CARBOCATIONICALLY HYDROSILYLATABLE MIXTURE

Abstract

Subject-matter of the invention is a hydrosilylatable mixture M comprising compound (C), which contains at least one carbocationic structure, and compound (A), which has at least one directly Si-bonded hydrogen atom and compound (B), which contains at least one carbon-carbon multiple bond, or compound (AB), where between the SiH group and the nearest adjacent carbon atom of the carbon-carbon multiple bond there are at least 6 atoms, or compound (A) and compound (AB) or compound (B) and compound (AB), where the compounds (A), (B) and (AB) are defined in claim 1.

Claims

1. A hydrosilylatable mixture M comprising: a compound (C), comprising at least one carbocationic structure, and a compound (A) having at least one hydrogen atom directly bonded to Si, and a compound (B), comprising at least one carbon-carbon multiple bond or a compound (AB), in which at least 6 atoms are arranged between the SiH group and the nearest carbon atom of the carbon-carbon multiple bond or the compound (A) and the compound (AB) or the compound (B) and the compound (AB), wherein the compound (A) has the general formula I
R.sup.1R.sup.2R.sup.3SH(I) where R.sup.1, R.sup.2 and R.sup.3 are each independently hydrogen, chlorine, C1-C3-alkyl or C1 -C3-alkylene radicals, phenyl radicals, C1-C4 alkoxy radicals or silyloxy radicals of the general formula II,
(SiO.sub.4/2).sub.a(R.sup.xSiO.sub.3/2).sub.b(R.sup.x.sub.2SiO.sub.2/2).sub.c(R.sup.x.sub.3SiO.sub.1/2).sub.d(II) in which R.sup.x are each independently hydrogen, chlorine, C1-C6 alkyl or alkylene, phenyl or C1-C6 alkoxy and a, b, c and d are each independently integral values from 0 to 100 000, wherein the sum total of a, b, c and d together have at least the value 1 and the compound (B) is selected from compounds having at least one carbon-carbon double bond of the general formula IIIa
R.sup.4R.sup.5CCR.sup.6R.sup.7(IIIa), wherein R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are each independently linear, branched, acyclic or cyclic, saturated or monounsaturated or polyunsaturated C1-C20 hydrocarbon radicals, wherein individual carbon atoms may be replaced by silicon, oxygen, halogen, nitrogen, sulfur or phosphorus, with the proviso that only one of the two radicals R.sup.4 and R.sup.5 comprises a double bond conjugated with the central CC double bond and with the proviso that only one of the two radicals R.sup.6 and R.sup.7 comprises a double bond conjugated with the central CC double bond, wherein the molar ratio between the compound (C) and the SiH groups present is from 1:10.sup.8 to 1:100.

2. A method for hydrosilylation, comprising: reacting a hydrosilylatable mixture M, mixture M comprising compound (C), which comprises at least one carbocationic structure and a compound (A) having at least one hydrogen atom directly bonded to Si, and a compound (B), which comprises at least one carbon-carbon multiple bond or a compound (AB), in which at least 6 atoms are arranged between the SiH group and the nearest carbon atom of the carbon-carbon multiple bond or the compound (A) and the compound (AB) or the compound (B) and the compound (AB), wherein the compound (A) has the general formula I
R.sup.1R.sup.2R.sup.3SH(I) where R.sup.1, R.sup.2 and R.sup.3 each independently have the definition hydrogen, halogen, silyloxy radical, hydrocarbon radical or hydrocarbonoxy radical, wherein individual carbon atoms may in each case be replaced by oxygen atoms, silicon atoms, nitrogen atoms, halogen, sulfur or phosphorus atoms and the compound (B) is selected from compounds having at least one carbon-carbon double bond of the general formula IIIa
R.sup.4R.sup.5CCR.sup.6R.sup.7(IIIa), and from compounds having at least one carbon-carbon triple bond of the general formula IIIb
R.sup.8CCR.sup.9(IIIb), where where R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are each independently linear, branched, acyclic or cyclic, saturated or monounsaturated or polyunsaturated C1-C20 hydrocarbon radicals, wherein individual carbon atoms may be replaced by silicon, oxygen, halogen, nitrogen, sulfur or phosphorus, with the proviso that only one of the two radicals R.sup.4 and R.sup.5 comprises a double bond conjugated with the central CC double bond and with the proviso that only one of the two radicals R.sup.6 and R.sup.7 comprises a double bond conjugated with the central CC double bond wherein the molar ratio between the compound (C) and the SiH groups present is from 1:10.sup.8 to 1:100.

