Selective hydrosilylation method
View Patent ↗An asymmetric siloxane is made by reacting a silicone having the formula M H D x M′ H where M H is R 1 R 2 HSiO 1/2 , M′ H is R 4 R 5 HSiO 1/2 and x is an integer 0≦x≦10 under selective hydrosilylation conditions in the presence of a precious metal hydrosilylation catalyst, with a first olefine compound and in a second step, a monohydridosiloxane produced in the first step is reacted under hydrosilylating condtions with another olefine compound different from the first olefine compound.
1. A method to make an asymmetric organosiloxane comprising in a first step, reacting a dihydridosiloxane under hydrosilylation conditions in the presence of a precious metal hydrosilylation catalyst, with a vinyl silane to form a monohydridosiloxane, and in a second step, hydrosilylating the monohydridosiloxane with a second and different hydrocarbon or heterocarbon compound containing a terminal carbon to carbon double bond and in the presence of the same or different hydrosilylation catalyst under hydrosilylation conditions to form an asymmetrically substituted organosiloxane, wherein the asymmetric organosiloxane product contains at least one polyalkylene oxide group.
2. The method of claim 1 , wherein a polyalkylene oxide reactant comprises a polyether defined by the general formula:
CH 2 ═CH(R 13 )(R 12 ) d O(C 2 H d O) a (C 3 H 6 O) b (C 4 H 8 O) c R 16
where R 13 is H or methyl; R 12 is a divalent alkyl radical of 1 to 6 carbons where the subscript d may be 0 or 1 and each of a, b and c is zero or positive; and R 16 is H, a monofunctional hydrocarbon radical of 1 to 6 carbons, or acetyl.
3. The method of claim 1 , wherein a polyalkylene oxide reactant comprises a polyether comprising a member selected from the group consisting of CH 2 ═CHCH 2 O(CH 2 CH 2 O) 8 H; CH 2 ═CHCH 2 O(CH 2 CH 2 O) 8 CH 3 ; CH 2 ═CHCH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 5 H; CH 2 ═CHO(CH 2 CH 2 O) 5 (CH 2 CH(CH 3 )O) 5 H; CH 2 ═C(CH 3 )CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 5 C(═O)CH 3 ; and CH 2 ═CHCH 2 O(CH 2 CH 2 O) 5 (CH 2 CH(CH 3 )O) 2 (CH 2 CH(CH 2 CH 3 )O) 2 H.
4. The method of claim 1 , comprising reacting the dihydridosiloxane with a vinylsilane selected from the group consisting of trimethylvinylsilane, triethylvinylsilane, dimethyl-tert-butoxyvinylsilane, dimethylisopropoxyvinylsilane, tris-(trimethylsiloxy)vinylsilane, methyl-bis-(tert-butoxy)vinylsilane and tris-(tert-butoxy)vinylsilane.
5. The method of claim 1 , comprising reacting the dihydridosiloxane with a vinylsilane and hydrosilylating the formed monohydridosiloxane in the second step with a terminally unsatured polyalkylene oxide.
6. The method of claim 1 , wherein the monohydridosiloxane is reacted in the presence of a hexachloroplatinic acid catalyst.
7. The method of claim 1 , wherein a molar ratio of the dihydridosiloxane compound to the vinyl silane in the first step hydrosilylation 1.3:1 to 1:1.
8. THe method of claim 1 , wherein the second step hydrosilylation of the monohydridosiloxane is catalyzed with a Speier's Catalyst [H 2 PtCl 6 ] or a Karstedt's Catalyst [Pt(H 2 C═CSiMe 2 OSiMe 2 CH═CH 2 ) n ].
9. The method of claim 1 , wherein the first step reaction is conducted in a batch process, a continuous process, or by a staged temperature controlled addition of reactants.
10. The method of claim 1 , wherein the second step hydrosilylation is conducted in a batch process, a continuous process, or by a staged temperature controlled addition of reactants.
11. A method to form an asymmetric siloxane, comprising effecting a monoselective hydrosilylation reaction between a molar excess of a dihydridosilance and a vinyl silane in the presence of a rhodium hydrosilylation catalyst to form a monohydridosiloxane; and hydrosilylating the monohydridosiloxane with an alkylene oxide compound to form an asymmetric siloxane.
12. The method of claim 1 , comprising reacting the monohydridosiloxane with a polyalkylene oxide having an alkenyl group of 2 to 10 carbon atoms.
13. The method of claim 1 , comprising reacting the monohydridosiloxane with an allyloxypolyethylene oxide or a methyallyloxypolyethylene oxide.
14. The method of claim 1 , wherein a polyalkylene oxide reactant comprises a polyether having mixed oxyalkylene oxide groups.
15. The method of claim 1 , wherein a polyalkylene oxide comprises a polyether having an oxyethylene group and at least one different oxyalkylene group.
16. The method of claim 1 , wherein a polyalkylene oxide comprises a polyether having an oxypropylene group and at least one different oxyalkylene group.
17. The method of claim 1 , wherein a polyalkylene oxide reactant comprises a polyether having an oxybutylene group and at least one different oxyalkylene group.
18. The method of claim 1 , wherein a polyalkylene oxide reactant comprises a polyether comprising a random or blocked configuration selected from the group consisting of -(oxyethylene) a (oxypropylene) b -, -(oxybutylene) c (oxyethylene) a - and -(oxypropylene) b (oxyethylene) a (oxybutylene) c -.
19. The method of claim 1 , comprising reacting the dihydridosiloxane with a vinylsilane selected from the group consisting of trimethylvinylsilane, triethylvinylsilane, dimethyl-tert-butoxyvinylsilane, dimethylisopropoxyvinylsilane, tris-(trimethylsiloxy)vinylsilane, methyl-bis-(tert-butoxy)vinylsilane and tris-(tert-butoxy)vinylsilane and hydrosilylating the formed monohydridosiloxane in the second step with a terminally unsatured polyalkylene oxide.
20. The method of claim 1 , comprising isolating the monohydridosiloxane reaction product of the first step.
21. The method of claim 1 , comprising isolating the monohydridosiloxane reaction product of the first step by distillation or stripping.
22. The method of claim 1 , wherein a molar ratio of the dihydridosiloxane compound to the vinyl silane in the first step hydrosilylation is 4:1 to 1.1:1.
23. The method of claim 1 , wherein a molar ratio of the dihydridosiloxane compound to the vinyl silane in the first step hydrosilylation is about 1:1.
24. The method of claim 1 , wherein the second step hydrosilylation of the monohydridosiloxane is catalyzed with a precious metal catalyst.
25. The method of claim 1 , wherein the second step hydrosilylation of the monohydridosiloxane is catalyzed with a rhodium, ruthenium, palladium, osmium, iridium or platinum complex.
26. The method of claim 1 , comprising employing from 1000 ppm to 0.5 ppm of a catalyst for either step.
27. The method of claim 1 , comprising employing from 10 ppm to 3 ppm to a catalyst in the first step or the second step.
28. The method of claim 1 , wherein the first step reaction or the second step hydrosilylation is conducted at a temperature in a range of 0 to 120° C.
29. The method of claim 1 , wherein the first step reaction is conducted at a temperature in a range of 20 to 80° C. and the second step hydrosilylation is conducted at a temperature of 80 to 100° C.
30. The method of claim 1 , conducted in the absence of a compatibilizing agent or solvent.
31. The method of claim 1 , conducted in a compatiblizing agent of solvent that is stripped or distilled at completion.
32. An asymmetric organosiloxane product of the method of claim 1 .