 carbon atoms, or a branched chain alkylene group of 3 to 16 carbon atoms, more preferably 5 to 11 carbon atoms, and even more preferably 6 to 9 carbon atoms; X 1 -OR 4 Group, where R 4 is an alkyl group of 1 to 4 carbon atoms, X 2 and X 3 is independent of X 1 or methyl, and a is 0.

[0015] In some embodiments of the composition according to the invention, the sulfur-containing silane (a) having no mercapto (HS-) functionality is selected from the group consisting of blocked mercaptosilanes of formula (I), where R 1 are independently a linear alkylene group having 1 to 6 carbon atoms or a branched alkylene group having 3 to 6 carbon atoms; R 2 each of R is a straight chain alkylene group of 2 to 8 carbon atoms or a branched chain alkylene group of 3 to 8 carbon atoms; 3 each independently represents a straight chain alkylene group of 1 to 6 carbon atoms or a branched chain alkylene group of 3 to 6 carbon atoms; Y 1 is -C(=O)R 9 , -C(=S)OR9 or -CN, where R 9 each independently represents a straight chain alkylene group of 1 to 16 carbon atoms, more preferably 5 to 11 carbon atoms, and even more preferably 6 to 9 carbon atoms, or a branched chain alkylene group of 3 to 16 carbon atoms, more preferably 5 to 11 carbon atoms, and even more preferably 6 to 9 carbon atoms; X 1 and X 2 -OR 4 , where R 4 is an alkyl group of 1 to 4 carbon atoms, and X 1 and X 2 Two-OR 4 The groups are bonded to each other through covalent bonds to form a ring structure that is bonded to the same silicon atom and contains 2 to 8 carbon atoms, 2 oxygen atoms, and a silicon atom, -OR 4 -R 4 Forming an O-group or X 1 and X 2 Each of -OR 5 OH group, where R 5 is a linear alkylene group having 2 to 8 carbon atoms or a branched alkylene group having 3 to 8 carbon atoms; X 3 and X 4 are independent -OR 4 is a group, where R 4 is an alkyl group of 1 to 4 carbon atoms, -OR 5 OH group, where R 5 is a straight chain alkylene group having 2 to 8 carbon atoms or a branched chain alkylene group having 3 to 8 carbon atoms, provided that X 3 and X 4 -OR 4 If it is, then two -OR 4 The groups are bonded to each other through covalent bonds to form a ring structure that is bonded to the same silicon atom and contains 2 to 8 carbon atoms, 2 oxygen atoms, and a silicon atom, -OR 4 -R 4 O-groups may be formed, where a is 1 to 8, preferably 1 to 3.

[0016] In some embodiments of the composition according to the invention, the sulfur-containing silane (a) without mercapto (HS-) functionality is selected from the group consisting of triethoxysilylmethyl thioformate, 2-triethoxysilylethyl thioacetate, 3-triethoxysilylpropyl thiopropanoate, 3-triethoxysilylpropyl thiohexanoate, 3-triethoxysilylpropyl thio-(2-ethyl)-hexanoate, 3-triethoxysilylpropyl thiooctanoate, 3-diethoxymethylsilylpropyl thiooctanoate, 3-triethoxy ... silylpropylthiooctanoate, 3-ethoxydimethylsilylpropylthiooctanoate, 3-triethoxysilylpropylthiododecanoate, 3-triethoxysilylpropylthiooctadecanoate, 3-trimethoxysilylpropylthiooctanoate, 3-triacetoxysilylpropylthioacetate, 3-dipropoxymethylsilylpropylthiopropanoate, 4-oxa-hexyloxydimethylsilylpropylthiooctanoate, 3-(2-{3-[2-(4-thia-5-oxo-dodecyl)-5-methyl -[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy}-5-methyl-[1,3,2]dioxasilinan-2-yl)-4-thia-5-oxo-dodecane;3-(2-{3-[2-(4-thia-5-oxo-dodecyl)-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy}-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yl)-4-thia-5-oxo-dodecane;3-(2-{3-[2-(4-thia a-5-oxo-dodecyl)-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yloxy]-1,1-dimethyl-butoxy}-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yl)-4-thia-5-oxo-dodecane; 3-({3-[2-thia-3-oxo-decyl)-5-methyl-[1,3,2]dioxasilinan-yloxy]-2-methyl-propoxy}-bis-[3-hydroxy-2-methyl-propoxy]-silanyl)-2-thia-3-oxo-decane;3-[{3-[{3-bis-(3-hydroxy-2-methyl-propyl)-(4-thia-5-oxo-dodecyl)-silanyloxy]-1-methyl-propoxy}-(3-hydroxy-2-methyl-propoxy)-(4-thia-5-oxo-dodecyl)-silanyloxy]-2-methyl-propan-1-ol;3-[[3-((3-hydroxy-3-methyl-propoxy)-4-thia-5-oxo-dodecyl)-{3-[2-(4-thia-5-oxo-dodecyl)-5-methyl-[1,3, 2]dioxasilinan-2-yloxy]-1-methyl-propoxy}-silanyloxy)-2-methyl-propoxy-(3-hydroxy-2-methyl-propoxy)-4-thia-5-oxo-dodecyl)-silanyl]-2-methylpropan-1-ol;3-(2-{3-[2-(4-thia-5-oxo-6-ethyl-decyl)-[1,3,2]dioxasilinan-2-yloxy]-propoxy}-[1,3,2]dioxasilinan-2-yl)-4-thia-5-oxo-6-ethyl-decyl 3-({3-[2-thia-3-oxo-octyl)-5-methyl-[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy}-diethoxy]-silanyl)-2-thia-3-oxo-octane;3-[{3-[{3-bis-(3-hydroxy-2,2-dimethyl-propyl)-(4-thia-5-oxo-dodecyl)-silanyloxy]-2,2-dimethyl-propoxy}-(3-hydroxy-2,2-dimethyl-propoxy)-(4-thia-5-oxo-dodecyl) )-silanyloxy]-2,2-dimethyl-propan-1-ol; 3-[{3-[(methyl)-(3-hydroxy-2-methyl-propoxy)-(4-thia-5-oxo-dodecyl)-silanyloxy]-2-methyl-propoxy}-methyl)-(4-thia-5-oxo-dodecyl)-silanyloxy]-2-methyl-propan-1-ol, 3-(triethoxysilyl)propyl thiocyanate, and combinations thereof;

[0017] In some embodiments of the composition according to the invention, the sulfur-containing silane (a) having no mercapto (HS-) functionality is 3-octanoylthio-1-propyltriethoxysilane (3-triethoxysilylpropylthiooctanoate).

[0018] In some embodiments of the compositions according to the present invention, the sulfur-containing silane (a), which is the component that does not have mercapto (HS-) functionality, contains at least one polysulfide moiety -S. x -, where x is an average value of from about 2 to about 12, preferably from about 2 to about 10, more preferably from about 2 to about 8, more preferably from about 2 to about 6, more preferably from about 2 to about 4, more preferably about 2 or about 4.

[0019] In some embodiments of the composition according to the present invention, the sulfur-containing silane (a), which is the component that does not have mercapto (HS-) functionality, is selected from the formula (II): [ka] R in the formula 1 is a linear alkylene group of 1 to 6 carbon atoms or a branched alkylene group of 3 to 6 carbon atoms, preferably 3 carbon atoms; X 1 , X 2 and X 3 are each independently as defined above, preferably each is ethoxy; and x is as defined above, preferably x is about 2 or about 4.

[0020] In some embodiments of the composition according to the present invention, the sulfur-containing silane (a) is selected from the group consisting of bis-3-triethoxysilylpropyl disulfide, bis-triethoxysilylpropyl tetrasulfide, and 3-octanoylthio-1-propyltriethoxysilane.

[0021] In some embodiments of compositions according to the present invention, the sulfur-containing silane (a) forms a major component relative to other components, based on the weight of the components in the composition.

[0022] In some embodiments of the composition according to the invention, the sulfur-containing silane (a) forms more than 50% by weight of the total composition. In this description and throughout the specification, the term "wt%" or "wt %" means "weight percent."

[0023] In some embodiments of the composition according to the present invention, the composition comprises from about 5 to about 95% by weight, preferably from about 10 to about 95% by weight, more preferably from about 20 to about 95% by weight, more preferably from about 30 to about 95% by weight, more preferably from about 40 to about 95% by weight, and even more preferably from about 50 to about 95% by weight of one or more sulfur-containing silanes (a) based on the total weight of the composition. The upper limit of the amount of sulfur-containing silane (a) can also be about 90% or about 85% by weight based on the total weight of the composition.

[0024] (b) Organic compounds with (free) mercapto (HS-) functionality The compositions according to the present invention comprise (b) one or more organic compounds with (free) mercapto (ie, HS-) functionality.

[0025] In some embodiments of the composition according to the invention, the organic compound (b) with mercapto (HS-) functionality is selected from mercaptosilanes.

[0026] In some embodiments of the composition according to the invention, the organic compound (b) with mercapto (HS-) functionality is selected from difunctional silanes having thiol and alkoxysilane functionality.

[0027] In some embodiments of the composition according to the invention, the organic compound (b) with mercapto (HS-) functionality is selected from mercapto-functional alkylalkoxysilanes.

[0028] In some embodiments of the composition according to the invention, the organic compound (b) with mercapto (HS-) functionality is selected from mercaptosilanes of formula (III): [ka] R in the formula 1 are each independently as defined above; R 2 each independently as defined above; R 3 each independently as defined above; X 1 , X 2 , X 3 and X 4 are each independently as defined above, and a is independently as defined above.

[0029] In some embodiments of the composition according to the invention, the organic compound (b) with mercapto (HS-) functionality is selected from mercaptosilanes of formula (III), where R 1 is a linear alkylene group having 1 to 6 carbon atoms or a branched alkylene group having 3 to 6 carbon atoms; X 1 -OR 4 Group, where R 4 is an alkyl group of 1 to 4 carbon atoms, X 2 and X 3 is independent of X 1 Or methyl and a is 0.

[0030] In some embodiments of the composition according to the invention, the organic compound (b) with mercapto (HS-) functionality is selected from mercaptosilanes of formula (III), where R 1 are independently a linear alkylene group having 1 to 6 carbon atoms or a branched alkylene group having 3 to 6 carbon atoms; R 2 each of R is a straight chain alkylene group of 2 to 8 carbon atoms or a branched chain alkylene group of 3 to 8 carbon atoms; 3 each independently represents a straight chain alkylene group of 1 to 6 carbon atoms or a branched chain alkylene group of 3 to 6 carbon atoms; 1 and X 2 -OR 4 , where R4 is an alkyl group of 1 to 4 carbon atoms, and X 1 and X 2 Two-OR 4 The groups are bonded to each other through covalent bonds to form a ring structure that is bonded to the same silicon atom and contains 2 to 8 carbon atoms, 2 oxygen atoms, and a silicon atom, -OR 4 -R 4 Forming an O-group or X 1 and X 2 Each of -OR 5 OH group, where R 5 is a linear alkylene group having 2 to 8 carbon atoms or a branched alkylene group having 3 to 8 carbon atoms; X 3 and X 4 are independent -OR 4 is a group, where R 4 is an alkyl group of 1 to 4 carbon atoms, -OR 5 OH group, where R 5 is a straight chain alkylene group having 2 to 8 carbon atoms or a branched chain alkylene group having 3 to 8 carbon atoms, provided that X 3 and X 4 -OR 4 If it is, then two -OR 4 The groups are bonded to each other through covalent bonds to form a ring structure that is bonded to the same silicon atom and contains 2 to 8 carbon atoms, 2 oxygen atoms, and a silicon atom, -OR 4 -R 4 O-groups may be formed, where a is 1 to 8, preferably 1 to 3.

