阅读说明：本技术 硅烷混合物及其制备方法 (Silane mixture and preparation method thereof ) 是由 A·克普费尔 C·勒本 A·哈塞 F·福斯特 于 2018-11-16 设计创作，主要内容包括：本发明涉及硅烷混合物,其包含式I的硅烷和式II的硅烷(R<Sup>1</Sup>)<Sub>y</Sub>(R<Sup>2</Sup>)<Sub>3-y</Sub>Si-R<Sup>3</Sup>-(S-R<Sup>4</Sup>)<Sub>n</Sub>-S<Sub>x</Sub>-R<Sup>5</Sup>(I)；(R<Sup>1</Sup>)<Sub>y</Sub>(R<Sup>2</Sup>)<Sub>3-y</Sub>Si-R<Sup>3</Sup>-S-R<Sup>3</Sup>-Si(R<Sup>1</Sup>)<Sub>y</Sub>(R<Sup>2</Sup>)<Sub>3-y</Sub>(II)；其中,式I的硅烷与式II的硅烷的摩尔比为15：85至90：10。可以通过混合式I的硅烷和式II的硅烷来制备根据本发明的硅烷混合物。(The invention relates to silane mixtures comprising silanes of formula I and silanes of formula II (R) 1 ) y (R 2 ) 3‑y Si‑R 3 ‑(S‑R 4 ) n ‑S x ‑R 5 (I)；(R 1 ) y (R 2 ) 3‑y Si‑R 3 ‑S‑R 3 ‑Si(R 1 ) y (R 2 ) 3‑y (II); wherein the molar ratio of silane of formula I to silane of formula II is 15: 85 to 90: 10. the silane mixture according to the invention can be prepared by mixing the silane of formula I and the silane of formula II.)

1. A silane mixture comprising a silane of formula I and a silane of formula II:

(R¹)_y(R²)_3-ySi-R³-(S-R⁴)_n-S_x-R⁵(I)

(R¹)_y(R²)_3-ySi-R³-S-R³-Si(R¹)_y(R²)_3-y(II)

wherein R is¹Are identical or different and are C1-C10 alkoxy, phenoxy, C4-C10 cycloalkoxy or alkylpolyether-O- (R)⁶-O)_r-R⁷Wherein R is⁶Are identical or different and are branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic divalent C1-C30 hydrocarbon radicals, R is an integer from 1 to 30, R is⁷Is unsubstituted or substituted, branched or unbranched, monovalent alkyl, alkenyl, aryl or aralkyl radical,

R²are identical or different and are C6-C20 aryl, C1-C10 alkyl, C2-C20 alkenyl, C7-C20 aralkyl or halogen,

R³are identical or different and are branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic divalent C1-C30 hydrocarbon radicals,

R⁴are identical or different and are branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic divalent C1-C30 hydrocarbon radicals,

x is an integer of 1 to 10 and,

when x is 1, R⁵Is hydrogen or R⁸-C (═ O) -R) being hydrogen⁸A group, C1-C20 alkyl, C6-C20 aryl, C2-C20 alkenyl or C7-C20 aralkyl, and n is 0, 1,2 or 3,

when x is 2 to 10, R⁵Is- (R)⁴-S)_n-R³-Si(R¹)_y(R²)_3-yAnd n is 1,2 or 3,

and y is identical or different and is 1,2 or 3,

and, the molar ratio of silane of formula I to silane of formula II is 20: 80 to 90: 10.

2. the silane mixture of claim 1, wherein n is 1.

3. The silane mixture as claimed in claim 2, characterized in that the silane of the formula I is

(EtO)₃Si-(CH₂)₃-S-(CH₂)₆-S₂-(CH₂)₆-S-(CH₂)₃-Si(OEt)₃、

(EtO)₃Si-(CH₂)₃-S-(CH₂)₆-S-C(＝O)-CH₃、

(EtO)₃Si-(CH₂)₃-S-(CH₂)₆-S-C(＝O)-C₇H₁₅Or

(EtO)₃Si-(CH₂)₃-S-(CH₂)₆-S-C(＝O)-C₁₇H₃₅And is and

the silane of the formula II is (EtO)₃Si-(CH₂)₃-S-(CH₂)₃-Si(OEt)₃。

4. The silane mixture of claim 1, wherein the molar ratio of silane of formula I to silane of formula II is 35: 65 to 90: 10.

