Selective molar excess hydrosilylation method and product

Abstract

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 .