3. The hydrosilylatable mixture M of claim 1, wherein the compound (C) comprises one or more carbocationic structures corresponding to the general formula IV
(R.sup.13R.sup.14R.sup.15)C.sup.+X.sup.(IV) wherein the radicals R.sup.13, R.sup.14 and R.sup.15 are aromatic radicals of the formula V, ##STR00002## in which R.sup.y are any radicals, which may also bond to one another to form fused rings and X.sup. is an anion, which does not react with the cationic carbon center under the reaction conditions.

4. The hydrosilylatable mixture M of claim 3, wherein the radicals R.sup.y are each independently hydrogen, linear or branched, acyclic or cyclic, saturated or mono- or polyunsaturated C1-C20 alkyl or aryl radicals, in which carbon moieties can be replaced by oxygen or sulfur, or halogen.

5. The method of claim 2, wherein the radicals R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are each independently hydrogen, linear, branched, acyclic or cyclic, saturated or monounsaturated or polyunsaturated C1-C6 hydrocarbon radicals, which can be substituted by one or more heteroatom moieties.

6. The method for hydrosilylation of claim 2, wherein the compound (C) comprises one or more carbocationic structures corresponding to the general formula IV:
(R.sup.13R.sup.14R.sup.15)C.sup.+X.sup.(IV) wherein the radicals R.sup.13, R.sup.14 and R.sup.15 are aromatic radicals of the formula V, ##STR00003## in which R.sup.y are any radicals, which may also bond to one another to form fused rings and X.sup. is an anion which does not react with the cationic carbon center under the reaction conditions.

7. The method for hydrosilylation of claim 6, wherein the radicals R.sup.y are each independently hydrogen, linear or branched acyclic or cyclic, saturated or mono- or polyunsaturated C1-C20 alkyl or aryl radicals, in which carbon moieties can be replaced by oxygen or sulfur, or halogen.

Description

EXAMPLE 1

[0064] 136 mg (1.00 mmol) of dimethylphenylsilane in 0.5 ml of d.sub.2-dichloromethane are mixed with a solution of 118 mg (1.00 mmol) of -metylstyrene in 0.5. ml of d.sub.2-dichloromethane and a solution of 0.9 mg (1.0 mol, 0.1 mol %) of trityl tetrakis(pentafluorophenyl)borate in 0.5 ml of d.sub.2-dichloromethane is added. After a reaction time of 10 min, the reaction is stopped by adding one drop of pyridine. .sup.1H-NMR spectroscopic investigation shows >97% conversion with formation of the hydrosilylation product PhCH(CH.sub.3)CH.sub.2SiPh(CH.sub.3).sub.2.

EXAMPLE 2

[0065] 148 mg (1.00 mmol) of pentamethyldisiloxane in 0.5 ml of d.sub.2-dichloromethane are mixed with a solution of 118 mg (1.00 mmol) of -methylstyrene in 0.5 ml of d.sub.2-dichloromethane and a solution of 1.0 mg (1.0 mol, 0.11 mol %) of trityl tetraakis(pentafluorophenyl)borate in 0.5 ml of d.sub.2-dichloromethane is added. After a reaction time of 10 min, the reaction is stopped by adding one drop of pyridine. .sup.1H-NMR spectroscopic investigation shows quantitative conversion with formation of the hydrosilylation product PhCH(CH.sub.3)CH.sub.2Si(CH.sub.3).sub.2OSi(CH.sub.3).sub.3.

EXAMPLE 3

[0066] 118 mg (1.00 mmol) of triethylsilane in 0.5 ml of d.sub.2-dichloromethane are mixed with a solution of 119 mg (1.01 mmol) of -methyl styrene in 0.5 ml of d.sub.2-dichloromethane and a solution of 1.0 mg (1.0 mol, 0.11 mol %) of trityl tetraakis(pentafluorophenyl)borate in 0.5 ml of d.sub.2-dichloromethane is added. The reaction is monitored by .sup.1H-NMR spectroscopy. After 19 min. the conversion is 79%, after 73 min. 88% and after 130 min. the conversion is quantitative with formation of the hydrosilylation product PhCH(CH.sub.3)CH.sub.2Si(CH.sub.2Si(CH.sub.3).sub.3.

EXAMPLE 4

[0067] 136 mg (1.00 mmol) of dimethylphenylsilane in 0.5 ml of d.sub.2-dichloromethane are mixed with a solution of 85 mg (1.00 mmol) of 1-hexene in 0.5 ml of d.sub.2-dichloromethane and a solution of 0.9 mg (1.0 mol, 0.10 mol %) of trityl tetraakis(pentafluorophenyl)borate in 0.5 ml of d.sub.2-dichloromethane is added and mixed by stirring. After 5 hours at room temperature, the solution is mixed with 1 drop of pyridine and the amount of product is determined by gas chromatography. Approx. 65% of the hydrosilylation product dimethylhexylphenylsilane was formed.