Silane mixtures and process for preparing same

Abstract

The invention relates to silane mixtures comprising a silane of the formula I
(R.sup.1).sub.y(R.sup.2).sub.3-ySi—R.sup.3—(S—R.sup.4).sub.n—S.sub.x—R.sup.5  (I)
and a silane of the formula II
(R.sup.1).sub.y(R.sup.2).sub.3-ySi—R.sup.3—Si(R.sup.1).sub.y(R.sup.2).sub.3-y  (II)
where the molar ratio of silane of the formula I to silane of the formula II is 15:85-90:10. The silane mixture according to the invention can be prepared by mixing the silanes of the formula I and silanes of the formula II.

Claims

1. A silane mixture, comprising: a silane of formula I
(R.sup.1).sub.y(R.sup.2).sub.3-ySi—R.sup.3—(S—R.sup.4).sub.n—S.sub.x—R.sup.5  (I) and a silane of formula II
(R.sup.1).sub.y(R.sup.2).sub.3-ySi—R.sup.3—Si(R.sup.1).sub.y(R.sup.2).sub.3-y  (II) where R.sup.1 is the same or different and is a C1-C10-alkoxy group, a phenoxy group, a C4-C10-cycloalkoxy group or an alkyl polyether group—O —(R.sup.6—O).sub.r—R.sup.7 where R.sup.6 is the same or different and is a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic divalent C1-C30 hydrocarbon group, r is an integer from 1 to 30, and R.sup.7 is an unsubstituted or substituted, branched or unbranched monovalent alkyl, alkenyl, aryl or aralkyl group, R.sup.2 is the same or different and is a C6-C20-aryl group, a C1-C10-alkyl group, a C2-C20-alkenyl group, a C7-C20-aralkyl group or halogen, R.sup.3 is the same or different and is a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic divalent C1-C30 hydrocarbon group, R.sup.4 is the same or different and is a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic divalent C1-C30 hydrocarbon group, x is an integer from 1 to 10” with “x is an integer of 1 or from 5 to 10, when x is 1, R.sup.5 is hydrogen or a —C(═O)—R.sup.8 group with R.sup.8=hydrogen, a C1-C20 alkyl group, a C6-C20-aryl group, a C2-C20-alkenyl group or a C7-C20-aralkyl group and n is 1, when x is 5 to 10, R.sup.5 is —(R.sup.4—S).sub.n—R.sup.3—Si(R.sup.1).sub.y(R.sup.2).sub.3-y and n is 1, and y is the same or different and is 1, 2 or 3, and the molar ratio of the silane of the formula I to the silane of the formula II is 15:85-90:10.

2. The silane mixture according to claim 1, wherein the silane of the formula I is (EtO).sub.3Si—(CH.sub.2).sub.3—S—(CH.sub.2).sub.6—S—C(═O)—CH.sub.3, (EtO).sub.3Si—(CH.sub.2).sub.3—S—(CH.sub.2).sub.6—S—C(═O)—C.sub.7H.sub.15 or (EtO).sub.3Si—(CH.sub.2).sub.3—S—(CH.sub.2).sub.6—S—C(=O)—C.sub.17H.sub.35 and the silane of the formula II is (EtO).sub.3Si—(CH.sub.2).sub.8—Si(OEt).sub.3.

3. The silane mixture according to claim 1, wherein the molar ratio of the silane of the formula I to the silane of the formula II is 30:70-86:14.

4. A process for preparing the silane mixture according to claim 1, wherein the silane of the formula I and the silane of the formula II are mixed in a molar ratio of 15:85-90:10.

5. The process for preparing the silane mixture according claim 4, wherein the molar ratio of the silane of the formula I to the silane of the formula II is 30:70-86:14.

6. The process for preparing the silane mixture according claim 4, wherein the silane of the formula I is (EtO).sub.3Si—(CH.sub.2).sub.3—S—(CH.sub.2).sub.6—S—C(═O)—CH.sub.3, (EtO).sub.3Si—(CH.sub.2).sub.3—S—(CH.sub.2).sub.6—S—C(═O)—C.sub.7H.sub.15 or (EtO).sub.3Si—(CH.sub.2).sub.3—S—(CH.sub.2).sub.6—S—C(═O)—C.sub.17H.sub.35 and the silane of the formula II is (EtO).sub.3Si—(CH.sub.2).sub.8—Si(OEt).sub.3.

7. A silane mixture, comprising: a silane of formula I
(R.sup.1).sub.y(R.sup.2).sub.3-ySi—R.sup.3—(S—R.sup.4).sub.n—S.sub.x—R.sup.5  (I) and a silane of formula II
(R.sup.1).sub.y(R.sup.2).sub.3-ySi—R.sup.3—Si(R.sup.1).sub.y(R.sup.2).sub.3-y  (II) where R.sup.1 is the same or different and is a C1-C10-alkoxy group, a phenoxy group, a C4-C10-cycloalkoxy group or an alkyl polyether group —O—(R.sup.6—O).sub.r—R.sup.7 where R.sup.6 is the same or different and is a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic divalent C1-C30 hydrocarbon group, r is an integer from 1 to 30, and R.sup.7 is an unsubstituted or substituted, branched or unbranched monovalent alkyl, alkenyl, aryl or aralkyl group, R.sup.2 is the same or different and is a C6-C20-aryl group, a C1-C10-alkyl group, a C2-C20-alkenyl group, a C7-C20-aralkyl group or halogen, R.sup.3 is the same or different and is a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic divalent C1-C30 hydrocarbon group, R.sup.4 is the same or different and is a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic divalent C1-C30 hydrocarbon group, x is an integer from 1 to 10, when x is 1, R.sup.5 is hydrogen or a —C(═O)—R.sup.8 group with R.sup.8=hydrogen, a C1-C20 alkyl group, a C6-C20-aryl group, a C2-C20-alkenyl group or a C7-C20-aralkyl group and n is 1, 2 or 3, when x is 2 to 4, R.sup.5 is —(R.sup.4—S).sub.n—R.sup.3—Si(R.sup.1).sub.y(R.sup.2).sub.3-y and n is 2 or 3, when x is 5 to 10, R.sup.5 is —(R.sup.4—S).sub.n—R.sup.3—Si(R.sup.1).sub.y(R.sup.2).sub.3-y and n is 0, 1, 2 or 3, and y is the same or different and is 1, 2 or 3, and the molar ratio of the silane of the formula I to the silane of the formula II is 15:85-90:10.