[0031] In some embodiments of the composition according to the invention, the organic compound (b) with mercapto (HS-) functionality is selected from the group consisting of 3-mercapto-1-propyltriethoxysilane, 2-mercapto-1-ethyltriethoxysilane, mercaptomethyltriethoxysilane, 6-mercapto-1-hexyltriethoxysilane, 4-mercapto-1-butyltriethoxysilane, 1-mercapto-1-ethyltriethoxysilane, 3-mercapto-1-propylmethyldiethoxysilane, 3-mercapto-1-propyldimethylethoxysilane. , 3-mercapto-1-propyltrimethoxysilane, 2-mercapto-1-ethyltrimethoxysilane, mercaptomethyltrimethoxysilane, 6-mercapto-1-hexyltrimethoxysilane, 4-mercapto-1-butyltrimethoxysilane, 1-mercapto-1-ethyltrimethoxysilane, 3-mercapto-1-propylmethyldimethoxysilane, 3-mercapto-1-propyldimethylmethoxysilane, 3-mercapto-1-propyltripoxysilane, 3-mercapto-1-propyltriisopropoxysilane, xysilane, 3-mercapto-1-propyltributoxysilane, 4-(3,6,9,12,15-penta-oxaoctacosyloxy)-4-ethoxy-5,8,11,14,17,20-hexaoxa-4-silatritriacontane-1-thiol, 3-(2-{3-[2-(3-mercapto-propyl)-5-methyl-[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy}-5-methyl-[1,3,2]dioxasilinan-2-yl)-propane-1-thiol; -(3-mercapto-propyl)-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy}-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yl)-propane-thiol;3-(2-{3-[2-(3-mercapto-propyl)-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yloxy]-1,1-dimethyl-butoxy}-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yl)-propane-1-thiol;3-({3-[2-mercapto-propyl)-5-methyl-[1,3,2]dioxasilinane-yloxy]-2-methyl-propoxy}-bis-[3-hydroxy-2-methyl-propoxy]-silanyl)-propane-1-thiol;3-[{3-[{3-bis-(3-hydroxy-2-methyl-propyl)-(3-mercapto-propyl)-silanyloxy]-1-methyl-propoxy}-(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-silanyloxy]-2-methyl-propane- 1-ol;3-[[3-((3-hydroxy-3-methyl-propoxy)-3-mercapto-propyl)-{3-[2-(3-mercapto-propyl)-5-methyl-[1,3,2]dioxasilinan-2-yloxy]-1-methyl-propoxy}-silanyloxy)-methyl-propoxy-(3-hydroxy-2-methyl-propoxy)-3-mercapto-propyl)-silanyl]-2-methylpropan-1-ol;3-(2-{3-[2-(3-mercapto-butyl)-[1,3,2]dioxasilinan-2-yloxy]-1-methyl-propoxy}-silanyloxy)-methyl-propoxy-(3-hydroxy-2-methyl-propoxy)-3-mercapto-propyl)-silanyl)-2-methylpropan-1-ol 3-({3-[2-mercapto-methyl)-5-methyl-[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy}-diethoxy]-silanyl)-methane-1-thiol;3-[{3-[{3-bis-(3-hydroxy-2,2-dimethyl-propyl)-(3-mercapto-propyl)-silanyloxy]-2,2-dimethyl-propoxy}-(3-hydroxy-2,2-dimethyl-propoxy) -(3-mercapto-propyl)-silanyloxy]-2,2-dimethyl-propan-1-ol; 3-[{3-[(methyl)-(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-silanyloxy]-2-methyl-propoxy}-methyl)-(3-mercapto-propyl)-silanyloxy]-2-methyl-propan-1-ol, 3-mercaptopropyl-ethyoxyl-di(tridecyl-pentamethoxy)-silane, and combinations thereof.

[0032] In some embodiments of the composition according to the invention, the organic compound (b) with mercapto (HS-) functionality is selected from the group of mercaptosilanes consisting of 3-mercapto-1-propyltriethoxysilane, and 4-(3,6,9,12,15-penta-oxaoctacosyloxy)-4-ethoxy-5,8,11,14,17,20-hexaoxa-4-silatritriacontane-1-thiol.

[0033] In some embodiments, the composition according to the present invention further comprises one or more organic compounds (b) with (free) mercapto (HS-) functionality that are free of silicone or silane moieties, such as alkyl mercaptans such as n-octyl mercaptan or tert-dodecanethiol, e.g., those of the formula HS(CH) n Mercapto acids of the type having a COOH group, where n is 1 to 5, and their esters, including thioglycolic acid, 3-mercaptopropionic acid, methyl-3-mercaptopropionate, pentaerythritol tetrakis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), etc., including hydroxyalkyl mercapto compounds such as thioglycerol, 1,3-dimercapto-2-propanol, or aromatic and heteroaromatic mercapto compounds such as mercapto-2-benzothiazole.

[0034] In some embodiments of the composition according to the invention, the composition comprises one or more organic compounds with mercapto (HS-) functionality (b) in an amount of about 5 to about 95% by weight, preferably about 5 to about 90% by weight, more preferably about 5 to about 80% by weight, more preferably about 5 to about 70% by weight, more preferably about 5 to about 60% by weight, and even more preferably about 5 to about 50% by weight, based on the total weight of the composition. The upper limit of the amount of organic compounds with mercapto (HS-) functionality (b) can also be about 90% by weight or about 85% by weight, based on the total weight of the composition.

[0035] As mentioned above, according to the present invention, the stability problem is presumed to essentially result from the presence of basic components or basic impurities in components (a) and / or (b), which may also result from the manufacturing process of components (a) and / or (b).

[0036] The basic component may be present in the silane component (a) or the mercapto component (b), or in both the silane component (a) and the mercapto component (b). Generally, the majority of the amount (weight) of the basic component is present in component (a). Thus, stabilization of the composition of components (a) and (b) is achieved especially for compositions of components (a) and (b) that contain at least one basic component or impurity. Such a basic component or basic impurity can generally be any basic component, such as a substance capable of accepting a proton, for example an organic base, in particular an amine, for example a trialkylamine, such as tributylamine, or an inorganic base, such as hydroxides, sulfides, and hydrosulfides, as well as for example an alkoxide.

[0037] Such basic components can be present in the compositions of the present invention in an amount, for example, up to about 4% by weight, preferably up to about 3% by weight, more preferably up to about 1% by weight, even more preferably up to about 0.5% by weight, even more preferably up to about 0.4% by weight, even more preferably up to about 0.2% by weight, based on the total weight of components (a) and (b). With respect to the lower limit, the basic components can be present in components (a) and (b) in an amount of, for example, > about 0% by weight (where ">" means "greater than", including elsewhere), or > about 0.01% by weight, or > about 0.1% by weight, based on the total weight of components (a) and (b). Further, according to the present invention, it is contemplated that the upper and lower limits of the basic components described form ranges, such as > about 0.1 to about 4% by weight or > about 0.1 to about 0.4% by weight.

[0038] Furthermore, such basic components can be present in component (a) in an amount, for example, with an upper limit of up to about 4% by weight, preferably up to about 3% by weight, more preferably up to about 1% by weight, even more preferably up to about 0.5% by weight, even more preferably up to about 0.4% by weight, even more preferably up to about 0.2% by weight, based on the amount of component (a). With respect to the lower limit, the basic component can be present in component (a) in an amount of, for example, > about 0% by weight, or > about 0.01% by weight, or > about 0.1% by weight, based on the total weight of component (a). Furthermore, according to the present invention, it is contemplated that the upper and lower limits of the basic component described form a range, such as > about 0.1 to about 4% by weight or > about 0.1 to about 0.4% by weight.

[0039] Furthermore, such basic component can be present in component (b) in an amount, for example, with an upper limit of up to about 1% by weight, preferably up to about 0.5% by weight, more preferably up to about 0.2% by weight, even more preferably up to about 0.1% by weight, even more preferably up to about 0.06% by weight, even more preferably up to about 0.01% by weight, based on the amount of component (b). With respect to the lower limit, the basic component can be present in component (b) in an amount of, for example, > about 0% by weight, or > about 0.001% by weight, or > about 0.01% by weight, or > about 0.1% by weight, based on the total weight of component (b). Furthermore, according to the present invention, it is considered to form ranges from the stated upper and lower limits of the basic component, such as > about 0.001 to about 0.5% by weight, or > about 0.001 to about 0.1% by weight, or about 0.001 to about 0.06% by weight.

[0040] acid(c) The composition of the present invention comprises at least one acid selected from (c1) acids having a pKa, determined in aqueous solution at a temperature of 25° C., of less than 3.75, and (c2) a Lewis acid.

[0041] In one embodiment, the at least one acid (c) comprises one or more acids (c1) having a pKa, determined in aqueous solution at a temperature of 25° C., of less than 3.75.

[0042] In one embodiment, the at least one acid (c) comprises one or more Lewis acids (c2).

[0043] In one embodiment, the at least one acid (c) comprises one or more acids (c1) having a pKa, determined in aqueous solution at a temperature of 25° C., of less than 3.75, in combination with one or more Lewis acids (c2).

[0044] This acid (c) has surprisingly been found to stabilize the compositions of the invention comprising the sulfur-containing silane (a) and the mercapto-functional organic compound (b), in particular against the formation of hydrogen sulfide on storage and against the formation of decomposition products which, for example, increase the content of disulfide silanes.

[0045] The acids can be used in combination, including, for example, more than one acid (c1), more than one acid (c2), or a combination of one or more acids (c1) and one or more acids (c2). Acids (c1) having a pKa of less than 3.75, determined in aqueous solution at a temperature of 25° C. pKa is an index that quantitatively expresses the strength of an acid, and is also called the acid dissociation constant, and is defined as reported in the reference "CRC Handbook of Chemistry and Physics," 95th Edition, Section 5, p. 94, which is incorporated herein by reference.

[0046] The pKa of the acids used in the present invention is in particular the pKa measured in dilute aqueous solution at a temperature of 25°C. Such pKa values ​​can be determined, for example, by methods known in the art (see, for example, Jethre Reijenga, Arno van Hoof, Antony van Loon, Bram Theunissen, Insights in Analytical Chemistry 2013:853-71, or X. Subiracz, E. Huguet, M. Rozes, E. Bosch, C. Lafols, "Elsevier Reference Module for Chemistry, Molecular Science and Chemical Engineering" (2015), http: / / dx.doi.org / 10.1016 / B978-0-12-409547-2.11559-8 1), for example by potentiometric, conductive, spectrophotometric or other measurements, or alternatively, various data compilations of such pKa values ​​of acids are commercially available, for example the pKa data edited by R. Williams (see https: / / organicchemistrydata.org / hansreich / ).

[0047] As will be appreciated, within the scope of the present invention, pKa values ​​may include normal deviations over the measurement uncertainty of ±0.25 pKa units, or ±0.20 pKa units, or ±0.15 pKa units, or ±0.10 pKa units.

[0048] In an embodiment of the present invention, the acid (c1) having a pKa of less than 3.75, determined in aqueous solution at a temperature of 25° C., is preferably selected from the group consisting of protic acids (proton donors), such as inorganic acids, organic acids, and mixtures thereof, as exemplified below.

[0049] In an embodiment of the invention, the acid (c1) having a pKa of less than 3.75, determined in aqueous solution at a temperature of 25° C., is selected from inorganic and organic protic acids, preferably from organic acids such as carboxylic acids, organic sulfonic acids, organic phosphonic acids, organic phosphoric acids etc.

[0050] Suitable acids (c) may generally be selected from the group consisting of the following formula (IV): H p E qO r (IV) During the ceremony p is ≧1, preferably 1 to 4; q is ≧1, preferably 1 to 3; r is 0 to 6, preferably 0 to 4; E is independently Ti, Mo, W, Cr, Mn, Tc, Re, Fe, Ru, Os, B, C, Si, Sb, CN, CNO, SCN, N, P, As, Te, S, Se, F, Cl, Br, and I.

[0051] In an embodiment of the present invention, the acid (c1) is preferably selected from the group consisting of organic acids having at least one acidic functional group A selected from the following group: -C(=O)(-OH); -C(=S)(-OH); -S(=O)2(-OH); -OS(=O)2(-OH); -S(=O)(-OH); -OS(=O)(-OH); (-O)2P(=O)(-OH); -OP(=O)(-OH); -OP(=O)2(-OH); and -ON(=O)(-OH), and Preferred is a carboxylic acid group (-C(=O)(-OH)-) or a sulfonic acid group (-S(=O)2(-OH)).

[0052] Such organic acids may be of the following general formula (V): R-(A) y (V) wherein R is an organic group, such as an optionally substituted aromatic or aliphatic group, which may have up to 30, preferably up to 20, more preferably up to 10 carbon atoms and may optionally contain additional heteroatoms, such as halogens (F, Cl, Br, I), O, N, S, P, Si, B, etc., apart from those provided by the acidic functional group A, where the optional substituents are preferably selected from halogens (F, Cl, Br, I), hydroxy, alkoxy, acyl, cyano, nitro, etc., wherein the acidic functional group A is as defined above, and wherein y is an integer from 1 to 4, preferably from 1 to 3, more preferably from 1 to 2.

[0053] In an embodiment of the invention, the acid (c1) is hydrochloric acid HCl, nitric acid HNO3, phosphoric acid H3PO4, sulfuric acid H2SO4, hydrofluoric acid HF, hydrobromic acid HBr, perchloric acid HClO4, hydroiodic acid HI, phosphomolybdic acid H5Mo 12 O 41 P, hypophosphorous acid HO2P, polyphosphoric acid (H) n+2 (P) n (O) 3n+1 , phosphonic acid H3O3P, iodic acid HIO3, periodic acid H5IO6, hexafluorosilicic acid F6H2Si, chloric acid ClHO3, oleum H2O7S2, pyrophosphoric acid H4O7P2, and others.