5. process for preparing a silane mixture according to claim 1, characterized in that a silane of the formula I and a silane of the formula II are reacted at a molar ratio of 15: 85 to 90: 10 in a molar ratio:

(R¹)_y(R²)_3-ySi-R³-(S-R⁴)_n-S_x-R⁵(I)

(R¹)_y(R²)_3-ySi-R³-S-R³-Si(R¹)_y(R²)_3-y(II)

wherein R is¹、R²、R³、R⁴、R⁵N, x and y have the definitions given above.

6. The process for preparing a silane mixture according to claim 5, wherein n is 1.

7. The process for preparing a silane mixture according to claim 5, characterized in that the molar ratio of silane of formula I to silane of formula II is 35: 65 to 90: 10.

8. process for preparing a silane mixture according to claim 5, characterized in that the silane of the formula I is (EtO)₃Si-(CH₂)₃-S-(CH₂)₆-S₂-(CH₂)₆-S-(CH₂)₃-Si(OEt)₃、

(EtO)₃Si-(CH₂)₃-S-(CH₂)₆-S-C(＝O)-CH₃、

(EtO)₃Si-(CH₂)₃-S-(CH₂)₆-S-C(＝O)-C₇H₁₅Or

(EtO)₃Si-(CH₂)₃-S-(CH₂)₆-S-C(＝O)-C₁₇H₃₅And is and

the silane of the formula II is (EtO)₃Si-(CH₂)₃-S-(CH₂)₃-Si(OEt)₃。

Examples

NMR method: the molar ratios and mass ratios reported in the examples as analytical results are derived from¹³C NMR measurement is carried out according to the following specific indexes: 100.6MHz, 1000 scans, solvent: CDCl₃Calibration internal standard: tetramethylsilane, relaxation aid (relaxation aid): cr (acac)₃(ii) a To determine the mass ratio in the products, a defined amount of dimethyl sulfone was added as an internal standard and the molar ratio of the products was used to calculate the mass ratio.

Comparative example 1: 3-octanoylthio-1-propyltriethoxysilane, NXT silane from Momentive Performance materials.

Comparative example 2: bis-triethoxysilyloctane from ABCR GmbH.

Comparative example 3: bis (triethoxysilylpropyl) disulfide from Evonik Industries AG.

Comparative example 4: 1-chloro-6-thiopropyltriethoxysilylhexane

NaOEt (21% in EtOH; 1562 g; 4.820 mol) was metered into mercaptopropyltriethoxysilane (1233 g; 5.170 mol) over 1 hour while stirring at room temperature. After the addition was complete, the reaction mixture was heated under reflux for 2 hours, and then allowed to stand to cool to room temperature. The intermediate formed is metered into 1, 6-dichlorohexane (4828 g; 31.14 mol) which has been heated to 80 ℃ within 30 minutes. After the addition was complete, the reaction mixture was heated to reflux for 3 hours, and then allowed to stand to cool to room temperature. The reaction mixture was filtered and the filter cake was rinsed with EtOH. Volatile components were removed under reduced pressure to give 1-chloro-6-thiopropyltriethoxysilylhexane intermediate (yield: 89%, molar ratio: 97% of 1-chloro-6-thiopropyltriethoxysilylhexane, 3% of bis (thiopropyltriethoxysilyl) hexane,% by weight: 95% by weight of 1-chloro-6-thiopropyltriethoxysilylhexane, 5% by weight of 1, 6-bis (thiopropyltriethoxysilyl) hexane) as a colorless to brown liquid.

Comparative example 5: 6-bis (thiopropyltriethoxysilylhexyl) disulfide

6-bis (thiopropyltriethoxysilylhexyl) disulfide was prepared according to synthetic example 1 and example 1 of EP 1375504.

In contrast to synthesis example 1 of EP1375504, the intermediate was not distilled.