8. The silane mixture according to claim 7, wherein when x is 2 to 10, R.sup.5 is —(R.sup.4—S).sub.n—R.sup.3—Si(R.sup.1), (R.sup.2).sub.3-y and n is 2 or 3.

9. The silane mixture according to claim 7, wherein n is 1.

10. The silane mixture according to claim 7, wherein the silane of the formula I is (EtO).sub.3Si—(CH.sub.2).sub.3—S—(CH.sub.2).sub.6—S—C(═O)—CH.sub.3, (EtO).sub.3Si—(CH.sub.2).sub.3—S—(CH.sub.2).sub.6—S—C(═O)—C.sub.7H.sub.15 or (EtO).sub.3Si—(CH.sub.2).sub.3—S—(CH.sub.2).sub.6—S—C(═O)—C.sub.17H.sub.35 and the silane of the formula II is (EtO).sub.3Si—(CH.sub.2).sub.8—Si(OEt).sub.3.

11. The silane mixture according to claim 7, wherein the molar ratio of the silane of the formula I to the silane of the formula II is 30:70-86:14.

Description

EXAMPLES

(1) NMR method: The molar ratios and proportions by mass reported as analysis results in the examples come from .sup.13C NMR measurements with the following indices: 100.6 MHz, 1000 scans, solvent: CDCl.sub.3, internal standard for calibration: tetramethylsilane, relaxation aid: Cr(acac).sub.3; for the determination of the proportion by mass in the product, a defined amount of dimethyl sulfone is added as internal standard and the molar ratios of the products are used to calculate the proportion by mass.

Comparative Example 1

(2) 3-octanoylthio-1-propyltriethoxysilane, NXT Silane from Momentive Performance Materials

Comparative Example 2

(3) bistriethoxysilyloctane from ABCR GmbH

Comparative Example 3

(4) bis(triethoxysilylpropyl) disulfide from Evonik Industries AG.

Comparative Example 4

(5) 1-chloro-6-thiopropyltriethoxysilylhexane NaOEt (21% in EtOH; 1562 g; 4.820 mol) was metered into mercaptopropyltriethoxysilane (1233 g; 5.170 mol) over the course of 1 h while stirring at room temperature. On completion of addition, the reaction mixture was heated at reflux for 2 h and then left to cool to room temperature. The intermediate formed was metered into 1,6-dichlorohexane (4828 g; 31.14 mol) that had been heated to 80° C. over the course of 30 min. On completion of addition, the reaction mixture was heated at reflux for 3 h, before being left to cool to room temperature. The reaction mixture was filtered and the filtercake was rinsed with EtOH. The volatile constituents were removed under reduced pressure and the 1-chloro-6-thiopropyltriethoxysilylhexane intermediate (yield: 89%, molar ratio: 97% 1-chloro-6-thiopropyltriethoxysilylhexane, 3% bis(thiopropyltriethoxysilyl)hexane; % by weight: 95% by weight of 1-chloro-6-thiopropyltriethoxysilylhexane, 5% by weight of 1,6-bis(thiopropyltriethoxysilyl)hexane) was obtained as a colourless to brown liquid.

Comparative Example 5

(6) 6-bis(thiopropyltriethoxysilylhexyl) disulfide 6-Bis(thiopropyltriethoxysilylhexyl) disulfide was prepared according to Synthesis Example 1 and Example 1 of EP 1375504.

(7) By contrast with Synthesis Example 1 of EP1375504, the intermediate was not distilled.

(8) Analysis: (88% yield, molar ratio: silane of the formula I: 94%

(9) (EtO).sub.3Si(CH.sub.2).sub.3S(CH.sub.2).sub.6S.sub.2(CH.sub.2).sub.6S(CH.sub.2).sub.3Si(OEt).sub.3 and 6% (EtO).sub.3Si(CH.sub.2).sub.3S(CH.sub.2).sub.6S(CH.sub.2).sub.3Si(OEt).sub.3, % by weight: silane of the formula: 95% by weight of (EtO).sub.3Si(CH.sub.2).sub.3S(CH.sub.2).sub.6S.sub.2(CH.sub.2).sub.6S(CH.sub.2).sub.3Si(OEt).sub.3 and 5% by weight of (EtO).sub.3Si(CH.sub.2).sub.3S(CH.sub.2)S(CH.sub.2).sub.3Si(OEt).sub.3)