[0054] In an embodiment of the invention, the acid (c1) is selected from the group consisting of organic acids selected from carboxylic acids, sulfonic acids, sulfinic acids, phosphonic acids, phosphinic acids and phosphoric acids, optionally bonded to organic groups such as alkyl, haloalkyl, perfluoroalkyl, cycloalkyl, alkenyl, aryl, aralkyl or substituted alkyl, substituted cycloalkyl, substituted alkenyl, substituted aryl, substituted aralkyl, etc., including halides such as F, Cl, Br, I, nitro groups, cyano groups, thiocyano groups, hydroxy groups, sulfhydryl groups, alkoxy groups, alkylthio groups or arylthio groups, acyl groups, carboxylic ester or acid groups, sulfonate ester or acid groups, phosphate ester or acid groups, etc.

[0055] Preferably, the acid is a sulfonic or sulfinic acid, such as chlorosulfonic acid, trifluoromethanesulfonic acid, methanesulfonic acid, benzenesulfinic acid, 4-dodecylbenzenesulfonic acid, p-toluenesulfonic acid, halogenated carboxylic acids, such as fluorinated or chlorinated, such as perfluorobutanoic acid, trifluoroacetic acid, dichloroacetic acid, chloroacetic acid, 2-bromobenzoic acid, phosphorus-based organic acids, such as octylphosphonic acid, 12-mercaptododecylphosphonic acid, carboxylic acids, such as oxalic acid, pyruvic acid, 3-oxobutanoic acid, maleic acid or fumaric acid, 2,3-dihydroxypropanoic acid, citric acid, tartaric acid, cis or trans-1,2-cyclopropanedicarboxylic acid, and terephthalic acid, among others, and combinations thereof.

[0056] Further examples include: trifluoromethanesulfonic acid, fluorosulfuric acid, salicylic acid, trifluoroacetic acid, tetrafluoroboric acid, salicylic acid, malic acid, 1-naphthalenesulfonic acid, 4-hydroxybenzenesulfonic acid, 1,5-naphthalenedisulfonic acid, 10-camparsulfonic acid, 1-hexanesulfonic acid, aminoethanesulfonic acid, diphenyl phosphate, phenylphosphonic acid, p-nitrobenzenesulfonic acid, 2,2-dichloroacetic acid, 2-hydroxyethanesulfonic acid, and the like, and combinations thereof.

[0057] In an embodiment of the invention, (c) the acid (c1) having a pKa of less than 3.75 determined in aqueous solution at a temperature of 25° C. can also be formed in situ by the addition of one or more hydrolyzable compounds that react with residual water present in components (a) and (b) of the composition to form said acid. Such hydrolyzable compounds are composed of groups capable of stabilizing a negative charge as a result of heterolytic bond cleavage, including halides, F, Cl, Br, I, alkyl, alkenyl or aryl carboxylate esters, alkyl, alkenyl or aryl sulfonate esters, perfluoroalkylsulfonate esters, alkyl, alkenyl or aryl phosphonate esters, which are linked to groups that undergo nucleophilic attack by water, including alkyl, acyl, carboxylate esters, sulfonyl, sulfonate esters, phosphoryl, phosphonate esters, thioether groups or epoxide rings. Such compounds which form acids in situ include, for example, acid anhydrides such as maleic anhydride, methanesulfonic anhydride, halogen boranes such as dichlorophenylborane, dibutylboron trifluoromethanesulfonate, halogen silanes such as halogenated trialkylsilanes such as chlorotrimethylsilane, or (3-chloropropyl)trichlorosilane, 1-chloroacyl halides such as alkanoyl halides such as octanoyl chloride, sulfonyl halides such as methanesulfonyl chloride, benzyl halides such as benzyl chloride, halohydrins or epihalohydrins such as epichlorohydrin, sulfenyl chloride, sulfuryl or thionyl chloride, phosphoryl chloride, dimethylmethylphosphonate, and the like. The corresponding chlorine compounds form HCl as acid (c1), whereas the corresponding compounds containing carboxylate, sulfonate, perfluorosulfonate or phosphonate groups form carboxylic, sulfonic, perfluorosulfonic or phosphonic acids as acids (c1).

[0058] Lewis Acid (C2) As is known in the art, a Lewis acid is generally a chemical species that contains a vacant orbital that can accept an electron pair from a Lewis base to form a Lewis adduct. In accordance with the present invention, such Lewis acids do not include protic acids according to (c1).

[0059] In an embodiment of the invention, the acid (c) is a Lewis acid (c2), which is preferably selected from the group consisting of lithium (Li) and alkali metals, beryllium (Be), magnesium (Mg) and alkaline earth metals, boron (B), aluminum (Al), silicon (Si), tin (Sn), d-block elements of the periodic table, such as scandium (Sc), titanium (Ti), vanadium (V), manganese (Mn), chromium (Cr), iron (Fe), cobalt (Co), and zinc (Zn), lanthanum (La) and compounds of the lanthanides, preferably the Lewis acid (c2) is an organoboron or titanium compound.

[0060] Examples include Lewis acid compounds containing a Group 13 metal atom, e.g., aluminum-based Lewis acids such as AlCl3, boron-based Lewis acids such as boron halides, organoboron compounds such as triorganylborons, e.g., triarylborons, e.g., B(C6H5)3 or B(C6F5)3 and their ether adducts.

[0061] Other examples include boron compounds such as beryllium (II) fluoride, beryllium (II) chloride, beryllium (II) bromide, boron (III) fluoride, boron (III) chloride, and boron (III) bromide; boron compounds such as phenylborane, triphenoxyborane, and phenyldichloroborane; aluminum compounds such as aluminum chloride (III), aluminum bromide (III), aluminum iodide (III), dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, and ethylaluminum dichloride; aluminum compounds such as trimethylaluminum, triethylaluminum, triphenylaluminum, aluminum trisbutyrate, and aluminum isopropoxide; trimethylsilyl triflate, tert-butyldimethylsilyl triflate, triisopropylsilyl triflate, trimethylsilyl iodide, tetraethylorthosilicate, and silicon tetrachloride. tin compounds such as tin dichloride or tin tetrachloride, organotin compounds such as dibutyltin acetate, dibutyltin dilaurate and dibutyltin oxide; titanium compounds such as titanium(IV) fluoride, titanium(IV) chloride, titanium(IV) bromide, tin(IV) chloride, tin titanium compounds such as titanium(IV) iodide, tetraalkylorthotitanates, tetra-n-butylorthotitanate, and other tetraalkylorthotitanates; titanium compounds such as titanium(IV) fluoride, titanium(IV) chloride, titanium(IV) bromide, tin(IV) chloride, tin titanium compounds such as titanium(IV) iodide, and other tetraalkylorthotitanates, such as tetra-n-butylorthotitanate; Chromium (II) fluoride, chromium (III) fluoride, chromium (II) chloride, chromium (III) chloride, chromium (II) bromide, chromium (III) bromide, iron (II) chloride, iron (III) chloride, iron (II) acetylacetonate, iron (II) bromide, iron (II) iodide, chromium (II) iodide; cobalt compounds such as cobalt (II) fluoride, cobalt (II) chloride, cobalt (II) bromide, and cobalt (II) iodide; zinc compounds such as zinc octanoate and zinc stearate. Among the above-mentioned Lewis acids, boron compounds and aluminum compounds are preferred, and trialkylborates such as triethylboric acid, tetraalkylorthotitanic acids such as tetra-n-butylorthotitanic acid, and aluminum alkoxides such as aluminum tri-sec-butylate are particularly preferred.

[0062] In an embodiment of the invention, the acid (c) is, for example, trifluoromethanesulfonic acid, sulfuric acid, trifluoroacetic acid, dichloroacetic acid, chloroacetic acid, and / or citric acid.

[0063] Most preferred are sulfonic acids such as methanesulfonic acid or 4-dodecylbenzenesulfonic acid.

[0064] In an embodiment of the invention, the acid (c1) preferably has a pKa of less than 3.5, or less than 3.0, or less than 2.5, or less than 2.0, or less than 1.5, or less than 1.0.

[0065] In an embodiment of the invention, the acid (c1) is selected from the group consisting of phosphoric acid, pyrophosphoric acid, phosphonic acid, polyphosphoric acid, methanesulfonic acid, benzenesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, sulfosalicylic acid, sulfamic acid, benzenedisulfonic acid, cumenesulfonic acid, sulfosalicylic acid, naphthalene monosulfonic acid or disulfonic acid, sulfosuccinic acid, isethionic acid, and phosphorus-based acids (e.g., phosphoric acid, pyrophosphoric acid, phosphonic acid, polyphosphoric acid), nitric acid, sulfuric acid, and hydrochloric acid, and combinations thereof.

[0066] In an embodiment of the invention, the acid (c1) is selected from the group consisting of benzenesulfonic acid, chloric acid, chromic acid, fluoroboric acid, fluorosulfuric acid, hexafluorophosphoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, methanesulfonic acid, nitric acid, p-toluenesulfonic acid, perchloric acid, periodic acid, permanganic acid, sulfuric acid, trifluoromethanesulfonic acid, and combinations thereof.

[0067] In an embodiment of the invention, the acid (c1) is selected from the group of hydrochloric, hydrobromic and hydroiodic acids, chlorous acid, chloric acid, perchloric acid, iodic acid, periodic acid, perchromic acid, nitric acid, phosphoric acid, phosphorous acid, hypophosphorous acid, diphosphoric acid, selenic acid, selenic acid, sulfurous acid, sulfuric acid, hydrogen sulfate, thiocyanic acid, the methyl, ethyl, n-propyl, n-butyl, dimethyl, di-(n-propyl), di-(n-butyl) and di-(2-ethylhexyl) esters of phosphoric acid, methanesulfonic acid, p-toluenesulfonic acid, 2,6-dihydroxybenzoic acid, amidosulfonic acid, nitroacetic acid, trimethylammonium acetic acid, dichloro-, difluoro-, tribromo-, trichloro- and trifluoroacetic acid, malonic acid, maleic acid, bromomaleic acid, chloromaleic acid, chlorofumaric acid. acid, bromo fumaric acid, oxalic acid, oxaluric acid, oxanilic acid, 4-nitrobenzoic acid, protonated amino acids with a pKa<2.5, and combinations thereof.

[0068] In the embodiment of the present invention, the acid (c) is used in the form of a solid, liquid or gas. Of these forms, the liquid form is preferred. These aggregation states are conveniently those at room temperature (25° C.) and normal pressure (1013.25 mbar).

[0069] In an embodiment of the invention, the acid (c) is used in a form having a concentration of about 98% by weight or greater, the remainder being preferably water.

[0070] In an embodiment of the invention, the acid (c) is used in a form having a concentration of at least about 30% by weight, based on the total weight of the acid, preferably at least about 50% by weight, more preferably at least about 70% by weight, more preferably at least about 90% by weight, and even more preferably at least about 98% by weight, with the remainder preferably being water.

[0071] In an embodiment of the invention, the acid (c) is used in a form having a concentration of about 50% to about 99% by weight, where the water content is up to 2% by weight, preferably up to 0.1% by weight, and the remainder is other components, preferably selected from solvents, oils, acids other than component (c), acid anhydrides, and acid esters.

[0072] In an embodiment of the invention, acid (c) is used in an amount that reduces the formation of H2S upon storage of a composition comprising components (a) and (b), e.g., compared to a composition that does not contain acid (c).

[0073] In this embodiment of the invention, the amount of acid (c) is preferably such that the pH of the composition, measured by the water-alcohol method as set forth below, is between 4 and 7, more preferably between 4 and 6, even more preferably between 5 and 6.

[0074] In an embodiment of the invention, the acid (c) is used in an amount of about 0.01 to about 5 wt.%, preferably about 0.01 to about 4 wt.%, more preferably about 0.01 to about 3 wt.%, more preferably about 0.01 to about 2 wt.%, more preferably about 0.01 to about 1 wt.%, more preferably about 0.01 to about 0.5 wt.%, and more preferably about 0.01 to about 0.1 wt.%, based on the total weight of the composition.

[0075] Other Acids In an embodiment of the invention, the composition optionally includes one or more acids with a pKa of 3.75≦pKa≦7, such as acetic acid, hexanoic acid, cyclohexanoic acid, heptanoic acid, octanoic acid, 4-methyloctanoic acid, 2-methylhexanoic acid, nonanoic acid, decanoic acid, benzoic acid, and 4-methoxybenzoic acid, among others.

[0076] In aspects of the invention, the composition optionally includes one or more hydrolyzable compounds that react in situ with residual water present in components (a) and (b) of the composition to form an acid with 3.75 < pKa < 7. Such compounds include, for example, esters such as ethyl octanoate, lactones such as gamma-butyrolactone, delta-valerolactone or lactide, lactams such as epsilon-caprolactam, carbonate esters such as propylene carbonate, ethylene carbonate or diethyl carbonate, acid anhydrides such as succinic anhydride, glycidyl esters such as glycidyl methacrylate, and combinations thereof.