And (3) analysis: (88% yield, molar ratio: silane of formula I: 94% (EtO)₃Si(CH₂)₃S(CH₂)₆S₂(CH₂)₆S(CH₂)₃Si(OEt)₃And a silane of formula II: 6% (EtO)₃Si(CH₂)₃S(CH₂)₆S(CH₂)₃Si(OEt)₃And weight percent: a silane of formula I: 95% by weight (EtO)₃Si(CH₂)₃S(CH₂)₆S₂(CH₂)₆S(CH₂)₃Si(OEt)₃And a silane of formula II: 5% by weight (EtO)₃Si(CH₂)₃S(CH₂)₆S(CH₂)₃Si(OEt)₃)。

Comparative example 6: s- (6- ((3- (triethoxysilyl) propyl) thio) hexyl) thioacetate

First, Na is added₂CO₃(59.78 g; 0.564 mol) and aqueous NaSH solution (40% in water; 79.04 g; 0.564 mol) were added together with water (97.52 g). Tetrabutylphosphonium bromide (TBPB) (50% in water; 3.190 g; 0.005 mol) was then added and acetyl chloride (40.58 g; 0.517 mol) was added dropwise over 1 hour, during which the reaction temperature was kept at 25 ℃ to 32 ℃. After the addition of acetyl chloride was complete, the mixture was stirred at room temperature for 1 hour. TBPB (50%; 3.190 g; 0.005 mole) and 1-chloro-6-thiopropyltriethoxysilylhexane (from comparative example 4; 167.8 g; 0.470 mole) were then added and the mixture heated to reflux for 3 to 5 hours. The progress of the reaction was monitored by gas chromatography. Once the 1-chloro-6-thiopropyltriethoxysilylhexane has reacted to a degree of greater than 96%, water is added until all salts are dissolved and the phases are separated. The volatile components of the organic phase were removed under reduced pressure and S- (6- ((3- (triethoxysilyl) propyl) thio) hexyl) thioacetate was obtained (yield: 90%, molar ratio: 97% S- (6- ((3- (triethoxysilyl) propyl) thio) hexyl) thioacetate, 3% bis (thiopropyltriethoxysilyl) hexane,% by weight: 96% S- (6- ((3- (triethoxysilyl) propyl) thio) hexyl) thioacetate, 4% by weight of 1, 6-bis (thiopropyltriethoxysilyl) hexane) as a yellow to brown liquid.

Comparative example 7: s- (6- ((3- (triethoxysilyl) propyl) thio) hexyl) thio-octanoate

First, Na is added₂CO₃(220.2 g; 2.077 mol) and an aqueous solution of NaSH (40%; 291.2 g; 2.077 mol in water) were added together with water (339.2 g). Tetrabutylammonium bromide (TBAB) (50% in water; 10.96 g; 0.017 mol) was then added and octanoyl chloride (307.2 g; 1.889 mol) was added dropwise over a period of 2.5 hours, during which the reaction temperature was maintained at 24 ℃ to 28 ℃. After the addition of octanoyl chloride was completed, the mixture was stirred at room temperature for 1 hour. TBAB (50% in water; 32.88 g; 0.051 moles) and 1-chloro-6-thiopropyltriethoxysilylhexane (from comparative example 4; 606.9 g; 1.700 moles) were then added and the mixture heated at reflux for 10 hours. Thereafter, water is added until all salts are dissolved and separatedThe phases were separated. The volatile components of the organic phase were removed under reduced pressure and S- (6- ((3- (triethoxysilyl) propyl) thio) hexyl) thiocaprylate was obtained (yield: 95%, molar ratio: 97% S- (6- ((3- (triethoxysilyl) propyl) thio) hexyl) thiocaprylate, 3% bis (thiopropyltriethoxysilyl) hexane,% by weight: 96% S- (6- ((3- (triethoxysilyl) propyl) thio) hexyl) thiocaprylate, 4% 1, 6-bis (thiopropyltriethoxysilyl) hexane) as a yellow to brown liquid.

Comparative example 8: 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) according to synthesis examples 1 and 3 in JP 2012149189.