Comparative Example 6

(10) S-(6-((3-(triethoxysilyl)propyl)thio)hexyl) thioacetate Na.sub.2CO.sub.3 (59.78 g; 0.564 mol) and an aqueous solution of NaSH (40% in water; 79.04 g; 0.564 mol) were initially charged together with water (97.52 g). Then tetrabutylphosphonium bromide (TBPB) (50% in water; 3.190 g; 0.005 mol) was added and acetyl chloride (40.58 g; 0.517 mol) was added dropwise over the course of 1 h, during which the reaction temperature was kept at 25-32° C. On completion of addition of the acetyl chloride, the mixture was stirred at room temperature for 1 h. Then TBPB (50% in water; 3.190 g; 0.005 mol) and 1-chloro-6-thiopropyltriethoxysilylhexane (from Comparative Example 4; 167.8 g; 0.470 mol) were added and the mixture was heated at reflux for 3-5 h. The progress of the reaction was monitored by means of gas chromatography. Once the 1-chloro-6-thiopropyltriethoxysilylhexane had reacted to an extent of >96%, water was added until all the salts had dissolved and the phases were separated. The volatile constituents of the organic phase were removed under reduced pressure, and S-(6-((3-(triethoxysilyl)propyl)thio)hexyl) thioacetate (yield: 90%, molar ratio: 97% S-(6-((3-(triethoxysilyl)propyl)thio)hexyl) thioacetate, 3% bis(thiopropyltriethoxysilyl)hexane; % by weight: 96% by weight of S-(6-((3-(triethoxysilyl)propyl)thio)hexyl) thioacetate, 4% by weight of 1,6-bis(thiopropyltriethoxysilyl)hexane) was obtained as a yellow to brown liquid.

Comparative Example 7

(11) S-(6-((3-(triethoxysilyl)propyl)thio)hexyl) thiooctanoate Na.sub.2CO.sub.3 (220.2 g; 2.077 mol) and an aqueous solution of NaSH (40% in water; 291.2 g; 2.077 mol) were initially charged together with water (339.2 g). Then tetrabutylammonium bromide (TBAB) (50% in water; 10.96 g; 0.017 mol) was added and octanoyl chloride (307.2 g; 1.889 mol) was added dropwise over the course of 2.5 h, during which the reaction temperature was kept at 24-28° C. On completion of addition of the octanoyl chloride, the mixture was stirred at room temperature for 1 h. Then TBAB (50% in water; 32.88 g; 0.051 mol) and 1-chloro-6-thiopropyltriethoxysilyhexane (from Comparative Example 4, 606.9 g; 1.700 mol) were added and the mixture was heated at reflux for 10 h. Then water was added until all the salts had dissolved and the phases were separated. The volatile constituents of the organic phase were removed under reduced pressure, and S-(6-((3-(triethoxysilyl)propyl)thio)hexyl) thiooctanoate (yield: 95%, molar ratio: 97% S-(6-((3-(triethoxysilyl)propyl)thio)hexyl) thiooctanoate, 3% bis(thiopropyltriethoxysilyl)hexane; % by weight: 96% by weight of S-(6-((3-(triethoxysilyl)propyl)thio)hexyl) thiooctanoate, 4% by weight of 1,6-bis(thiopropyltriethoxysilyl)hexane) was obtained as a yellow to brown liquid.

Comparative Example 8

(12) S-(6-((3-(triethoxysilyl)propyl)thio)hexyl) thiooctadecanoate S-(6-((3-(Triethoxysilyl)propyl)thio)hexyl) thiooctadecanoate was prepared from 1-chloro-6-thiopropyltriethoxysilylhexane (from Comparative Example 4) in accordance with Synthesis Examples 1 and 3 in JP2012149189.

(13) S-(6-((3-(Triethoxysilyl)propyl)thio)hexyl) thiooctadecanoate (yield: 89%, molar ratio: 97% S-(6-((3-(triethoxysilyl)propyl)thio)hexyl) thiooctadecanoate, 3% bis(thiopropyltriethoxysilyl)hexane; % by weight: 97% by weight of S-(6-((3-(triethoxysilyl)propyl)thio)hexyl) thiooctadecanoate, 3% by weight of 1,6-bis(thiopropyltriethoxysilyl)hexane) was obtained as a yellow to brown liquid.

Comparative Example 9

(14) 6.84 parts by weight of Comparative Example 1 together with 1.65 parts by weight of Comparative Example 2 were weighed into a flat PE bag and mixed. This mixture corresponds to a molar ratio: 83% (EtO).sub.3Si(CH.sub.2).sub.3SCO(CH.sub.2).sub.6CH.sub.3 and 17% (EtO).sub.3Si(CH.sub.2).sub.8Si(OEt).sub.3.

Comparative Example 10

(15) 6.84 parts by weight of Comparative Example 1 together with 2.47 parts by weight of Comparative Example 2 were weighed into a flat PE bag and mixed. This mixture corresponds to a molar ratio: 77% (EtO).sub.3Si(CH.sub.2).sub.3SCO(CH.sub.2).sub.6CH.sub.3 and 23% (EtO).sub.3Si(CH.sub.2).sub.8Si(OEt).sub.3.

Comparative Example 11

(16) 6.84 parts by weight of Comparative Example 1 together with 3.29 parts by weight of Comparative Example 2 were weighed into a flat PE bag and mixed. This mixture corresponds to a molar ratio: 71% (EtO).sub.3Si(CH.sub.2).sub.3SCO(CH.sub.2).sub.6CH.sub.3 and 29% (EtO).sub.3Si(CH.sub.2).sub.8Si(OEt).sub.3.