[0077] Sulfur-free silanes (d) In some aspects, the composition according to the invention further includes one or more sulfur-free silanes, such as alkoxysilanes such as (alkoxy)(alkyl)silanes, such as Si(OEt)4, MeSi(OEt)3, MeSi(OCH2CH2OMe)3, ViSi(OEt)3, ViSi(OCH2CH2OMe)3, PhSi(OEt)3, PhSi(OCH2CH2OEt)3, 3-methacryloxypropyltriethoxysilane, 3-chloropropyltriethoxysilane, CH3(CH2)2Si(OEt)3, CH3(CH2)7Si(OEt)3, bis(triethoxysilyl)octane and others.

[0078] Composition Features pH of water-alcohol solution In some embodiments, the composition according to the present invention has a pH of the hydroalcoholic solution of less than about 7, preferably between about 3 and about 7, more preferably between about 4 and about 6, and even more preferably between about 5 and about 6 at 25° C. The pH of the hydroalcoholic solution is generally measured at 25° C. by using a pH meter, preferably including a glass electrode responsive to pH and a silver / silver chloride electrode as a reference electrode. First, a 2:1 volumetric ratio solution of isopropanol and deionized water (hydroalcoholic solution) is prepared, and 60 mL is poured into a beaker. The pH is adjusted to 7 using 0.01 M aqueous NaOH and 0.01 M aqueous HCl. Then, 10 g of the composition is dissolved in the hydroalcoholic solution with stirring, and the pH is then measured.

[0079] Scope of composition In some embodiments, the compositions according to the present invention comprise: from about 5 to about 95% by weight, preferably from about 50 to about 95% by weight, of one or more sulfur-containing silanes (a); from about 5 to about 95% by weight, preferably from about 5 to about 50% by weight, of one or more organic compounds (b), and from about 0.01 to about 5% by weight, preferably from about 0.01 to about 2% by weight, more preferably from about 0.01 to about 1% by weight, and even more preferably from about 0.01 to about 0.1% by weight of at least one acid (c); Each of these percentages is based on the total weight of the composition.

[0080] In some embodiments of the compositions according to the invention, the weight ratio of compound (a) to compound (b) is from about 1:1 to about 50:1 w / w, preferably from about 50 / 50 w / w to about 90 / 10, more preferably from about 60 / 40 to about 80 / 20, even more preferably from about 70 / 30 to about 80 / 20, and most preferably 75 / 25 w / w, or preferably within + / - 5% by weight of this ratio.

[0081] In some embodiments of the composition according to the invention, the weight ratio of compound (a) to compound (b) is: - From about 75 to about 25, - from about 4.8 to about 1.6, - about 7 to about 0.35, - Approximately 6.25 to approximately 0.7, -About 5.75 to about 1, - from about 5.2 to about 1.3, - about 4.4 to about 1.9, - about 3.6 to about 2.4, - from about 3 to about 1, or - selected from about 2.85 to about 3.15.

[0082] In some embodiments of the composition according to the present invention, the composition consists or consists essentially of: (a) one or more sulfur-containing silanes that are free of (free) mercapto (HS-) functionality; (b) one or more organic compounds with (free) mercapto (HS-) functionality; (c) at least one acid selected from an acid having a pKa, determined in aqueous solution at a temperature of 25° C., of less than 3.75, and one or more Lewis acids; wherein components (a) and (b) may contain basic components or basic impurities, as described in more detail below.

[0083] In some embodiments of the compositions according to the present invention, the concentration of H2S as determined by gas chromatography headspace analysis is less than 300 ppm, preferably less than 200 ppm, more preferably less than 100 ppm, and even more preferably less than 50 ppm.

[0084] Preferably, after storing the compositions of the invention for at least 1 day, or at least 2 days, or at least 3 days, or at least 4 days, or at least 5 days, or at least 6 days, or at least 7 days, or at least 30 days, or at least 60 days, or at least 120 days, or at least 365 days, the concentration of H2S as determined by gas chromatography headspace analysis is less than 300 ppm, preferably less than 200 ppm, more preferably less than 100 ppm, and even more preferably less than 50 ppm.

[0085] Preferably, after storage of the compositions of the invention between -20°C and 130°C, preferably between 0°C and 50°C, more preferably between 10°C and 40°C, even more preferably between 20°C and 30°C, the concentration of H2S as determined by gas chromatography headspace analysis is less than 300 ppm, preferably less than 200 ppm, more preferably less than 100 ppm, and even more preferably less than 50 ppm.

[0086] In some embodiments of the compositions according to the present invention, no rubber component is included because that is the form in which the compositions are typically used, manufactured and sold.

[0087] In a further embodiment of the composition according to the invention, one or more further additives are included, such as conventional rubber additives.

[0088] Manufacturing method In a further embodiment, the composition is prepared by a method for making a composition according to the invention, which includes at least one step of combining, contacting, or mixing components (a), (b) and / or (c).

[0089] In a further embodiment, the composition is prepared by a method for producing a composition according to the invention, (i) combining one or more sulfur-containing silanes (a) with at least one acid (c) and then with one or more organic compounds (b); or (ii) combining one or more organic compounds (b) with at least one acid (c) and then with one or more sulfur-containing silanes (a).

[0090] In some embodiments of the method for making a composition according to the present invention, components (a), (b) and (c) are contacted in a stirred vessel at a temperature suitable for mixing, preferably from about 10° C. to about 40° C., more preferably from about 20° C. to about 40° C., and even more preferably from about 20° C. to about 30° C., for up to about one hour, preferably up to half an hour.

[0091] In some embodiments of the process for preparing the composition according to the present invention, at least one acid (c) is added during the production of the sulfur-containing silane (a) or during the production of the organic compound (b) through unit operations such as raw material processing, mixing, reaction steps, washing steps, purification steps, filtration steps, heat treatment and post-treatment steps.

[0092] In a further aspect, the present invention relates to a method for reducing hydrogen sulfide release from a sulfur-containing silane composition, comprising the step of adding to the composition an effective amount of at least one acid selected from an acid having a pKa of less than 3.75, determined in aqueous solution at a temperature of 25° C., and a Lewis acid, each of which is as described above. In such a method of the present invention for reducing hydrogen sulfide release from a sulfur-containing silane composition, the acid is preferably added in an amount of about 0.01 to about 5 wt %, based on the total weight of the composition.

[0093] Use in rubber compositions In a further aspect, the present invention relates to the use of the composition according to the invention as an additive for rubber compositions containing a filler such as carbon black or silica, preferably silica.

[0094] Such rubber compositions preferably contain a filler such as silica and one or more compositions according to the invention and include, for example: (A) at least one diene-based polymer; (B) Fillers such as precipitated silica, preferably having a viscosity of 50 m, as determined by, for example, ISO 9277 2 / g or higher BET specific surface area; (C) at least one composition according to the invention as defined above; (D) at least one deblocking agent; (E) a vulcanization package comprising at least one vulcanizing agent comprising sulfur and at least one accelerator; and (F) at least one scorch modifier The rubber composition includes:

[0095] The at least one diene-based polymer (a) includes, for example, at least one diene-based polymer containing at least one functional group, a diene-based polymer not containing a functional group, and combinations thereof, or a combination of a diene-based polymer containing at least one functional group and a diene-based polymer not containing a functional group, or a diene-based polymer containing at least one functional group, which is at least one functional group selected from the group consisting of, for example, amino groups, alkoxysilyl groups, stanyl groups, hydroxyl groups, thiol groups, sulfide groups, thioisocyanate groups, isocyanate groups, imino groups, pyridino groups, epoxy groups, thioepoxy groups, thioketone groups, ketone groups, ketimine groups, isocyanuric acid groups, amide groups, silazano groups, hydroxysilyl (silanol) groups, siloxane groups, phthalocyanino groups, silane-sulfide groups, carboxylic acid groups, carboxylic acid ester groups, and combinations thereof.

[0096] The rubber composition comprises: (i) about 100 parts rubber, where the weight of rubber is the sum of the weight of each diene based polymer used in the formulation that contains at least one functional group and the sum of the weight of each diene based polymer used in the formulation that does not contain the at least one functional group; (ii) from about 5 to about 140 parts by weight of precipitated silica per 100 parts of rubber (i); (iii) from about 1 to about 20 parts by weight per 100 parts of rubber (i) of a composition of this invention as defined above; (iv) from about 0.1 to about 20 parts by weight per 100 parts of rubber (i) of a conventional deblocking agent; (v) from about 0.1 to about 10 parts by weight per 100 parts of rubber (i) of a vulcanization package comprising sulfur and at least one accelerator; and (vi) from about 0.1 to about 5 parts by weight per 100 parts of rubber (i) of a conventional scorch modifier; may include:

[0097] In a further aspect, the present invention relates to a vulcanized article made from the rubber composition according to the present invention.

[0098] explanation As used above, and throughout the detailed description, the following terms, unless otherwise stated, shall be understood to have the following meanings:

[0099] As used in this application, the term "about" encompasses the range of experimental error that occurs in any measurement.

[0100] The term "comprising" is understood to include three alternatives: (i) "comprising" or "including," where any additional, e.g., ingredients or method steps, can be present; (ii) "consisting of," where no additional, e.g., ingredients or method steps can be present; and (iii) "consisting essentially of," where, e.g., additional specified ingredients or method steps, e.g., which do not materially affect the essential characteristics of the composition or method, can be present.

[0101] Furthermore, as used herein, "and / or" is to be understood as a specific disclosure of all of the indicated components or features, or one or any combination of one or more components or features, e.g., a, b and / or c includes a, b, c, ab, ac, bc, and abc.

[0102] The expression "blocked mercaptosilane(s)" is understood to include partial hydrolysates, which may result from any process for their production and / or may arise during storage, especially under humid conditions.

[0103] The term "filler" refers to substances added to diene-based polymers (rubbers) to increase the weight of the rubber or to reinforce the elastomeric network. Reinforcing fillers are materials that have a higher modulus than the diene-based polymer of the elastomeric composition and can absorb stress from the diene-based polymer when the elastomer is strained. Fillers include fibers, needles, nanotubes, particles, and sheet-like structures and can be composed of inorganic minerals, silicates, silica, clays, ceramics, carbon, organic polymers, and diatomaceous earth.

[0104] The term "organic," as in "organic group" or "organic compound," refers to any chemical structure that contains one or more carbon atoms, hydrogen, and optionally one or more heteroatoms, such as N, O, S, Si, P, B, etc.

[0105] As used herein, the term "hydrocarbon" or "hydrocarbyl group" refers to any chemical structure containing hydrogen and carbon atoms, and optionally one or more heteroatoms, such as N, O, S, Si, P, B, etc.

[0106] As used herein, "alkyl" preferably includes straight-chain, branched-chain, and cyclic, substituted or unsubstituted alkyl groups; "alkenyl" preferably includes any straight-chain, branched-chain, or cyclic, substituted or unsubstituted alkyl group containing one or more carbon-carbon double bonds, where the alkenyl group contains one or more carbon-carbon double bonds and the substitution positions can be at the carbon-carbon double bonds or elsewhere in the group; and "alkynyl" preferably includes any straight-chain, branched-chain, or cyclic, substituted or unsubstituted alkyl group, where the alkynyl group contains one or more carbon-carbon triple bonds and optionally one or more carbon-carbon double bonds and the substitution positions can be at the carbon-carbon triple bonds, carbon-carbon double bonds, or elsewhere in the group.

[0107] Specific, non-limiting examples of substituted or unsubstituted alkyl groups include methyl, ethyl, propyl, and isobutyl groups, as well as halogenated alkyl groups. Specific, non-limiting examples of alkenyls include vinyl, propenyl, allyl, and methallyl. Specific, non-limiting examples of alkynyls include acetylenyl, propargyl, and methylacetylenyl.

[0108] As used herein, "aryl" or "aromatic group" includes any substituted or unsubstituted aromatic hydrocarbon with one hydrogen atom removed; "aralkyl" includes any alkyl group as described above with one or more hydrogen atoms replaced with an equal number of similar and / or different aryl (as defined herein) substituents; and "allenyl" includes any aryl group as described above with one or more hydrogen atoms replaced with an equal number of similar and / or different alkyl (as defined herein) substituents. Specific non-limiting examples of aryl groups include phenyl and naphthalenyl. Specific non-limiting examples of aralkyl groups include benzyl and phenethyl. Specific non-limiting examples of arenyl groups include tolyl and xylyl.

[0109] As used herein, "alkylene" means a substituted or unsubstituted divalent saturated aliphatic radical derived by removing two hydrogen atoms from an alkane.

[0110] Optional substituents on organic groups, such as aromatic or aliphatic groups, may include halogens, such as F, Cl, Br, I, hydroxy, alkoxy, acyl, amino, and the like.

[0111] Other than in the examples, or unless otherwise noted, all numbers expressing quantities of ingredients, reaction conditions, lengths of time, quantified properties of substances, and the like described in the specification and claims are understood to be modified in all instances by the term "about."

