INHIBITED NOBLE METAL-FREE MIXTURE THAT CAN BE HYDROSILYLATED

Abstract

The invention provides a mixture M containing compound A which contains at least one hydrogen atom bound directly to Si, compound B which contains at least one carbon-carbon multiple bond, compound C which contains at least one cationic Si(II) group and compound D which contains at least one alkoxy group bound directly to silicon, and also a method for hydrosilylating the mixture M, wherein the mixture M is heated.

Claims

1. A mixture M containing; compound A which contains al least one hydrogen atom bound directly to Si; compound B which contains at least one carbon-carbon multiple bond; compound C which contains at least one cationic Si(II) group; and compound D which contains at least one alkoxy group bound directly to silicon, wherein the molar ratio of the compounds A and B, based on SiH groups present and unsaturated carbon groups, is at least 1:100 and not more than 100:1, wherein the molar ratio between the compound C and the SiH groups present in the compound A is at least 1:10.sup.7 and not more than 1:1, and wherein the molar ratio of the compounds C and D, based on the cationic Si(II) groups present in the compound C, to the alkoxy groups bound directly to silicon in the compound D is at least 1:1 and not more than 1:200.

2. A method for hydrosilylating a mixture M of claim 1, wherein the mixture M is heated to at least 40 C. and not more than 150 C.

3. The mixture M of claim 1, wherein the compound A has the general formula I
R.sup.1R.sup.2R.sup.3SiH(1), where the radicals R.sup.1, R.sup.2 and R.sup.3 are each, independently of one another, hydrogen, halogen, a silyloxy radical or a hydrocarbon radical, in which individual carbon atoms can in each case be replaced by oxygen atoms, silicon atoms, nitrogen atoms, halogen, sulfur or phosphorus atoms.

4. The mixture M of claim 3, wherein the compound B is selected from among compounds of the general formula IIIa
R.sup.4R.sup.5CCR.sup.6R.sup.7(IIIa), and compounds of the genera formula IIIb
R.sup.8CCR.sup.9(IIIb), where R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are each, independently of one another, a linear, branched, acyclic or cyclic, saturated or monounsaturated or polyunsaturated C1-C20-hydrocarbon radical, in which individual carbon atoms can be replaced by silicon, oxygen, halogen, nitrogen, sulfur or phosphorus.

5. The mixture M of claim 4, wherein the compound C is a cationic Si(II) compound of the general formula IV
([Si(II)Cp].sup.+).sub.nX.sup.a(IV) where Cp is a -bonded cyclopentadienyl radical of the general formula V, which is substituted by the radicals R.sup.y, ##STR00004## the radicals R.sup.y are monovalent radicals or polyvalent radicals which can also be joined to one another to form fused rings, and X.sup. is an a-valent anion which does not react with the cationic silicon(II) center under the reaction conditions of a hydrosilylation.

6. The mixture M of claim 4, wherein the compound C is selected from among the cationic Si(II) compounds: ##STR00005## where the radicals R.sup.a are, independently of one another, hydrocarbon radicals and Hal is halogen.

7. The mixture M of claim 5, wherein compound D has the general formula VI
R.sup.13R.sup.14R.sup.15SiOCH.sub.2R.sup.16(VI) where the radicals R.sup.13, R.sup.14 and R.sup.15 are each, independently of one another, hydrogen, halogen, a silyloxy radical, or a hydrocarbon radical, in which individual carbon atoms can in each case be replaced by oxygen atoms, halogen, sulfur or phosphorus atoms, and R.sup.16 is hydrogen or a hydrocarbon radical in which individual nonadjacent carbon atoms can be replaced by oxygen atoms, silicon, halogen, sulfur or phosphorus atoms.

8. (canceled)

9. (canceled)

10. The mixture M of claim 6, wherein compound D has the general formula VI
R.sup.13R.sup.14R.sup.15SiOCH.sub.2R.sup.16(VI) where the radicals R.sup.13, R.sup.14 and R.sup.15 are each, independently of one another, hydrogen, halogen, a silyloxy radical, or a hydrocarbon radical, in which individual carbon atoms can in each case be replaced by oxygen atoms, halogen, sulfur or phosphorus atoms, and R.sup.16 is hydrogen or a hydrocarbon radical in which individual nonadjacent carbon atoms can be replaced by oxygen atoms, silicon, halogen, sulfur or phosphorus atoms.