Comparative Example 12

(17) 6.30 parts by weight of Comparative Example 1 together with 2.53 parts by weight of Comparative Example 2 were weighed into a flat PE bag and mixed. This mixture corresponds to a molar ratio: 75% (EtO).sub.3Si(CH.sub.2).sub.3SCO(CH.sub.2).sub.6CH.sub.3 and 25% (EtO).sub.3Si(CH.sub.2).sub.8Si(OEt).sub.3.

Comparative Example 13

(18) 4.20 parts by weight of Comparative Example 1 together with 3.79 parts by weight of Comparative Example 2 were weighed into a flat PE bag and mixed. This mixture corresponds to a molar ratio: 57% (EtO).sub.3Si(CH.sub.2).sub.3SCO(CH.sub.2).sub.6CH.sub.3 and 43% (EtO).sub.3Si(CH.sub.2).sub.8Si(OEt).sub.3.

Comparative Example 14

(19) 2.10 parts by weight of Comparative Example 1 together with 5.06 parts by weight of Comparative Example 2 were weighed into a flat PE bag and mixed. This mixture corresponds to a molar ratio: 33% (EtO).sub.3Si(CH.sub.2).sub.3SCO(CH.sub.2).sub.6CH.sub.3 and 67% (EtO).sub.3Si(CH.sub.2).sub.8Si(OEt).sub.3.

Example 1

(20) 6.84 parts by weight of Comparative Example 3 together with 2.53 parts by weight of Comparative Example 2 were weighed into a flat PE bag and mixed. This mixture corresponds to a molar ratio: 71% (EtO).sub.3Si(CH.sub.2).sub.3S.sub.2(CH.sub.2).sub.3Si(OEt).sub.3 and 29% (EtO).sub.3Si(CH.sub.2).sub.8Si(OEt).sub.3.

Example 2

(21) 6.84 parts by weight of Comparative Example 3 together with 3.79 parts by weight of Comparative Example 2 were weighed into a flat PE bag and mixed. This mixture corresponds to a molar ratio: 63% (EtO).sub.3Si(CH.sub.2).sub.3S.sub.2(CH.sub.2).sub.3Si(OEt).sub.3 and 37% (EtO).sub.3Si(CH.sub.2).sub.8Si(OEt).sub.3.

Example 3

(22) 6.84 parts by weight of Comparative Example 5 together with 1.70 parts by weight of Comparative Example 2 were weighed into a flat PE bag and mixed. This mixture corresponds to a molar ratio: 66% (EtO).sub.3Si(CH.sub.2).sub.3S(CH.sub.2).sub.6S.sub.2(CH.sub.2).sub.6S(CH.sub.2).sub.3Si(OEt).sub.3 and 34% (EtO).sub.3Si(CH.sub.2).sub.8Si(OEt).sub.3.

Example 4

(23) 6.84 parts by weight of Comparative Example 5 together with 2.55 parts by weight of Comparative Example 2 were weighed into a flat PE bag and mixed. This mixture corresponds to a molar ratio: 58% (EtO).sub.3Si(CH.sub.2).sub.3S(CH.sub.2).sub.6S.sub.2(CH.sub.2).sub.6S(CH.sub.2).sub.3Si(OEt).sub.3 and 42% (EtO).sub.3Si(CH.sub.2).sub.8Si(OEt).sub.3.

Example 5

(24) 6.84 parts by weight of Comparative Example 6 together with 1.51 parts by weight of Comparative Example 2 were weighed into a flat PE bag and mixed. This mixture corresponds to a molar ratio: 80% (EtO).sub.3Si(CH.sub.2).sub.3S(CH.sub.2).sub.6SCOCH.sub.3 and 20% (EtO).sub.3Si(CH.sub.2).sub.8Si(OEt).sub.3.

Example 6

(25) 6.84 parts by weight of Comparative Example 6 together with 2.27 parts by weight of Comparative Example 2 were weighed into a flat PE bag and mixed. This mixture corresponds to a molar ratio: 74% (EtO).sub.3Si(CH.sub.2).sub.3S(CH.sub.2).sub.6SCOCH.sub.3 and 26% (EtO).sub.3Si(CH.sub.2).sub.8Si(OEt).sub.3.

Example 7

(26) 6.84 parts by weight of Comparative Example 7 together with 1.25 parts by weight of Comparative Example 2 were weighed into a flat PE bag and mixed. This mixture corresponds to a molar ratio: 80% (EtO).sub.3Si(CH.sub.2).sub.3S(CH.sub.2).sub.6SCO(CH.sub.2).sub.6CH.sub.3 and 20% (EtO).sub.3Si(CH.sub.2).sub.8Si(OEt).sub.3.

Example 8

(27) 6.84 parts by weight of Comparative Example 7 together with 1.87 parts by weight of Comparative Example 2 were weighed into a flat PE bag and mixed. This mixture corresponds to a molar ratio: 74% (EtO).sub.3Si(CH.sub.2).sub.3S(CH.sub.2).sub.6SCO(CH.sub.2).sub.6CH.sub.3 and 26% (EtO).sub.3Si(CH.sub.2).sub.8Si(OEt).sub.3.

Example 9

(28) 6.84 parts by weight of Comparative Example 8 together with 0.97 parts by weight of Comparative Example 2 were weighed into a flat PE bag and mixed. This mixture corresponds to a molar ratio: 80% (EtO).sub.3Si(CH.sub.2).sub.3S(CH.sub.2).sub.6SCO(CH.sub.2).sub.16CH.sub.3 and 20% (EtO).sub.3Si(CH.sub.2).sub.8Si(OEt).sub.3.