[0112] Any numerical range recited herein is understood to include all subranges within that range, and any combination of the various endpoints of that range or subrange.

[0113] Furthermore, all compounds, materials or substances explicitly or implicitly disclosed and / or claimed herein as belonging to a group of structurally, compositionally and / or functionally related compounds, materials or substances are understood to include the individual members of that group and all combinations thereof.

[0114] The invention may be better understood by reference to the following examples, in which parts and percentages are by weight unless otherwise specified.

[0115] Preferred Embodiments of the Invention In the following preferred embodiments of the present invention are described.

[0116] 1. A composition comprising: (a) one or more sulfur-containing silanes having no (free) mercapto (HS-) functionality; (b) one or more organic compounds with (free) mercapto (HS-) functionality; (c) at least one acid selected from (c1), an acid having a pKa, determined in aqueous solution at a temperature of 25° C., of less than 3.75, and one or more Lewis acids (c2); A composition comprising:

[0117] 2. The composition according to embodiment 1, further comprising (d) one or more sulfur-free silanes.

[0118] 3. A composition according to any of the previous embodiments, wherein the sulfur-containing silane (a) having no mercapto (HS-) functionality is selected from the group consisting of blocked mercaptosilanes, organosilane polysulfides, and mixtures thereof.

[0119] 4. A composition according to any of the previous embodiments, wherein the sulfur-containing silane (a) having no mercapto (HS-) functionality is selected from blocked mercaptosilanes.

[0120] 5. A composition according to any of the previous embodiments, wherein the sulfur-containing silane (a) having no mercapto (HS-) functionality is selected from the group consisting of blocked mercaptosilanes having blocked thiol and alkoxysilane functionality.

[0121] 6. A composition according to any of the previous embodiments, wherein the sulfur-containing silane (a) having no mercapto (HS-) functionality is selected from blocked mercapto-functional alkylalkoxysilanes.

[0122] 7. A composition according to any of the previous embodiments, wherein the organic compound (b) with mercapto (HS-) functionality is selected from the group consisting of mercaptosilanes and organic mercapto compounds not containing a silane moiety, such as alkyl mercaptans, such as n-octyl mercaptan or tert-dodecanethiol, thioglycolic acid, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, pentaerythritol tetrakis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), and the like, having the formula HS(CH) n They are selected from aromatic and heteroaromatic mercapto compounds such as mercapto acids and their esters having COOH and n=1 to 5, hydroxyalkyl mercapto compounds, for example thioglycerol, 1,3-dimercapto-2-propanol, or mercapto-2-benzothiazole.

[0123] 8. A composition according to any of the previous embodiments, wherein the organic compound (b) with mercapto (HS-) functionality is selected from the group consisting of mercaptosilanes, such as difunctional silanes having thiol and alkoxysilane functionality.

[0124] 9. A composition according to any of the previous embodiments, wherein the organic compound (b) with mercapto (HS-) functionality is selected from mercapto-functional alkylalkoxysilanes.

[0125] 10. A composition according to any of the previous embodiments, wherein at least one acid (c) is selected from acids (c1) having a pKa, determined in aqueous solution at a temperature of 25° C., of less than 3.75.

[0126] 11. A composition according to any of the previous embodiments, wherein at least one acid (c) is selected from Lewis acids (c2).

[0127] 12. A composition according to any of the previous embodiments, wherein the acid (c), which is an acid having a pKa of less than 3.75 as determined in aqueous solution at a temperature of 25° C., is selected from the group consisting of protic acids, such as inorganic acids, organic acids, and mixtures thereof.

[0128] 13. A composition according to any of the previous embodiments, wherein acid (c), an acid having a pKa of less than 3.75 determined in aqueous solution at a temperature of 25° C., is formed in situ through the addition of a hydrolyzable compound, which reacts with residual water present in the components of the composition to form the acid.

[0129] 14. A composition according to any of the previous embodiments, wherein the acid (c), which is an acid having a pKa of less than 3.75 determined in aqueous solution at a temperature of 25° C., is formed in situ through the addition of a hydrolyzable compound selected from the group consisting of an acid anhydride such as maleic anhydride, methanesulfonic anhydride, a borane halide such as dichlorophenylborane, dibutylboron trifluoromethanesulfonate, a trialkylsilane halide such as chlorotrimethylsilane or a silane halide such as (3-chloropropyl)trichlorosilane, a 1-chloroacyl halide such as an alkanoyl halide such as octanoyl chloride, a sulfonyl halide such as methanesulfonyl chloride, a benzyl halide such as benzyl chloride, a halohydrin or epihalohydrin such as epichlorohydrin, and a sulfenyl chloride, a sulfuryl or thionyl chloride, a phosphoryl chloride, and a dimethylmethylphosphonate.

[0130] 15. A composition according to any of the previous embodiments, wherein the acid (c) is a Lewis acid (c2), preferably selected from the group consisting of lithium (Li) and alkali metals, beryllium (Be), magnesium (Mg) and alkaline earth metals, boron (B), aluminum (Al), silicon (Si), tin (Sn), elements of the d block of the periodic table, such as scandium (Sc), titanium (Ti), vanadium (V), manganese (Mn), chromium (Cr), iron (Fe), cobalt (Co), and zinc (Zn), lanthanum (La) and compounds of the lanthanides, and combinations thereof, preferably the Lewis acid (c2) is an organoboron or organotitanium compound.

[0131] 16. A composition according to any of the previous embodiments, wherein the sulfur-containing silane (a) having no mercapto (HS-) functionality is selected from the group consisting of blocked mercaptosilanes of formula (I): [ka] During the ceremony R 1 independently a straight chain alkylene group of 1 to 6 carbon atoms or a branched chain alkylene group of 3 to 6 carbon atoms; R 2 each of which is a straight chain alkylene group of from 2 to 8 carbon atoms or a branched chain alkylene group of from 3 to 8 carbon atoms; R 3 each independently is a straight chain alkylene group of 1 to 6 carbon atoms or a branched chain alkylene group of 3 to 6 carbon atoms; X 1 -OR 4 Group, where R 4 is an alkyl group of 1 to 4 carbon atoms, -OR 5 OH group, where R 5 is a straight chain alkylene group having 2 to 8 carbon atoms or a branched chain alkylene group having 3 to 8 carbon atoms, or X 1 -OR 6 (OR 7 )cOR 8 , where R 6is a linear alkylene group having 2 to 6 carbon atoms or a branched alkylene group having 3 to 6 carbon atoms, preferably 3 carbon atoms; R 7 each independently represents an alkylene group of 2 to 4 carbon atoms, and R 8 is a straight chain alkyl group of 1 to 16 carbon atoms or a branched chain alkyl group of 3 to 16 carbon atoms, and c is an integer from 1 to 20; X 2 and X 3 is independent of X 1 or methyl; X 4 Each of X is independent. 1 or methyl; Y 1 Each of these is -C(=O)R 9 , -C(=S)OR 9 or -CN, where R 9 each is independently a straight chain alkylene group of 1 to 16 carbon atoms, more preferably 5 to 11 carbon atoms, and even more preferably 6 to 9 carbon atoms, or a branched chain alkylene group of 3 to 16 carbon atoms, more preferably 5 to 11 carbon atoms, and even more preferably 6 to 9 carbon atoms; and a is an integer from 0 to 8, with the proviso that (iii) X 1 and X 2 -OR 4 In the case of two -OR 4 are bonded to each other via covalent bonds to form a ring structure containing two oxygen atoms and a silicon atom bonded to the same silicon atom, -OR 4 -R 4 may form O-groups; (iv) a is 1 to 8 and X 3 and X 4 -OR 4 In the case of two -OR 4 The groups are bonded to each other through covalent bonds and to the same silicon atom to form a ring structure containing two oxygen atoms and a silicon atom, -OR 4 -R 4 An O-group may be formed.

[0132] 17. A composition according to any of the previous embodiments, wherein the sulfur-containing silane (a) having no mercapto (HS-) functionality is selected from the group consisting of blocked mercaptosilanes of formula (XI), R 1 is a linear alkylene group having 1 to 6 carbon atoms or a branched alkylene group having 3 to 6 carbon atoms; Y 1 is -C(=O)R 9 , -C(=S)OR 9 or -CN, where R 9 each independently represents a straight chain alkylene group of 1 to 16 carbon atoms, more preferably 5 to 11 carbon atoms, and even more preferably 6 to 9 carbon atoms, or a branched chain alkylene group of 3 to 16 carbon atoms, more preferably 5 to 11 carbon atoms, and even more preferably 6 to 9 carbon atoms; X 1 -OR 4 Group, where R 4 is an alkyl group of 1 to 4 carbon atoms, X 2 and X 3 is independent of X 1 or methyl, and a is 0.

[0133] 18. A composition according to any of the previous embodiments, wherein the sulfur-containing silane (a) having no mercapto (HS-) functionality is selected from the group consisting of blocked mercaptosilanes of formula (I), R 1 are independently a linear alkylene group having 1 to 6 carbon atoms or a branched alkylene group having 3 to 6 carbon atoms; R 2 each of R is a straight chain alkylene group of 2 to 8 carbon atoms or a branched chain alkylene group of 3 to 8 carbon atoms; 3 each independently represents a straight chain alkylene group of 1 to 6 carbon atoms or a branched chain alkylene group of 3 to 6 carbon atoms; Y 1 is -C(=O)R 9 , -C(=S)OR 9 or -CN, where R 9each independently represents a straight chain alkylene group of 1 to 16 carbon atoms, more preferably 5 to 11 carbon atoms, and even more preferably 6 to 9 carbon atoms, or a branched chain alkylene group of 3 to 16 carbon atoms, more preferably 5 to 11 carbon atoms, and even more preferably 6 to 9 carbon atoms; X 1 and X 2 -OR 4 , where R 4 is an alkyl group of 1 to 4 carbon atoms; 1 and X 2 Two-OR 4 The groups are bonded to each other through covalent bonds to form a ring structure that is bonded to the same silicon atom and contains 2 to 8 carbon atoms, 2 oxygen atoms, and a silicon atom, -OR 4 -R 4 forming an O-group; or X 1 and X 2 Each of -OR 5 OH group, where R 5 is a linear alkylene group having 2 to 8 carbon atoms or a branched alkylene group having 3 to 8 carbon atoms; X 3 and X 4 are independent -OR 4 is a group, where R 4 is an alkyl group of 1 to 4 carbon atoms, -OR 5 OH group, where R 5 is a straight chain alkylene group having 2 to 8 carbon atoms or a branched chain alkylene group having 3 to 8 carbon atoms, provided that X 3 and X 4 -OR 4 If it is, then two -OR 4 The groups are bonded to each other through covalent bonds to form a ring structure that is bonded to the same silicon atom and contains 2 to 8 carbon atoms, 2 oxygen atoms, and a silicon atom, -OR 4 -R 4 O-groups may be formed, where a is 1 to 8, preferably 1 to 3.

[0134] 19. A composition according to any of the previous embodiments, wherein the sulfur-containing silane (a) having no mercapto (HS-) functionality is selected from the group consisting of triethoxysilylmethyl thioformate, 2-triethoxysilylethyl thioacetate, 3-triethoxysilylpropyl thiopropanoate, 3-triethoxysilylpropyl thiohexanoate, 3-triethoxysilylpropyl thio-(2-ethyl)-hexanoate, 3-triethoxysilylpropyl thiooctanoate, 3-diethoxymethylsilylpropyl thiooctanoate, 3-triethoxy ... Silylpropylthiooctanoate, 3-ethoxydimethylsilylpropylthiooctanoate, 3-triethoxysilylpropylthiododecanoate, 3-triethoxysilylpropylthiooctadecanoate, 3-trimethoxysilylpropylthiooctanoate, 3-triacetoxysilylpropylthioacetate, 3-dipropoxymethylsilylpropylthiopropanoate, 4-oxa-hexyloxydimethylsilylpropylthiooctanoate, 3-(2-{3-[2-(4-thia-5-oxo-dodecyl)-5-methyl 3-(2-{3-[2-(4-thia-5-oxo-dodecyl)-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy}-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yl)-4-thia-5-oxo-dodecane;3-(2-{3-[2-(4-thia-5-oxo-dodecyl)-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy}-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yl)-4-thia-5-oxo-dodecane;3-(2-{3-[2-(4- thia-5-oxo-dodecyl)-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yloxy]-1,1-dimethyl-butoxy}-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yl)-4-thia-5-oxo-dodecane;3-({3-[2-thia-3-oxo-decyl)-5-methyl-[1,3,2]dioxasilinan-yloxy]-2-methyl-propoxy}-bis-[3-hydroxy-2-methyl-propoxy]-silanyl)-2-thia-3-oxo-decane;3-[{3-[{3-bis-(3-hydroxy-2-methyl-propyl)-(4-thia-5-oxo-dodecyl)-silanyloxy]-1-methyl-propoxy}-(3-hydroxy-2-methyl-propoxy)-(4-thia-5-oxo-dodecyl)-silanyloxy]-2-methyl-propan-1-ol;3-[[3-((3-hydroxy-3-methyl-propoxy)-4-thia-5-oxo-dodecyl)-{3-[2-(4-thia-5-oxo-dodecyl)-5-methyl-[1,3, 2]dioxasilinan-2-yloxy]-1-methyl-propoxy}-silanyloxy)-2-methyl-propoxy-(3-hydroxy-2-methyl-propoxy)-4-thia-5-oxo-dodecyl)-silanyl]-2-methylpropan-1-ol;3-(2-{3-[2-(4-thia-5-oxo-6-ethyl-decyl)-[1,3,2]dioxasilinan-2-yloxy]-propoxy}-[1,3,2]dioxasilinan-2-yl)-4-thia-5-oxo-6-ethyl-decyl 3-({3-[2-thia-3-oxo-octyl)-5-methyl-[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy}-diethoxy]-silanyl)-2-thia-3-oxo-octane;3-[{3-[{3-bis-(3-hydroxy-2,2-dimethyl-propyl)-(4-thia-5-oxo-dodecyl)-silanyloxy]-2,2-dimethyl-propoxy}-(3-hydroxy-2,2-dimethyl-propoxy)-(4-thia-5-oxo-dodecyl) -silanyloxy]-2,2-dimethyl-propan-1-ol; 3-[{3-[(methyl)-(3-hydroxy-2-methyl-propoxy)-(4-thia-5-oxo-dodecyl)-silanyloxy]-2-methyl-propoxy}-methyl)-(4-thia-5-oxo-dodecyl)-silanyloxy]-2-methyl-propan-1-ol, 3-(triethoxysilyl)propyl thiocyanate, and combinations thereof;

