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>-SH (I)；(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>z</Sub>-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20：80至85：15。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 ‑SH (I)；(R 1 ) y (R 2 ) 3‑y Si‑R 3 ‑(S‑R 4 ) z ‑Si(R 1 ) y (R 2 ) 3‑y (II) wherein the molar ratio of silane of formula I to silane of formula II is 20: 80 to 85: 15. 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-SH (I)

(R¹)_y(R²)_3-ySi-R³-(S-R⁴)_z-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)⁵-O)_r-R⁶Wherein R is⁵Are 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 is⁶Is 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,

and y is identical or different and is 1,2 or 3, z is 0, 1,2 or 3,

and, the molar ratio of silane of formula I to silane of formula II is 20: 80 to 85: 15.

2. the silane mixture according to claim 1, wherein z is 0, 1 or 2.

3. Silane mixture according to claim 1Characterised in that the silane of the formula I is (EtO)₃Si-(CH₂)₃-SH, and

the silane of the formula II is (EtO)₃Si-(CH₂)₃-S-(CH₂)₆-S-(CH₂)₃-Si(OEt)₃、(EtO)₃Si-(CH₂)₈-Si(OEt)₃Or (EtO)₃Si-(CH₂)₃-S-(CH₂)₃Si(OEt)₃。

4. The silane mixture of claim 1, wherein the molar ratio of silane of formula I to silane of formula II is 50: 50 to 85: 15.

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 20: 80 to 85: 15 in a molar ratio:

((R¹)_y(R²)_3-ySi-R³-SH (I)

(R¹)_y(R²)_3-ySi-R³-(S-R⁴)_z-Si(R¹)_y(R²)_3-y(II)

wherein R is¹、R²、R³、R⁴Y and z have the definitions given above.

6. The process for preparing a silane mixture according to claim 5, wherein z is 0, 1 or 2.

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 50: 50 to 85: 15.

8. the process for preparing a silane mixture according to claim 7,

the silane of the formula I is (EtO)₃Si-(CH₂)₃-SH, and

the silane of the formula II is (EtO)₃Si-(CH₂)₃-S-(CH₂)₆-S-(CH₂)₃-Si(OEt)₃、(EtO)₃Si-(CH₂)₈-Si(OEt)₃Or (EtO)₃Si-(CH₂)₃-S-(CH₂)₃Si(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: bis (triethoxysilylpropyl) disulfide, from Evonik Industries AG.

Comparative example 2: 3-octanoylthio-1-propyltriethoxysilane, NXT silane from Momentive Performance materials.

Comparative example 3: (3-mercaptopropyl) triethoxysilane.

Comparative example 4: bis-triethoxysilyloctane from ABCR GmbH.

Comparative example 5: 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 completed, the mixture was heated under reflux for 3 hours, and then allowed to stand to cool to room temperature. The precipitated salt was removed from the reaction product by filtration. Purification by distillation (0.04 mbar; 110 ℃ C.) gave the product (yield: 73%, purity: > 99% by use of¹³C NMR) as a transparent liquid.

Comparative example 6: 1, 6-bis (thiopropyltriethoxysilyl) hexane

Sodium ethoxide (21% in EtOH; 82.3 g; 0.254 mol; 2.05 equiv) was metered into mercaptopropyltriethoxysilane (62.0 g; 0.260 mol; 2.10 equiv) at such a rate that the reaction temperature did not exceed 35 ℃. After the addition was complete, the mixture was heated to reflux for 2 hours. The reaction mixture was then added to 1, 6-dichlorohexane (19.2 g; 0.124 mol; 1.00 eq.) at 80 ℃ over 1.5 hours. After the addition was complete, the mixture was heated to reflux for 3 hours and then allowed to cool to room temperature. The precipitated salt was filtered off and the solvent was removed from the product under reduced pressure. The product was obtained (yield: 88%, purity: 99%,¹³c NMR) as a transparent liquid.

Comparative example 7: 6.84 parts by weight of comparative example 1 together with 2.65 parts by weight of comparative example 5 were weighed into a flat PE bag 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 8: 6.84 parts by weight of comparative example 1 together with 3.65 parts by weight of comparative example 5 are weighed into a flat PE bag 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 9: 6.84 parts by weight of comparative example 1 were weighed into a flat PE bag together with 4.87 parts by weight of comparative example 5 and mixed. This mixture corresponds to the molar ratio: 57% (EtO)₃Si(CH₂)₃S₂(CH₂)₃Si(OEt)₃And 43% (EtO)₃Si(CH₂)₃S(CH₂)₃Si(OEt)₃。

Comparative example 10: 6.84 parts by weight of comparative example 2 and 2.10 parts by weightComparative example 6 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)₃S(CH₂)₆S(CH₂)₃Si(OEt)₃。

Comparative example 11: 6.84 parts by weight of comparative example 2 were weighed into a flat PE bag together with 3.15 parts by weight of comparative example 6 and mixed. This mixture corresponds to the molar ratio: 77% (EtO)₃Si(CH₂)₃SCO(CH₂)₆CH₃And 23% (EtO)₃Si(CH₂)₃S(CH₂)₆S(CH₂)₃Si(OEt)₃。

Comparative example 12: 6.84 parts by weight of comparative example 2 were weighed into a flat PE bag together with 4.20 parts by weight of comparative example 6 and mixed. This mixture corresponds to the molar ratio: 71% (EtO)₃Si(CH₂)₃SCO(CH₂)₆CH₃And 29% (EtO)₃Si(CH₂)₃S(CH₂)₆S(CH₂)₃Si(OEt)₃。

Comparative example 13: 6.84 parts by weight of comparative example 2 were weighed into a flat PE bag together with 1.65 parts by weight of comparative example 4 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 14: 6.84 parts by weight of comparative example 2 were weighed into a flat PE bag together with 2.47 parts by weight of comparative example 4 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 15: 6.84 parts by weight of comparative example 2 were weighed into a flat PE bag together with 3.29 parts by weight of comparative example 4 and mixedAnd (6) mixing. This mixture corresponds to the molar ratio: 71% (EtO)₃Si(CH₂)₃SCO(CH₂)₆CH₃And 29% (EtO)₃Si(CH₂)₈Si(OEt)₃。