Example 10

(29) 6.84 parts by weight of Comparative Example 8 together with 1.45 parts by weight of Comparative Example 2 were weighed into a flat PE bag and mixed. This mixture corresponds to a molar ratio: 74% (EtO).sub.3Si(CH.sub.2).sub.3S(CH.sub.2).sub.6SCO(CH.sub.2).sub.16CH.sub.3 and 26% (EtO).sub.3Si(CH.sub.2).sub.8Si(OEt).sub.3.

Example 11

(30) 5.47 parts by weight of Comparative Example 3 together with 1.26 parts by weight of Comparative Example 2 were weighed into a flat PE bag and mixed. This mixture corresponds to a molar ratio: 80% (EtO).sub.3Si(CH.sub.2).sub.3S.sub.2(CH.sub.2).sub.3Si(OEt).sub.3 and 20% (EtO).sub.3Si(CH.sub.2).sub.8Si(OEt).sub.3.

Example 12

(31) 4.10 parts by weight of Comparative Example 3 together with 2.53 parts by weight of Comparative Example 2 were weighed into a flat PE bag and mixed. This mixture corresponds to a molar ratio: 60% (EtO).sub.3Si(CH.sub.2).sub.3S.sub.2(CH.sub.2).sub.3Si(OEt).sub.3 and 40% (EtO).sub.3Si(CH.sub.2).sub.8Si(OEt).sub.3.

Example 13

(32) 2.74 parts by weight of Comparative Example 3 together with 3.79 parts by weight of Comparative Example 2 were weighed into a flat PE bag and mixed. This mixture corresponds to a molar ratio: 40% (EtO).sub.3Si(CH.sub.2).sub.3S.sub.2(CH.sub.2).sub.3Si(OEt).sub.3 and 60% (EtO).sub.3Si(CH.sub.2).sub.8Si(OEt).sub.3.

Example 14

(33) 1.37 parts by weight of Comparative Example 3 together with 5.06 parts by weight of Comparative Example 2 were weighed into a flat PE bag and mixed. This mixture corresponds to a molar ratio: 20% (EtO).sub.3Si(CH.sub.2).sub.3S.sub.2(CH.sub.2).sub.3Si(OEt).sub.3 and 80% (EtO).sub.3Si(CH.sub.2).sub.8Si(OEt).sub.3.

Example 15

(34) 8.15 parts by weight of Comparative Example 5 together with 1.26 parts by weight of Comparative Example 2 were weighed into a flat PE bag and mixed. This mixture corresponds to a molar ratio: 74% (EtO).sub.3Si(CH.sub.2).sub.3S(CH.sub.2).sub.6S.sub.2(CH.sub.2).sub.6S(CH.sub.2).sub.3Si(OEt).sub.3 and 26% (EtO).sub.3Si(CH.sub.2).sub.8Si(OEt).sub.3.

Example 16

(35) 6.11 parts by weight of Comparative Example 5 together with 2.53 parts by weight of Comparative Example 2 were weighed into a flat PE bag and mixed. This mixture corresponds to a molar ratio: 56% (EtO).sub.3Si(CH.sub.2).sub.3S(CH.sub.2).sub.6S.sub.2(CH.sub.2).sub.6S(CH.sub.2).sub.3Si(OEt).sub.3 and 44% (EtO).sub.3Si(CH.sub.2).sub.8Si(OEt).sub.3.

Example 17

(36) 4.08 parts by weight of Comparative Example 5 together with 3.79 parts by weight of Comparative Example 2 were weighed into a flat PE bag and mixed. This mixture corresponds to a molar ratio: 38% (EtO).sub.3Si(CH.sub.2).sub.3S(CH.sub.2).sub.6S.sub.2(CH.sub.2).sub.6S(CH.sub.2).sub.3Si(OEt).sub.3 and 62% (EtO).sub.3Si(CH.sub.2).sub.8Si(OEt).sub.3.

Example 18

(37) 2.04 parts by weight of Comparative Example 5 together with 5.06 parts by weight of Comparative Example 2 were weighed into a flat PE bag and mixed. This mixture corresponds to a molar ratio: 19% (EtO).sub.3Si(CH.sub.2).sub.3S(CH.sub.2).sub.6S.sub.2(CH.sub.2).sub.6S(CH.sub.2).sub.3Si(OEt).sub.3 and 81% (EtO).sub.3Si(CH.sub.2).sub.8Si(OEt).sub.3.

(38) Example 19: 9.14 parts by weight of Comparative Example 6 together with 1.26 parts by weight of Comparative Example 2 were weighed into a flat PE bag and mixed. This mixture corresponds to a molar ratio: 87% (EtO).sub.3Si(CH.sub.2).sub.3S(CH.sub.2).sub.6SCOCH.sub.3 and 13% (EtO).sub.3Si(CH.sub.2).sub.8Si(OEt).sub.3.

Example 20

(39) 6.86 parts by weight of Comparative Example 6 together with 2.53 parts by weight of Comparative Example 2 were weighed into a flat PE bag and mixed. This mixture corresponds to a molar ratio: 72% (EtO).sub.3Si(CH.sub.2).sub.3S(CH.sub.2).sub.6SCOCH.sub.3 and 28% (EtO).sub.3Si(CH.sub.2).sub.8Si(OEt).sub.3.