[0135] 20. A composition according to any of the previous embodiments, wherein the sulfur-containing silane (a) having no mercapto (HS-) functionality is 3-octanoylthio-1-propyltriethoxysilane (3-triethoxysilylpropylthiooctanoate).

[0136] 21. A composition according to any of the previous embodiments, wherein the sulfur-containing silane (a) having no mercapto (HS-) functional components has at least one polysulfide moiety, -S. x -, where x is an average value of from about 2 to about 12, preferably from about 2 to about 10, more preferably from about 2 to about 8, more preferably from about 2 to about 6, more preferably from about 2 to about 4, more preferably about 2 or about 4.

[0137] 22. A composition according to any of the previous embodiments, wherein the component without mercapto (HS-) functionality, the sulfur-containing silane (a), is selected from formula (II): [ka] During the ceremony R 1 is a linear alkylene group of 1 to 6 carbon atoms or a branched alkylene group of 3 to 6 carbon atoms, preferably 3 carbon atoms; X 1 , X 2 and X 3 are each independently as defined above, preferably each is ethoxy, x is as defined above, and preferably x is about 2 or about 4.

[0138] 23. A composition according to any of the previous embodiments, wherein the sulfur-containing silane (a) is selected from the group consisting of bis-3-triethoxysilylpropyl disulfide, bis-triethoxysilylpropyl tetrasulfide, and 3-octanoylthio-1-propyltriethoxysilane.

[0139] 24. A composition according to any of the previous embodiments, wherein the sulfur-containing silane (a) forms a major component relative to other components, based on the weight of the components in the composition.

[0140] 25. A composition according to any of the previous embodiments, wherein the sulfur-containing silane (a) comprises greater than 50% by weight of the total composition.

[0141] 26. A composition according to any of the previous embodiments, wherein the organic compound (b) with mercapto (HS-) functionality is selected from mercaptosilanes of formula (III): [ka] During the ceremony R 1 are each independently as defined above; R 2 each independently as defined above; R 3 each independently as defined above; X 1 , X 2 , X 3 and X 4 are, independently of one another, as defined above, and a is as defined above.

[0142] 27. A composition according to any of the previous embodiments, wherein the organic compound (b) with mercapto (HS-) functionality is selected from mercaptosilanes of formula (III): During the ceremony R 1 is a linear alkylene group having 1 to 6 carbon atoms or a branched alkylene group having 3 to 6 carbon atoms; X 1 -OR 4 Group, where R 4 is an alkyl group of 1 to 4 carbon atoms, X 2 and X 3 is independent of X 1 or methyl, and a is 0.

[0143] 28. A composition according to any of the previous embodiments, wherein the organic compound (b) with mercapto (HS-) functionality is selected from mercaptosilanes of formula (III): During the ceremony R 1 are independently a linear alkylene group having 1 to 6 carbon atoms or a branched alkylene group having 3 to 6 carbon atoms; R 2 each of R is a straight chain alkylene group of 2 to 8 carbon atoms or a branched chain alkylene group of 3 to 8 carbon atoms; 3 each independently represents a straight chain alkylene group of 1 to 6 carbon atoms or a branched chain alkylene group of 3 to 6 carbon atoms; 1 and X 2 -OR 4 , where R 4 is an alkyl group of 1 to 4 carbon atoms; 1 and X 2 Two-OR 4 The groups are bonded to each other through covalent bonds to form a ring structure that is bonded to the same silicon atom and contains 2 to 8 carbon atoms, 2 oxygen atoms, and a silicon atom, -OR 4 -R 4 Forming an O-group or X 1 and X 2 Each of -OR 5 OH group, where R 5 is a linear alkylene group having 2 to 8 carbon atoms or a branched alkylene group having 3 to 8 carbon atoms; X 3 and X 4 are independent -OR 4 Group, where R 4 is an alkyl group of 1 to 4 carbon atoms, -OR 5 OH group, where R 5 is a straight chain alkylene group having 2 to 8 carbon atoms or a branched chain alkylene group having 3 to 8 carbon atoms, provided that X 3 and X 4 -OR 4 In the case of two -OR 4 are bonded to each other via covalent bonds to form a ring structure containing two oxygen atoms and a silicon atom bonded to the same silicon atom, -OR 4 -R 4O-groups may be formed, where a is 1 to 8, preferably 1 to 3.

[0144] 29. A composition according to any of the previous embodiments, wherein the organic compound (b) having mercapto (HS-) functionality is selected from the group consisting of 3-mercapto-1-propyltriethoxysilane, 2-mercapto-1-ethyltriethoxysilane, mercaptomethyltriethoxysilane, 6-mercapto-1-hexyltriethoxysilane, 4-mercapto-1-butyltriethoxysilane, 1-mercapto-1-ethyltriethoxysilane, 3-mercapto-1-propylmethyldiethoxysilane, 3-mercapto-1-propyldimethylethoxysilane, 4-mercapto-1-propyltriethoxysilane, 5-mercapto-1-propyltriethoxysilane, 6-mercapto-1-hexyltriethoxysilane, 7-mercapto-1-propyltriethoxysilane, 8-mercapto-1-propyltriethoxysilane, 9-mercapto-1-propyltriethoxysilane, 10-mercapto-1-propyltriethoxysilane, 11-mercapto-1-propyltriethoxysilane, 12-mercapto-1-propyltriethoxysilane, 13-mercapto-1-propyltriethoxysilane, 14-mercapto-1-propyltriethoxysilane, 15-mercapto-1-propyltriethoxysilane, 16-mercapto-1-propyltriethoxysilane, 17-mercapto-1-propyltriethoxysilane, 18-mercapto-1-propyltriethoxysilane, 19-mercapto-1-propyltriethoxysilane, 20-mercapto-1-propyltriethoxysilane, 21-mercapto-1-propyltriethoxysilane, 22-mercapto-1-ethyltriethoxysilane, 23-mercapto-1-propyltriethoxysilane, 24-mercapto-1-propyltrieth Silane, 3-mercapto-1-propyltrimethoxysilane, 2-mercapto-1-ethyltrimethoxysilane, mercaptomethyltrimethoxysilane, 6-mercapto-1-hexyltrimethoxysilane, 4-mercapto-1-butyltrimethoxysilane, 1-mercapto-1-ethyltrimethoxysilane, 3-mercapto-1-propylmethyldimethoxysilane, 3-mercapto-1-propyldimethylmethoxysilane, 3-mercapto-1-propyltripropoxysilane, 3-mercapto-1-propyltriisopropyl propyloxysilane, 3-mercapto-1-propyltributoxysilane, 4-(3,6,9,12,15-penta-oxaoctacosyloxy)-4-ethoxy-5,8,11,14,17,20-hexaoxa-4-silatritriacontane-1-thiol, 3-(2-{3-[2-(3-mercapto-propyl)-5-methyl-[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy}-5-methyl-[1,3,2]dioxasilinan-2-yl)-propane-1-thiol; 3-(2-{3-[ 2-(3-mercapto-propyl)-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy}-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yl)-propane-thiol;3-(2-{3-[2-(3-mercapto-propyl)-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yloxy]-1,1-dimethyl-butoxy}-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yl)-propane-1-thiol;3-({3-[2-mercapto-propyl)-5-methyl-[1,3,2]dioxasilinane-yloxy]-2-methyl-propoxy}-bis-[3-hydroxy-2-methyl-propoxy]-silanyl)-propane-1-thiol;3-[{3-[{3-bis-(3-hydroxy-2-methyl-propyl)-(3-mercapto-propyl)-silanyloxy]-1-methyl-propoxy}-(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-silanyloxy]-2-methyl-propane -1-ol;3-[[3-((3-hydroxy-3-methyl-propoxy)-3-mercapto-propyl)-{3-[2-(3-mercapto-propyl)-5-methyl-[1,3,2]dioxasilinan-2-yloxy]-1-methyl-propoxy}-silanyloxy)-methyl-propoxy-(3-hydroxy-2-methyl-propoxy)-3-mercapto-propyl)-silanyl]-2-methylpropan-1-ol;3-(2-{3-[2-(3-mercapto-butyl) ... 3-({3-[2-mercapto-methyl)-5-methyl-[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy}-diethoxy]-silanyl)-methane-1-thiol;3-[{3-[{3-bis-(3-hydroxy-2,2-dimethyl-propyl)-(3-mercapto-propyl)-silanyloxy]-2,2-dimethyl-propoxy}-(3-hydroxy-2,2-dimethyl-propoxy) )-(3-mercapto-propyl)-silanyloxy]-2,2-dimethyl-propan-1-ol; 3-[{3-[(methyl)-(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-silanyloxy]-2-methyl-propoxy}-methyl)-(3-mercapto-propyl)-silanyloxy]-2-methyl-propan-1-ol, 3-mercaptopropyl-ethyoxyl-di(tridecyl-pentamethoxy)-silane and combinations thereof.;

[0145] 30. A composition according to any of the previous embodiments, wherein the organic compound (b) having mercapto (HS-) functionality is selected from the group of mercaptosilanes consisting of 3-mercapto-1-propyltriethoxysilane, and 4-(3,6,9,12,15-penta-oxaoctacosyloxy)-4-ethoxy-5,8,11,14,17,20-hexaoxa-4-silatritriacontane-1-thiol.

[0146] 31. A composition according to any of the previous embodiments, wherein the acid (c) is selected from inorganic protonic acids and organic protonic acids, preferably from organic acids such as carboxylic acids, organic sulfonic acids, organic sulfinic acids, organic phosphinic acids, and organic phosphoric acids.

[0147] 32. A composition according to any of the previous embodiments, wherein the acid (c) is selected from the group consisting of formula (IV): H p E q O r (IV) During the ceremony p is ≧1, preferably 1 to 4; q is ≧1, preferably 1 to 3; r is 0 to 6, preferably 0 to 4; E is independently Ti, Mo, W, Cr, Mn, Tc, Re, Fe, Ru, Os, B, C, Si, Sb, CN, CNO, SCN, N, P, As, Te, S, Se, F, Cl, Br or I.

[0148] 33. A composition according to any of the previous embodiments, wherein the acid (c) is selected from the group consisting of organic acids having at least one acidic functional group, preferably a functional group selected from the following group: -C(=O)(-OH); -C(=S)(-OH); -S(=O)2(-OH); -OS(=O)2(-OH); -S(=O)(-OH); -OS(=O)(-OH); (-O)2P(=O)(-OH); -OP(=O)(-OH); -OP(=O)2(-OH); -ON(=O)(-OH), and Preferred is a carboxylic acid group (-C(=O)(-OH)-) or a sulfonic acid group (-S(=O)2(-OH)).

