SELECTIVE MOLAR EXCESS HYDROSILYLATION METHOD AND PRODUCT
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 olefinic compound and in a second step, a monohydridosiloxane produced in the first step is reacted under hydrosilylating conditions with another olefinic compound different from the first olefinic compound.
1 . (canceled)
2 . (canceled)
3 . (canceled)
4 . The method of claim 41 , wherein the compound with an unsaturated double bond is a polyalkylene oxide reactant comprising a polyether defined by the general formula:
CH 2 ═CH(R 13 )(R 12 ) d O(C 2 H 4 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.
5 . The method of claim 41 , wherein the compound with an unsaturated double bond is a polyalkylene oxide reactant comprising a polyether having mixed oxyalkylene oxide groups.
6 . The method of claim 41 , wherein the compound with an unsaturated double bond is a polyalkylene oxide reactant comprising a polyether having an oxyethylene group and at least one different oxyalkylene group.
7 . The method of claim 41 , wherein the compound with an unsaturated double bond is a polyalkylene oxide reactant comprising a polyether having an oxypropylene group and at least one different oxyalkylene group.
8 . The method of claim 41 , wherein the compound with an unsaturated double bond is a polyalkylene oxide reactant comprising a polyether having an oxybutylene group and at least one different oxyalkylene group.
9 . The method of claim 41 , wherein the compound with an unsaturated double bond is a polyalkylene oxide reactant comprising 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 -.
10 . The method of claim 41 , wherein the compound with an unsaturated double bond is a polyalkylene oxide reactant comprising 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.
11 . The method of claim 41 , comprising reacting the dihydridosiloxane with a vinylsilane.
12 . The method of claim 41 , 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.
13 . The method of claim 41 , comprising reacting the dihydridosiloxane with a vinylsilane and hydrosilylating the formed monohydridosiloxane in the second step with a terminally unsaturated polyalkylene oxide.
14 . The method of claim 41 , 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 unsaturated polyalkylene oxide.
15 . The method of claim 41 , comprising reacting the dihydridosiloxane with an olefin selected from the group consisting of 1-octane, 1-hexene, amylene, and 1-octadecene.
16 . The method of claim 41 , comprising reacting the dihydridosiloxane with an olefin.
17 . The method of claim 41 , comprising reacting the dihydridosiloxane with an olefin started alcohol.
18 . The method of claim 41 , comprising reacting the dihydridosiloxane with an olefin substituted epoxide.
19 . The method of claim 41 , comprising reacting the dihydridosiloxane with an olefin substituted epoxide selected from the group consisting of allyl glycidyl ether and vinylcyclohexene monoxide.
20 . The method of claim 41 , wherein the rhodium hydrosilylation catalyst is tris(dibutylsulfide) rhodium trichloride.
21 . The method of claim 41 , wherein rhodium hydrosilylation catalyst is tris(triphenylphosphine) rhodium chloride.
22 - 24 . (canceled)
25 . The method of claim 41 , wherein a molar ratio of the dihydridosiloxane compound greater than 1.1:1.
26 . The method of claim 41 , wherein a molar ratio of the dihydridosiloxane compound is 1.3:1 to 1:1.
27 . The method of claim 41 , wherein a molar ratio of the dihydridosiloxane compound is about 1:1.
28 . The method of claim 41 , wherein the catalyst is a complex of Rh(III) or Rh(I).
29 . The method of claim 41 , wherein the catalyst is trichlorotris (dibutyl sulfide) rhodium (III).
30 - 32 . (canceled)
33 . The method of claim 41 , comprising employing from 1000 ppm to 0.5 ppm of a catalyst.
34 . The method of claim 41 , comprising employing from 10 ppm to 3 ppm of a the catalyst.
35 . The method of claim 41 , wherein the hydrosilylation is conducted at a temperature in a range of 0 to 120° C.
36 . The method of claim 41 , wherein the hydrosilylation 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.
37 . The method, of claim 41 , wherein the hydrosilylation is conducted in a batch process, a continuous process, or by a staged temperature controlled, addition of reactants.
38 . The method of claim 1 , wherein the hydrosilylation is conducted in a hatch process, a continuous process, or by a staged temperature controlled addition of reactants.
39 . The method of claim 41 , conducted in the absence of a compatibilizing agent or solvent.
40 . The method of claim 41 , conducted in a compatibilizing agent or solvent that is stripped or distilled at completion.
41 . A method to form a monohydridosiloxane, comprising effecting a hydrosilylation of a molar excess of greater than 1:1 up to less than 4:1 of dihydridosiloxane of 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 such that 0≦x≦10, in the presence of a rhodium hydrosilylation catalyst, with a compound having an aliphatic unsaturated double bond; where D=(R) 2 SiO, and x is an integer 0≦x≦10; each of R, R 1 , R 2 , R 4 and R 5 is independently the same or different and each is a hydrocarbon radical, an alkoxy radical or alkenyloxy radical; and recovering a monohydridosiloxane.
42 - 81 . (canceled)
82 . A monohydridosiloxane product of the method of claim 41 .