Example 21

(40) 4.57 parts by weight of Comparative Example 6 together with 3.79 parts by weight of Comparative Example 2 were weighed into a flat PE bag and mixed. This mixture corresponds to a molar ratio: 55% (EtO).sub.3Si(CH.sub.2).sub.3S(CH.sub.2).sub.6SCOCH.sub.3 and 45% (EtO).sub.3Si(CH.sub.2).sub.8Si(OEt).sub.3.

Example 22

(41) 2.29 parts by weight of Comparative Example 6 together with 5.06 parts by weight of Comparative Example 2 were weighed into a flat PE bag and mixed. This mixture corresponds to a molar ratio: 32% (EtO).sub.3Si(CH.sub.2).sub.3S(CH.sub.2).sub.6SCOCH.sub.3 and 68% (EtO).sub.3Si(CH.sub.2).sub.8Si(OEt).sub.3.

Example 23

(42) 11.08 parts by weight of Comparative Example 7 together with 1.26 parts by weight of Comparative Example 2 were weighed into a flat PE bag and mixed. This mixture corresponds to a molar ratio: 85% (EtO).sub.3Si(CH.sub.2).sub.3S(CH.sub.2).sub.6SCO(CH.sub.2).sub.6CH.sub.3 and 15% (EtO).sub.3Si(CH.sub.2).sub.8Si(OEt).sub.3.

Example 24

(43) 8.31 parts by weight of Comparative Example 7 together with 2.53 parts by weight of Comparative Example 2 were weighed into a flat PE bag and mixed. This mixture corresponds to a molar ratio: 72% (EtO).sub.3Si(CH.sub.2).sub.3S(CH.sub.2).sub.6SCO(CH.sub.2).sub.6CH.sub.3 and 28% (EtO).sub.3Si(CH.sub.2).sub.8Si(OEt).sub.3.

Example 25

(44) 5.54 parts by weight of Comparative Example 7 together with 3.79 parts by weight of Comparative Example 2 were weighed into a flat PE bag and mixed. This mixture corresponds to a molar ratio: 55% (EtO).sub.3Si(CH.sub.2).sub.3S(CH.sub.2).sub.6SCO(CH.sub.2).sub.6CH.sub.3 and 45% (EtO).sub.3Si(CH.sub.2).sub.8Si(OEt).sub.3.

Example 26

(45) 2.77 parts by weight of Comparative Example 7 together with 5.06 parts by weight of Comparative Example 2 were weighed into a flat PE bag and mixed. This mixture corresponds to a molar ratio: 32% (EtO).sub.3Si(CH.sub.2).sub.3S(CH.sub.2).sub.6SCO(CH.sub.2).sub.6CH.sub.3 and 68% (EtO).sub.3Si(CH.sub.2).sub.8Si(OEt).sub.3.

Example 27

(46) 14.32 parts by weight of Comparative Example 8 together with 1.26 parts by weight of Comparative Example 2 were weighed into a flat PE bag and mixed. This mixture corresponds to a molar ratio: 85% (EtO).sub.3Si(CH.sub.2).sub.3S(CH.sub.2).sub.6SCO(CH.sub.2).sub.16CH.sub.3 and 15% (EtO).sub.3Si(CH.sub.2).sub.8Si(OEt).sub.3.

Example 28

(47) 10.74 parts by weight of Comparative Example 8 together with 2.53 parts by weight of Comparative Example 2 were weighed into a flat PE bag and mixed. This mixture corresponds to a molar ratio: 72% (EtO).sub.3Si(CH.sub.2).sub.3S(CH.sub.2).sub.6SCO(CH.sub.2).sub.16CH.sub.3 and 28% (EtO).sub.3Si(CH.sub.2).sub.8Si(OEt).sub.3.

Example 29

(48) 7.16 parts by weight of Comparative Example 8 together with 3.79 parts by weight of Comparative Example 2 were weighed into a flat PE bag and mixed. This mixture corresponds to a molar ratio: 55% (EtO).sub.3Si(CH.sub.2).sub.3S(CH.sub.2).sub.6SCO(CH.sub.2).sub.16CH.sub.3 45% (EtO).sub.3Si(CH.sub.2).sub.8Si(OEt).sub.3.

Example 30

(49) 5.06 parts by weight of Comparative Example 8 together with 3.58 parts by weight of Comparative Example 2 were weighed into a flat PE bag and mixed. This mixture corresponds to a molar ratio: 48% (EtO).sub.3Si(CH.sub.2).sub.3S(CH.sub.2).sub.6SCO(CH.sub.2).sub.16CH.sub.3 and 52% (EtO).sub.3Si(CH.sub.2).sub.8Si(OEt).sub.3.

Example 31: Rubber Tests

(50) The formulation used for the rubber mixtures is specified in Table 1 below. The unit phr means parts by weight based on 100 parts of the raw rubber used. The silane mixtures all contain an identical phr amount of silane which reacts with the rubber during the vulcanization. The second silane is added additionally.