S- (6- ((3- (triethoxysilyl) propyl) thio) hexyl) thiooctadecanoate (yield: 89%, molar ratio: 97% of S- (6- ((3- (triethoxysilyl) propyl) thio) hexyl) thiooctadecanoate, 3% of 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: bis (triethoxysilylpropyl) sulfide

To a solution of chloropropyltriethoxysilane (361 g; 1.5 mol; 1.92 eq) in ethanol (360ml) was added Na in portions₂S (61.5 g; 0.78 mol; 1.00 eq) is added at such a rate that it does not exceed 60 ℃. After the addition was complete, the mixture was heated under reflux for 3 hours and then cooled to room temperature. The precipitated salt was removed from the reaction product by filtration. The product can be obtained as a clear liquid by purification by distillation (0.04 mbar; 110 ℃ C.) (yield: 73%, purity: > 99% by means of¹³CNMR)。

Comparative example 10: 6.84 parts by weight of comparative example 1 and 1.65 parts by weight of comparative example2 were weighed together into a flat PE bag and mixed. This mixture corresponds to the molar ratio: 83% (EtO)₃Si(CH₂)₃SCO(CH₂)₆CH₃And 17% (EtO)₃Si(CH₂)₈Si(OEt)₃。

Comparative example 11: 6.84 parts by weight of comparative example 1 were weighed into a flat PE bag together with 2.47 parts by weight of comparative example 2 and mixed. This mixture corresponds to the molar ratio: 77% (EtO)₃Si(CH₂)₃SCO(CH₂)₆CH₃And 23% (EtO)₃Si(CH₂)₈Si(OEt)₃。

Comparative example 12: 6.84 parts by weight of comparative example 3 were weighed into a flat PE bag together with 2.65 parts by weight of comparative example 2 and mixed. This mixture corresponds to the molar ratio: 71% (EtO)₃Si(CH₂)₃S₂(CH₂)₃Si(OEt)₃And 29% (EtO)₃Si(CH₂)₃S(CH₂)₃Si(OEt)₃。

Comparative example 13: 6.84 parts by weight of comparative example 3 were weighed into a flat PE bag together with 3.65 parts by weight of comparative example 9 and mixed. This mixture corresponds to the molar ratio: 64% (EtO)₃Si(CH₂)₃S₂(CH₂)₃Si(OEt)₃And 36% (EtO)₃Si(CH₂)₃S(CH₂)₃Si(OEt)₃。

Comparative example 14: 6.30 parts by weight of comparative example 1 were weighed into a flat PE bag together with 2.53 parts by weight of comparative example 2 and mixed. This mixture corresponds to the molar ratio: 75% (EtO)₃Si(CH₂)₃SCO(CH₂)₆CH₃And 25% (EtO)₃Si(CH₂)₈Si(OEt)₃。

Comparative example 15: 4.20 parts by weight of comparative example 1 were weighed into a flat PE bag together with 3.79 parts by weight of comparative example 2 and mixed. This mixture corresponds to the molar ratio: 57% (EtO)₃Si(CH₂)₃SCO(CH₂)₆CH₃And 43% (EtO)₃Si(CH₂)₈Si(OEt)₃。

Comparative example 16: 2.10 parts by weight of comparative example 1 were weighed into a flat PE bag together with 5.06 parts by weight of comparative example 2 and mixed. This mixture corresponds to the molar ratio: 33% (EtO)₃Si(CH₂)₃SCO(CH₂)₆CH₃And 67% (EtO)₃Si(CH₂)₈Si(OEt)₃。

Comparative example 17: 4.10 parts by weight of comparative example 3 were weighed into a flat PE bag together with 2.44 parts by weight of comparative example 9 and mixed. This mixture corresponds to the molar ratio: 61% (EtO)₃Si(CH₂)₃S₂(CH₂)₃Si(OEt)₃And 39% (EtO)₃Si(CH₂)₃S(CH₂)₃Si(OEt)₃。

Comparative example 18: 2.74 parts by weight of comparative example 3 were weighed into a flat PE bag together with 3.65 parts by weight of comparative example 9 and mixed. This mixture corresponds to the molar ratio: 41% (EtO)₃Si(CH₂)₃S₂(CH₂)₃Si(OEt)₃And 59% (EtO)₃Si(CH₂)₃S(CH₂)₃Si(OEt)₃。