[0149] 34. A composition according to any of the previous embodiments, wherein the acid (c) is a carboxylic acid having attached as a substituent an organic group such as an alkyl group, a haloalkyl group, a perfluoroalkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, or an optionally substituted alkyl group containing a halide such as F, Cl, Br, I, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, a nitro group, a cyano group, a thiocyano group, a hydroxy group, a sulfhydryl group, an alkoxy group, an alkylthio or arylthio group, an acyl group, a carboxylate or carboxylic acid group, a sulfonate or sulfonic acid group, and a phosphate or phosphate group. , sulfonic acids, sulfinic acids, phosphonic acids, and phosphinic acids, preferably chlorosulfonic acid, trifluoromethanesulfonic acid, perfluorobutyric acid, methanesulfonic acid, benzenesulfinic acid, trifluoroacetic acid, dichloroacetic acid, chloroacetic acid, 2-bromobenzoic acid, 4-dodecylbenzenesulfonic acid, octylphosphonic acid, 12-mercaptododecylphosphonic acid, oxalic acid, pyruvic acid, 3-oxobutanoic acid, maleic acid or fumaric acid, 2,3-dihydroxypropanoic acid, citric acid, tartaric acid, cis or trans-1,2-cyclopropanedicarboxylic acid, and terephthalic acid, and combinations thereof.

[0150] 35. A composition according to any of the previous embodiments, further comprising one or more acids with 3.75≦pKa≦7, such as acetic acid.

[0151] 36. A composition according to any of the previous embodiments, wherein the pH of the hydroalcoholic solution at 25° C. is less than about 7, preferably between about 3 and about 7, more preferably between about 4 and about 6, and even more preferably between about 5 and about 6.

[0152] 37. A composition according to any of the previous embodiments, from about 5 to about 95% by weight, preferably from about 50 to about 95% by weight, of one or more sulfur-containing silanes (a); from about 5 to about 95% by weight, preferably from about 5 to about 50% by weight, of one or more organic compounds (b); and from about 0.01 to about 5% by weight, preferably from about 0.01 to about 2% by weight, more preferably from about 0.01 to about 1% by weight, even more preferably from about 0.01 to about 0.1% by weight of at least one acid (c); or The acid (c) is used in an amount of about 0.01 to about 5% by weight, preferably of about 0.01 to about 4% by weight, more preferably of about 0.01 to about 3% by weight, more preferably of about 0.01 to about 2% by weight, more preferably of about 0.01 to about 1% by weight, more preferably of about 0.01 to about 0.5% by weight, and more preferably of about 0.01 to about 0.1% by weight, each percentage being based on the total weight of the composition.

[0153] 38. A composition according to any of the previous embodiments, wherein the weight ratio of compound (a) to compound (b) is from about >1:1 to about 50:1 w / w, preferably from about 50 / 50 w / w to about 90 / 10, more preferably from about 60 / 40 to about 80 / 20, even more preferably from about 70 / 30 to about 80 / 20, and most preferably 75 / 25 w / w.

[0154] 39. A composition according to any of the previous embodiments, wherein the weight ratio of compound (a) to compound (b) is - From about 75 to about 25, - from about 4.8 to about 1.6, - about 7 to about 0.35, - Approximately 6.25 to approximately 0.7, -About 5.75 to about 1, - from about 5.2 to about 1.3, - about 4.4 to about 1.9, - about 3.6 to about 2.4, - from about 3 to about 1, or - selected from about 2.85 to about 3.15.

[0155] 40. A composition according to any of the previous embodiments, wherein the concentration of H2S as determined by gas chromatography headspace analysis is less than 300 ppm, preferably less than 200 ppm, more preferably less than 100 ppm, and even more preferably less than 50 ppm.

[0156] 41. A composition according to any of the previous embodiments, wherein the acid (c) is used in a form having a concentration of at least about 30% by weight, preferably at least about 50% by weight, more preferably at least about 70% by weight, more preferably at least about 90% by weight, and even more preferably at least about 98% by weight, based on the total weight of the acid, with the remainder preferably being water.

[0157] 42. A composition according to any of the previous embodiments, wherein the acid (c) is used in a form having a concentration of about 50% to about 99% by weight, wherein the water content is up to 2% by weight, preferably up to 0.1% by weight, and the remainder is another component, preferably selected from a solvent, an oil, an acid other than component (c), an acid anhydride, and an acid ester.

[0158] 43. A composition according to any of the previous embodiments, which does not include a rubber component.

[0159] 44. A method for producing a composition according to any of the previous embodiments, comprising at least one step of combining or contacting components (a), (b) and / or (c).

[0160] 45. A method of making a composition according to any of the previous embodiments, comprising: (i) combining one or more sulfur-containing silanes (a) with at least one acid (c) and then with one or more organic compounds (b); or (ii) combining one or more organic compounds (b) with at least one acid (c) and then with one or more sulfur-containing silanes (a).

[0161] 46. ​​A method for preparing a composition according to any of the previous embodiments, wherein components (a), (b) and (c) are contacted in a stirred vessel at a temperature suitable for mixing, preferably from about 20° C. to about 40° C., for up to half an hour.

[0162] 47. A method for producing a composition according to the previous embodiment, wherein at least one acid (c) is added during the production of the sulfur-containing silane (a) or during the production of the organic compound (b) through unit operations including raw material processing, mixing, reaction steps, washing steps, purification steps, filtration steps, heat treatment and post-treatment steps.

[0163] 48. A method for reducing hydrogen sulfide emissions from a sulfur-containing silane composition, comprising the step of adding to the composition an effective amount of at least one acid (c2) selected from acids having a pKa of less than 3.75, determined in aqueous solution at a temperature of 25° C., and Lewis acids.

[0164] 49. A method for reducing hydrogen sulfide emissions from a sulfur-containing silane composition according to the previous embodiment, wherein the acid is added at least one acid (c) in an amount of about 0.01 to about 5 wt. %, preferably about 0.01 to about 2 wt. %, more preferably about 0.01 to about 1 wt. %, and even more preferably about 0.01 to about 0.1 wt. %, based on the total weight of the composition.

[0165] 50. A composition according to any of the previous embodiments, further comprising one or more additives, such as a rubber additive.

[0166] 51. Use of a composition according to any of the previous embodiments as an additive for a rubber composition comprising a filler such as carbon black or silica, preferably silica.

[0167] 52. A rubber composition comprising silica and one or more compositions according to any of the previous embodiments.

[0168] 53. A rubber composition according to the previous embodiment, comprising: (A) at least one diene-based polymer; (B) Preferably, 50 m as determined by, for example, ISO 9277 2 / g or higher BET specific surface area; precipitated silica; (C) at least one composition as defined above; (D) at least one deblocking agent; (E) a vulcanization package comprising at least one vulcanizing agent comprising sulfur and at least one accelerator; and (F) at least one scorch modifier.

[0169] 54. A vulcanized article made from the rubber composition of the previous embodiment.

[0170] Working Example method The composition of the silane raw materials and the blend compositions were determined by gas chromatography (GC). The chemical structures were confirmed by mass spectrometry (GC-MS). Heptadecane (CAS#629-78-7) from Sigma-Aldrich was used as an internal standard.

[0171] The amount of H2S evolved from neat (solvent-free) silane or blends of silanes was determined by GC-headspace (GC-HS) analysis (hereafter referred to as "H2S-HS"). A 5 g sample of the composition was weighed and sealed in a suitable vial, preferably a 20 mL long-neck glass headspace vial, heated to 50°C for 1 hour, and the gas in the headspace of the vial was sampled, injected, and measured using an automated sequence.

[0172] The pH of the hydroalcoholic solution of the acid-doped silane blend was measured at room temperature (25°C) preferably by using a pH meter including a pH-sensitive glass electrode and a silver / silver chloride electrode as a reference electrode. First, a 2:1 volumetric ratio solution of isopropanol and deionized water was prepared and 60 mL was poured into a beaker. The pH was adjusted to 7 using 0.01 M aqueous NaOH and 0.01 M aqueous HCl. Then, 10 g of the silane blend was dissolved in the hydroalcoholic solution with stirring, and the pH was then measured.

[0173] Case 1 A 75 wt% (3-octanoylthio-1-propyltriethoxysilane, abbreviated as OTPTES):25 wt% (mercaptopropyltriethoxysilane, abbreviated as MPTES) blend was prepared by placing 3.75 g of OTPTES and 1.25 g of MPTES in a 20 mL vial suitable for GC-HS analysis. Each vial was sealed and then agitated for 5 min at 300 rpm using an orbital shaker.

[0174] The ternary blend OTPTES / MPTES / DBSA (3-octanoylthio-1-propyltriethoxysilane / mercaptopropyltriethoxysilane / DBSA (4-dodecylbenzenesulfonic acid)) according to the present invention was prepared by first adding DBSA at different weight percentages relative to the total mass of the ternary blend to a 40 mL glass vial containing OTPTES in an amount equal to 75% by weight of the OTPTES / MPTES silane blend. The vial was sealed and then agitated for 5 minutes at 300 rpm using an orbital shaker. Then, MPTES in an amount equal to 25% by weight of the OTPTES / MPTES silane blend was added to the same vial containing the acidified OTPTES. The vial was sealed and again agitated for 5 minutes at 300 rpm using an orbital shaker. In a typical experiment targeting DBSA at 0.1 wt% of the total mass of the ternary blend, 0.03 g of DBSA was added to 22.48 g of OTPTES, and then 7.49 g of MPTES was added to the acidified OTPTES, following the procedure described above. For each blend containing different percentages of DBSA, the pH of the hydroalcoholic solution was measured and GC analysis was performed. Then, 5 g samples from each blend were taken in 20 mL vials suitable for GC-HS analysis, the vials were sealed, and the samples were aged in an oven at 50 °C for 7 to 30 days. Both the freshly prepared samples and the aged samples were subjected to GC-HS and GC analysis. As a control, similar data was collected for both the starting silanes, OTPTES and MPTES. In this case, 5 g of the silane was used for GC-HS analysis.

[0175] Table 1 shows the effect of adding a strong sulfonic acid such as DBSA to mitigate H2S release from a silane blend of 75 wt% OTPTES:25 wt% MPTES (see Runs 1 and 2), while the mercapto-rich 75:25 w / w blend increases H2S-HS from 261 ppm at 7 days to 547 ppm at 30 days at 50°C (see Run 3). As the percentage of DBSA in the blend increases, the pH of the hydroalcoholic solution decreases, dropping from 6.16 (see Run 4) to 4.71 (see Run 5). The corresponding amount of H2S-HS at 30 days of aging decreases dramatically as the pH decreases, down to 25 ppm at pH = 4.71 (see Run 5).

[0176] [Table 1]

[0177] Table 2 shows the analytical results of Runs 3 and 4 from Table 1 and reveals that the organosilane disulfide TESPD is formed in situ and its content increases from 0.15 to 0.28 wt% when comparing the composition of the blend after aging for 30 days at 50° C. with the composition of the same blend as made (Run No. 3 in Table 1). The composition of the silane blend containing 0.24 wt% DBSA (Run No. 4) has an acceptable stability when aged for 30 days at 50° C. and only a slight decrease in the TESPD organosilane disulfide content is observed when compared with the simple blend without acid (Run No. 3).

[0178] [Table 2]

[0179] Case 2 OTPTES / MPTES blends containing different amounts of MPTES were prepared using a procedure similar to that reported in Case 1. In a typical experiment targeting 50 wt% MPTES in the OTPTES / MPTES silane blend, 2.50 g of OTPTES and 2.50 g of MPTES were injected into a 20 mL vial suitable for GC-HS analysis.

[0180] Ternary blends of OTPTES / MPTES / DBSA containing different amounts of MPTES were also prepared using a procedure similar to that reported in Example 1.

[0181] Table 3 shows the variation of H2S-HS formation in OTPTES / MPTES blends with increasing MPTES content. A maximum value of 1391 ppm H2S-HS after 30 days of aging was reached by the 50 wt% OTPTES:50 wt% MPTES silane blend (see Run No. 8). A dramatic reduction in H2S formation is also observed, since all ternary compositions obtained by adding DBSA show reduced H2S-HS already at the time of sample creation / preparation, and the mercapto-rich 50:50 w / w blend with DBSA added (Run No. 13) has a H2S-HS content of 33 ppm after 30 days at 50°C (a 98% reduction with respect to Run No. 8).

[0182] [Table 3]

[0183] Case 3 Blends of polysulfide silanes (compound (a)), such as bis-3-triethoxysilylpropyl tetrasulfide, abbreviated as TESPD and TESPT, and MPTES (compound (b)) as a mercaptosilane, were prepared using a procedure similar to that reported in Example 1. In a typical experiment targeting a silane blend of 75 wt % TESPD:25 wt % MPTES, 3.75 g of TESPD and 1.25 g of MPTES were injected into a 20 mL vial suitable for performing GC-HS analysis.