(51) TABLE-US-00001 TABLE 1 Mixture Mixture Mixture Mixture Mixture Mixture Mixture Mixture Mixture Mixture Mixture Mixture Mixture 4/phr 5/phr 6/phr 7/phr 8/phr 9/phr 10/phr 11/phr 12/phr 13/phr 1/phr 2/phr 3/phr Inv. Inv. Inv. Inv. Inv. Inv. Inv. Inv. Inv. Inv. 1st stage NR.sup.a) 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 BR.sup.b) 18.0 18.0 18.0 18.0 18.0 18.0 18.0 18.0 18.0 18.0 18.0 18.0 18.0 S-SBR.sup.c) 72.0 72.0 72.0 72.0 72.0 72.0 72.0 72.0 72.0 72.0 72.0 72.0 72.0 Silica.sup.d) 95.0 95.0 95.0 95.0 95.0 95.0 95.0 95.0 95.0 95.0 95.0 95.0 95.0 TDAE oil.sup.e) 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 6PPD.sup.f) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Antiozonant wax 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Zinc oxide 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Stearic acid 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Comp. Ex. 9 8.49 Comp. Ex. 10 9.31 Comp. Ex. 11 10.13 Example 1 9.37 Example 2 10.63 Example 3 8.54 Example 4 9.39 Example 5 8.35 Example 6 9.11 Example 7 8.09 Example 8 8.71 Example 9 7.81 Example 10 8.29 2nd stage Stage 1 batch 3rd stage Stage 2 batch DPG.sup.g) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 CBS.sup.h) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Sulfur.sup.i) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Substances used: .sup.a)NR TSR SMR 10: natural rubber (TSR = technically specified rubber; SMR = standard .sup.a)NR TSR: natural rubber (TSR = technically specified rubber). .sup.b)Europrene Neocis BR 40, from Polimeri. .sup.c)S-SBR: Sprintan ® SLR-4601, from Trinseo. .sup.d)Silica: ULTRASIL ® VN 3 GR from Evonik Industries AG (precipitated silica, BET surface area = 175 m.sup.2/g). .sup.e)TDAE oil: TDAE = treated distillate aromatic extract. .sup.f)6PPD: N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine (6PPD). .sup.g)DPG: N,N′-diphenylguanidine (DPG). .sup.h)CBS: N-cyclohexyl-2-benzothiazolesulfenamide. .sup.i)Sulfur: ground sulfur.

(52) The mixture was produced by processes customary in the rubber industry in three stages in a laboratory mixer of capacity 300 millilitres to 3 litres, by first mixing, in the first mixing stage (base mixing stage), all the constituents apart from the vulcanization system (sulfur and vulcanization-influencing substances) at 145 to 165° C., target temperatures of 152 to 157° C., for 200 to 600 seconds. In the second stage, the mixture from stage 1 was thoroughly mixed once more, performing what is called a remill. Addition of the vulcanization system in the third stage (ready-mix stage) produced the finished mixture, with mixing at 90 to 120° C. for 180 to 300 seconds. All the mixtures were used to produce test specimens by vulcanization under pressure at 160° C.−170° C. after t95-t100 (measured on a moving disc rheometer to ASTM D 5289-12/ISO 6502).

(53) The general process for producing rubber mixtures and vulcanizates thereof is described in “Rubber Technology Handbook”, W. Hofmann, Hanser Verlag 1994.

(54) Rubber testing was effected in accordance with the test methods specified in Table 2. The results of the rubber testing are reported in Table 3.

(55) TABLE-US-00002 TABLE 2 Physical testing Standard/conditions Viscoelastic properties of the RPA (“rubber process analyzer”) vulcanizate at 70° C., 1.0 Hz in accordance with ASTM D6601 from the second strain sweep Dynamic storage modulus G′ at 100% elongation/MPa Loss factor tan δ at 10% elongation

(56) TABLE-US-00003 TABLE 3 Mixture Mixture Mixture Mixture Mixture 1 2 3 4 Inv. 5 Inv. G′(100%) RPA/MPa 427 400 422 784 758 tan δ (10%) RPA 0.210 0.217 0.205 0.167 0.170 Mixture Mixture Mixture Mixture Mixture 6 Inv. 7 Inv. 8 Inv. 9 Inv. 10 Inv. G′(100%) RPA/MPa 729 746 688 702 601 tan δ (10%) RPA 0.160 0.156 0.164 0.164 0.169 Mixture Mixture Mixture 11 Inv. 12 Inv. 13 Inv. G′(100%) RPA/MPa 626 598 585 tan δ (10%) RPA 0.164 0.170 0.171

(57) Compared to the comparative mixtures, the inventive mixtures feature improved rolling resistance (tan δ measured at 70° C.). Moreover, the silane mixtures according to the invention lead to advantages in dynamic stiffness (G′(100%) measured at 70° C.).

Example 32: Rubber Tests

(58) The formulation used for the rubber mixtures is specified in Table 4 below. The unit phr means parts by weight based on 100 parts of the raw rubber used. In the silane mixtures, some of the silane that reacts with the rubber during the vulcanization is replaced by the second silane which is unreactive toward the rubber.