Description

EXAMPLE 1

[0063] A mixture of 239 mg (2.02 mmol) of -methylstyrene and 300 mg (2.02 mmol) of pentamethyldisiloxane is admixed under an inert gas atmosphere (argon) with a solution of 1.8 mg (2.14 mol) of the compound (-Me.sub.5C.sub.5)Si.sup.+ B(C.sub.6F.sub.5).sub.4.sup. and 4.8 mg (0.041 mmol) of ethoxytrimethylsilane in 540 mg of dideuterodichloromethane with shaking and allowed to stand at 25 C. for 8 days. The reaction mixture is examined by NMR spectroscopy after this time: -methylstyrene and pentamethyldisiloxane are present in an unchanged amount, and no hydrosilylation product can be detected. The catalyst (-Me.sub.5C.sub.5)Si.sup.+ B(C.sub.6F.sub.5).sub.4.sup. is detectable in an unchanged amount by NMR spectroscopy (singlet at =2.2 ppm). The sample is subsequently heated at 60 C. for 1 hour and then examined again by NMR spectroscopy: formation of the hydrosilylation product, 1,1,1,3,3-pentamethyl-3-(2-phenylpropyl)disiloxane, conversion >99%.

EXAMPLE 2

[0064] A mixture of 239 mg (2.02 mmol) of -methylstyrene and 300 mg (2.02 mmol) of pentamethyldisiloxane is admixed under an inert gas atmosphere (argon) with a solution of 1.7 mg (2.02 mol) of the compound (-Me.sub.5C.sub.5)Si.sup.+ B(C.sub.6F.sub.5).sub.4.sup. and 7.8 mg (0.041 mmol) of ethoxypentamethyldisiloxane in 860 mg of dideuterodichloromethane with shaking and allowed to stand at 25 C. for 9 days. The reaction mixture is examined by NMR spectroscopy after this time: -methylstyrene and pentamethyldisiloxane are present in an unchanged amount, and no hydrosilylation product can be detected. The catalyst (-Me.sub.5C.sub.5)Si.sup.+ B(C.sub.6F.sub.5).sub.4.sup. is detectable in an unchanged amount by NMR spectroscopy (singlet at =2.2 ppm).

[0065] The sample is subsequently heated at 60 C. for 1 hour and then examined again by NMR spectroscopy: formation of the hydrosilylation product, 1,1,1,3,3-pentamethyl-3-(2-phenylpropyl)disiloxane, conversion >99%.

EXAMPLE 3

[0066] A mixture of 239 mg (2.02 mmol) of -methylstyrene and 300 mg (2.02 mmol) of pentamethyldisiloxane is admixed under an inert gas atmosphere (argon) with a solution of 1.9 mg (2.26 mol) of the compound (-Me.sub.5C.sub.5)Si.sup.+ B(C.sub.6F.sub.5).sub.4.sup. and 7.5 mg (0.042 mmol) of dimethylphenylethoxysilane in 741 mg of dideuterodichloromethane with shaking and allowed to stand at 25 C. for 8 days. The reaction mixture is examined by NMR spectroscopy after this time: -methylstyrene and pentamethyldisiloxane are present in an unchanged amount, and no hydrosilylation product can be detected. The catalyst (-Me.sub.5C.sub.5)Si.sup.+ B(C.sub.6F.sub.5).sub.4.sup. is detectable in an unchanged amount by NMR spectroscopy (singlet at =2.2 ppm).

[0067] The sample is subsequently heated at 60 C. for 1 hour and then examined again by NMR spectroscopy: formation of the hydrosilylation product, 1,1,1,3,3-pentamethyl-3-(2-phenylpropyl)disiloxane, conversion >99%.

EXAMPLE 4, NOT ACCORDING TO THE INVENTION

[0068] Analogous to example 1 using B(C.sub.6F.sub.5).sub.3 instead of (-Me.sub.5C.sub.5)Si.sup.+ B(C.sub.6F.sub.5).sub.4.sup..

Hydrosilylation with Addition of Inhibitor

[0069] A mixture of 289 mg (2.02 mmol) of -methylstyrene and 300 mg (2.02 mmol) of pentamethyldisiloxane is admixed under an inert gas atmosphere (argon) with a solution of 1.8 mg (2.14 mol) of the compound (-Me.sub.5C.sub.5)Si.sup.+ B(C.sub.6F.sub.5).sub.4.sup. in 540 mg of dideuterodichloromethane with shaking and allowed to stand at 25 C. for 20 minutes and after this time is examined by NMR spectroscopy. The hydrosilylation to form the hydrosilylation product has proceeded to completion.