[0184] Ternary blends TESPD / MPTES / DBSA (polysulfide as compound (a) / mercaptosilane as compound (b) / DBSA as compound (c)) and TESPT / MPTES / DBSA (polysulfide as compound (a) / mercaptosilane as compound (b) / DBSA as compound (c)) were also prepared using a procedure similar to that reported in Example 1. Acid was first added to a vial containing TESPD or TESPT in an amount equal to 75% by weight of the TESPD / MPTES or TESPT / MPTES silane blend. Then, MPTES in an amount equal to 25% by weight of the TESPD / MPTES or TESPT / MPTES silane blend was added to the vial containing the acidified TESPD or acidified TESPT. Each was added to the same vial containing the silane. In a typical experiment, 3.70 g of TESPD was first mixed with 0.06 g of DBSA in a 20 mL vial suitable for GC-HS analysis. Then, 1.23 g of MPTES was added to the acidified TESPD. For the TESPT / MPTES / DBSA blend, 3.58 g of TESPT was first mixed with 0.23 g of DBSA, and then 1.19 g of MPTES was added to the acidified TESPT. Both freshly prepared samples and samples aged in an oven at 50° C. for up to 7 days were subjected to GC-HS analysis. As a control, similar data were collected for both the starting silanes, TESPD and TESPT. In this case, 5 g of silane was used for GC-HS analysis.

[0185] The stabilizing effect of the addition of acid is also illustrated for blends of mercapto-rich polysulfide silanes. Table 4 shows that the 75:25 w / w mercapto-rich blends (see Runs No. 18 and 19) readily produce more than 1 wt. % H2S when exposed to temperatures as high as 50°C, whereas the neat silanes TESPD and TESPT are more stable under the same conditions (see Runs No. 16 and 17). Removal of alkalinity from the commercial TESPD / MPTES blends also dramatically stabilizes the mercapto-rich polysulfide silane blends.

[0186] [Table 4]

[0187] Case 4 Blends of OTPTES, MPTES, and methanesulfonic acid (MSA) were prepared with different ppm levels of methanesulfonic acid using a procedure similar to that reported in Example 1. Both freshly prepared and aged samples were subjected to GC-HS and GC analysis.

[0188] Table 5 shows similar trends in the data for H2S-HS as a function of the amount of MSA added to the 75 wt% OTPTES:25 wt% MPTES silane blend over 30 days of aging compared to the data in Table 1. The amount of H2S-HS from these blends (Runs 23, 24, and 25) is dramatically lower compared to the simple blend (Run 22). In addition, Table 6 shows that the composition of the acidified silane blend (see Run 24) has acceptable stability when aged at 50°C for 30 days and does not increase the TESPD silane content compared to the simple blend (Run 22).

[0189] Table 7 shows that samples stored at 25°C for up to 365 days (Run No. 27) showed a 99% reduction in hydrogen sulfide formation compared to the simple blend (Run No. 26), demonstrating that the stability of the blend as a result of the addition of acid can be maintained over time.

[0190] [Table 5]

[0191] [Table 6]

[0192] [Table 7]

[0193] Case 5 (Comparative Example): Compound (a) is 3-octanoylthio-1-propyltriethoxysilane (OTPTES) / Compound (b) is mercaptopropyltriethoxysilane (MPTES) / Comparative compound (c') is acetic acid

[0194] Using a procedure similar to that reported in Example 1, acetic acid was dosed at different levels into the blends of OTPTES and MPTES.

[0195] The addition of weak acids as low in strength as acetic acid does not prevent the formation of H2S-HS over time, as shown in Table 8.

[0196] [Table 8]

[0197] Case 6: Compound (a) is 3-octanoylthio-1-propyltriethoxysilane; compound (b) is mercaptopropyltriethoxysilane; compound (c) is an acid of different strength. Using a procedure similar to that reported in Example 1, acetic acid was dosed at different levels into the blends of OTPTES and MPTES.

[0198] Acids of strength having a pKa value lower than 4.89 were dosed to blends of OTPTES and MPTES to identify the minimum acid strength capable of reducing the formation of hydrogen sulfide upon aging. Table 9 shows that acids with pKa values ​​lower than 3.75 effectively reduce the formation of hydrogen sulfide at 50° C. for 7 days (Runs 35-41) compared to the simple blend without acid (Run 34). Acids with pKa values ​​equal to or higher than 3.75 (Runs 42-45) are consequently ineffective in mitigating the formation of hydrogen sulfide upon aging.

[0199] [Table 9]

[0200] Cases 7 and 8 The blends of OTPTES and MPTES, and the blends of TESPD and MPTES were dosed with the additive components as shown in Tables 10 and 11.

[0201] Tables 10 and 11 show that the use of compounds that form HCl in situ as component (c) (Run Nos. 51, 52, 53, 54 and 56 in Table 10) or that form methanesulfonic acid in situ as component (c) (Run No. 55 in Table 10), as well as the use of Lewis acids (Run Nos. 58 and 59 in Table 11), also reduces the formation of hydrogen sulfide upon aging.

[0202] [Table 10]

[0203] [Table 11]

[0204] Case 9 Using a procedure similar to that reported in Example 1, blends of OTPTES, MPTES, and methanesulfonic acid (MSA) were prepared.

[0205] Both the freshly prepared and aged samples were subjected to GC-HS and GC analysis.

[0206] Table 12 shows that the H2S-HS content of the acidified silane blend also dramatically decreases when aged for 7 days at temperatures above 50°C, especially at 130°C (see Run No. 62), when compared to the plain blend (Run No. 61). In addition, Table 13 shows that the composition of the acidified silane blend (Run No. 62) has acceptable stability when aged for 7 days at 130°C, whereas the composition of the plain blend under the same conditions changes and the TESPD increases dramatically (Run No. 61).

[0207] [Table 12]

[0208] [Table 13]

Claims

1. A composition: (a) One or more sulfur-containing silanes that do not have (free) mercapto(HS-) functionality, (b) One or more organic compounds having (free) mercapto(HS-) functionality, (c) an acid having a pKa of less than 3.75 as determined in aqueous solution at a temperature of 25°C, and at least one acid selected from one or more Lewis acids. A composition containing the following:

2. The composition according to claim 1, wherein the sulfur-containing silane (a) that does not have mercapto(HS-) functionality is selected from the group consisting of blocked mercaptosilanes, organosilane polysulfides, and mixtures thereof.

3. The organic compound (b) possessing mercapto(HS-) functionality is comprised of organic mercapto compounds that do not contain mercaptosilane and silane moieties, such as alkyl mercaptans like n-octyl mercaptan or tert-dodecanethiol, thioglycolic acid, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, pentaerythritol tetrakis(3-mercaptopropionate), and trimethylolpropanetris(3-mercaptopropionate), with formula HS(CH) ｎ The composition according to claim 1, selected from mercapto acids and their esters having a COOH group and n being 1 to 5, hydroxyalkyl mercapto compounds such as thioglycerol, 1,3-dimercapto-2-propanol, or aromatic and heteroaromatic mercapto compounds such as mercapto-2-benzothiazole.

4. The composition according to claim 1, wherein acid (c), which is an acid having a pKa of less than 3.75 as determined in an aqueous solution at a temperature of 25°C, is selected from the group consisting of protic acids such as inorganic acids, organic acids, and mixtures thereof, or acid (c), which is an acid having a pKa of less than 3.75 as determined in an aqueous solution at a temperature of 25°C, is formed in situ by the addition of a hydrolyzable compound, the hydrolyzable compound reacts with residual water present in the components of the composition to form an acid.

5. The composition according to claim 1, wherein acid (c) is a Lewis acid (c2), preferably selected from the group consisting of lithium (Li) and alkali metals, beryllium (Be), magnesium (Mg) and alkaline earth metals, boron (B), aluminum (Al), silicon (Si), tin (Sn), elements of block d of the periodic table, such as scandium (Sc), titanium (Ti), vanadium (V), manganese (Mn), chromium (Cr), iron (Fe), cobalt (Co), and zinc (Zn), lanthanum (La) and lanthanoid compounds and combinations thereof, and preferably Lewis acid (c2) is an organoboron or organotitanium compound.

6. Sulfur-containing silanes (a) that do not possess mercapto(HS-) functionality are selected from the group consisting of blocked mercaptosilanes of the following formula (I): 【Transformation 7】 During the ceremony R １ These are independently linear alkylene groups of 1 to 6 carbon atoms or branched alkylene groups of 3 to 6 carbon atoms; R ２ Each of these is either a linear alkylene group of 2 to 8 carbon atoms or a branched alkylene group of 3 to 8 carbon atoms; R ３ Each of these is independently a linear alkylene group of 1 to 6 carbon atoms or a branched alkylene group of 3 to 6 carbon atoms; X １ is -OR ４ group, where R ４ is an alkyl group of 1 to 4 carbon atoms, -OR ５ OH group, where R ５ is a straight-chain alkylene group of 2 to 8 carbon atoms or a branched-chain alkylene group of 3 to 8 carbon atoms, or X １ is -OR ６ (OR ７ )cOR ８ , where R ６ is a straight-chain alkylene group of 2 to 6 carbon atoms or a branched-chain alkylene group of 3 to 6 carbon atoms, preferably 3 carbon atoms, R ７ each of which is independently an alkylene group of 2 to 4 carbon atoms, and R ８ is a straight-chain alkyl group of 1 to 16 carbon atoms or a branched-chain alkyl group of 3 to 16 carbon atoms, and c is an integer from 1 to 20; X ２ and X ３ X is independent １ or methyl; X ４ Each of them is independently X １ or methyl; Y １ Each of these is -C(=O)R ９ , -C (=S) OR ９ Or -CN, where R ９ Each of these is independently a linear alkylene group of 1 to 16 carbon atoms, more preferably 5 to 11 carbon atoms, and even more preferably 6 to 9 carbon atoms, or a branched alkylene group of 3 to 16 carbon atoms, more preferably 5 to 11 carbon atoms, and even more preferably 6 to 9 carbon atoms; and a is an integer from 0 to 8, however (iii)X １ and X ２ ga- OR ４ In this case, two -OR ４ They are bonded to each other via covalent bonds, forming a cyclic structure containing two oxygen atoms and one silicon atom, bonded to the same silicon atom -OR ４ -R ４ It can form an O- group; also (iv) a is from 1 to 8 and X ３ and X ４ ga- OR ４ In this case, two -OR ４ The groups are bonded to each other via covalent bonds, and are bonded to the same silicon atom, forming a cyclic structure containing two oxygen atoms and one silicon atom -OR ４ -R ４ The composition according to claim 1, which may form an O-group.

7. Sulfur-containing silane (a) that does not have a mercapto(HS-) functional component has at least one polysulfide moiety-S ｘ The composition according to claim 1, selected from silanes containing -, where x is an average value of about 2 to about 12, preferably about 2 to about 10, more preferably about 2 to about 8, more preferably about 2 to about 6, more preferably about 2 to about 4, more preferably about 2 or about 4.

8. The composition according to claim 1, wherein sulfur-containing silane (a) constitutes more than 50% by weight of the total composition.

9. Organic compound (b) possessing mercapto(HS-) functionality is selected from mercaptosilanes of the following formula: 【Transformation 8】 During the ceremony R １ These are mutually independent as defined above; R ２ Each of them is defined independently as previously defined; R ３ Each of them is defined independently as previously defined; X １ , X ２ , X ３ and X ４ These are mutually independent as defined above, And a is as defined above, the composition according to claim 1.

10. The composition according to claim 1, wherein the pH of the aqueous alcohol solution at 25°C is less than about 7, preferably between about 3 and about 7, more preferably between about 4 and about 6, and even more preferably between about 5 and about 6.

11. One or more sulfur-containing silanes (a) in approximately 5 to approximately 95% by weight, preferably approximately 50 to approximately 95% by weight. One or more organic compounds (b) in approximately 5 to approximately 95% by weight, preferably approximately 5 to approximately 50% by weight, and The present invention comprises at least one acid (c) in an amount of about 0.01 to about 5% by weight, preferably about 0.01 to about 2% by weight, more preferably about 0.01 to about 1% by weight, and even more preferably about 0.01 to about 0.1% by weight. The composition according to claim 1, wherein each percentage is based on the total weight of the composition.

12. A method for producing the composition according to any one of claims 1 to 11, comprising at least one step of combining or bringing into contact components (a), (b) and / or (c), preferably (i) a step of combining one or more sulfur-containing silanes (a) with at least one acid (c) and then one or more organic compounds (b), or (ii) a step of combining one or more organic compounds (b) with at least one acid (c) and then one or more sulfur-containing silanes (a), A method for producing a product, wherein at least one acid (c) is added during the production of a sulfur-containing silane (a) or during the production of an organic compound (b) by a unit operation including processing of raw materials, mixing, reaction, washing, purification, filtration, heat treatment and post-treatment.

13. A method for reducing the emission of hydrogen sulfide from a sulfur-containing silane composition, comprising the step of adding to the composition an effective amount of at least one acid (c2) selected from acids having a pKa of less than 3.75 as determined in aqueous solution at a temperature of 25°C, and Lewis acids.

14. Use of the composition according to any one of claims 1 to 11 as an additive for a rubber composition containing a filler such as carbon black or silica, preferably silica.

15. A rubber composition comprising silica and one or more compositions according to any one of claims 1 to 11, and a vulcanized article thereof.

Images