(59) TABLE-US-00004 TABLE 4 Mixture Mixture Mixture Mixture Mixture Mixture Mixture Mixture Mixture Mixture Mixture Mixture 17/phr 18/phr 19/phr 20/phr 21/phr 22/phr 23/phr 24/phr 25/phr 14/phr 15/phr 16/phr Inv. Inv. Inv. Inv. Inv. Inv. Inv. Inv. Inv. 1st stage NR.sup.a) 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 BR.sup.b) 18.0 18.0 18.0 18.0 18.0 18.0 18.0 18.0 18.0 18.0 18.0 18.0 S-SBR.sup.c) 72.0 72.0 72.0 72.0 72.0 72.0 72.0 72.0 72.0 72.0 72.0 72.0 Silica.sup.d) 95.0 95.0 95.0 95.0 95.0 95.0 95.0 95.0 95.0 95.0 95.0 95.0 TDAE oil.sup.e) 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 6PPD.sup.f) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Antiozonant wax 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Zinc oxide 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Stearic acid 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Comp. Ex. 12 8.83 Comp. Ex. 13 7.99 Comp. Ex. 14 7.16 Example 11 6.73 Example 12 6.63 Example 13 6.53 Example 14 6.43 Example 15 9.41 Example 16 8.64 Example 17 7.87 Example 18 7.10 Example 19 10.40 2nd stage Stage 1 batch 3rd stage Stage 2 batch DPG.sup.g) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 CBS.sup.h) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Sulfur.sup.i) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Mixture Mixture Mixture Mixture Mixture Mixture Mixture Mixture Mixture Mixture Mixture 26/phr 27/phr 28/phr 29/phr 30/phr 31/phr 32/phr 33/phr 34/phr 35/phr 36/phr Inv. Inv. Inv. Inv. Inv. Inv. Inv. Inv. Inv. Inv. Inv. 1st stage NR.sup.a) 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 BR.sup.b) 18.0 18.0 18.0 18.0 18.0 18.0 18.0 18.0 18.0 18.0 18.0 S-SBR.sup.c) 72.0 72.0 72.0 72.0 72.0 72.0 72.0 72.0 72.0 72.0 72.0 Silica.sup.d) 95.0 95.0 95.0 95.0 95.0 95.0 95.0 95.0 95.0 95.0 95.0 TDAE oil.sup.e) 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 6PPD.sup.f) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Antiozonant wax 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Zinc oxide 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Stearic acid 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Example 20 9.39 Example 21 8.36 Example 22 7.35 Example 23 12.34 Example 24 10.84 Example 25 9.33 Example 26 7.83 Example 27 15.58 Example 28 13.27 Example 29 10.95 Example 30 8.64 2nd stage Stage 1 batch 3rd stage Stage 2 batch DPG.sup.g) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 CBS.sup.h) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Sulfur.sup.i) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Substances used: .sup.a)NR TSR: natural rubber (TSR = technically specified rubber). .sup.b)Europrene Neocis BR 40, from Polimeri. .sup.c)S-SBR: Sprintan ® SLR-4601, from Trinseo. .sup.d)Silica: ULTRASIL ® VN 3 GR from Evonik Industries AG (precipitated silica, BET surface area = 175 m.sup.2/g). .sup.e)TDAE oil: TDAE = treated distillate aromatic extract. .sup.f)6PPD: N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine (6PPD). .sup.g)DPG: N,N′-diphenylguanidine (DPG). .sup.h)CBS: N-cyclohexyl-2-benzothiazolesulfenamide. .sup.i)Sulfur: ground sulfur.

(60) The mixture was produced in processes customary in the rubber industry in three stages in a laboratory mixer of capacity 300 millilitres to 3 litres, by first mixing, in the first mixing stage (base mixing stage), all the constituents apart from the vulcanization system (sulfur and vulcanization-influencing substances) at 145 to 165° C., target temperatures of 152 to 157° C., for 200 to 600 seconds. In the second stage, the mixture from stage 1 was thoroughly mixed once more, performing what is called a remill. Addition of the vulcanization system in the third stage (ready-mix stage) produced the finished mixture, with mixing at 90 to 120° C. for 180 to 300 seconds. All the mixtures were used to produce test specimens by vulcanization under pressure at 160° C.−170° C. after t95-t100 (measured on a moving disc rheometer to ASTM D 5289-12/ISO 6502).

(61) The general process for producing rubber mixtures and vulcanizates thereof is described in “Rubber Technology Handbook”, W. Hofmann, Hanser Verlag 1994.

(62) Rubber testing was effected in accordance with the test method specified in Table 2. The results of the rubber testing are reported in Table 5.

(63) TABLE-US-00005 TABLE 5 Mixture Mixture Mixture Mixture Mixture 14 15 16 17 Inv. 18 Inv. G′(100%) RPA/MPa 417 387 403 684 678 tan δ (10%) RPA 0.214 0.221 0.223 0.187 0.180 Mixture Mixture Mixture Mixture Mixture 19 Inv. 20 Inv. 21 Inv. 22 Inv. 23 Inv. G′(100%) RPA/MPa 708 571 731 726 683 tan δ (10%) RPA 0.172 0.196 0.155 0.158 0.166 Mixture Mixture Mixture Mixture Mixture 24 Inv. 25 Inv. 26 Inv. 27 Inv. 28 Inv. G′(100%) RPA/MPa 598 689 700 678 695 tan δ (10%) RPA 0.183 0.164 0.163 0.167 0.163 Mixture Mixture Mixture Mixture Mixture 29 Inv. 30 Inv. 31 Inv. 32 Inv. 33 Inv. G′(100%) RPA/MPa 639 632 642 589 569 tan δ (10%) RPA 0.148 0.161 0.171 0.179 0.147 Mixture Mixture Mixture 34 Inv. 35 Inv. 36 Inv. G′(100%) RPA/MPa 594 603 573 tan δ (10%) RPA 0.154 0.165 0.179

(64) The partial exchange of the rubber-reactive silane for the second silane leads to improved rolling resistance (tan δ measured at 70° C.) in the mixtures according to the invention compared to the comparative mixtures. Moreover, the silane mixtures according to the invention lead to advantages in dynamic stiffness (G′(100%) measured at 70° C.).