Selective hydrosilylation rhodium catalyst 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 . A method to make an asymmetric organosiloxane comprising in a first step, reacting a dihydridosiloxane under hydrosilylation conditions in the presence of a rhodium hydrosilylation catalyst, with an hydrocarbon or heterocarbon compound containing a terminal carbon to carbon double bond 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 . (canceled) 
     
     
         3 . (canceled) 
     
     
         4 . The method of  claim 1 , wherein a polyalkylene oxide react ant comprises 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 .- 9 . (canceled) 
     
     
         10 . 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. 
     
     
         11 . (canceled) 
     
     
         12 . 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. 
     
     
         13 . The method of  claim 1 , comprising reacting the dihydridosiloxane with a vinylsilane and hydrosilylating the formed monohydridosiloxane in the second step with a terminally unsaturated polyalkylene oxide. 
     
     
         14 . (canceled) 
     
     
         15 . The method of  claim 1 , comprising reacting the dihydridosiloxane with an olefin selected from the group consisting of 1-octene, 1-hexene, amylene, and 1-octadecene. 
     
     
         16 . The method of  claim 1 , comprising reacting the dihydridosiloxane with an olefin. 
     
     
         17 . The method of  claim 1 , comprising reacting the dihydridosiloxane with an olefin started alcohol. 
     
     
         18 . The method of  claim 1 , comprising reacting the dihydridosiloxane with an olefin substituted epoxide. 
     
     
         19 . (canceled) 
     
     
         20 . The method of  claim 1 , wherein a first step catalyst is tris(dibutylsuifide) rhodium trichloride. 
     
     
         21 . The method of  claim 1 , wherein a first step catalyst, is tris(triphenylphosphine) rhodium chloride. 
     
     
         22 . The method of  claim 1 , wherein the monohydridosiloxane is reacted in the presence of a hexachloroplatinic acid catalyst. 
     
     
         23 . (canceled) 
     
     
         24 . (canceled) 
     
     
         25 . (canceled) 
     
     
         26 . The method of  claim 1 , wherein a molar ratio of the dihydridosiloxane compound to the olefin in the first step hydrosilylation 1.3:1 to 1:1. 
     
     
         27 . (canceled) 
     
     
         28 . (canceled) 
     
     
         29 . The method of  claim 1 , wherein the first step catalyst is trichlorotris(dibutyl sulfide)rhodium (III). 
     
     
         30 .- 36 . (canceled) 
     
     
         37 . 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. 
     
     
         38 . 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. 
     
     
         39 .- 42 . (canceled) 
     
     
         43 . A method to form an asymmetric siloxane, comprising effecting a monoselective hydrosilylation reaction between a molar excess of a dihydridosiloxane and a first aliphatic unsaturated compound in the presence of a rhodium hydrosilylation catalyst to form a monohydridosiloxane; and hydrosilylating the monohydridosiloxane with alkylene oxide compound to form an asymmetric siloxane. 
     
     
         44 .- 81 . (canceled) 
     
     
         82 . The method of  claim 1 , wherein the first step catalyst is tri(dibutyl)rhodium chloride. 
     
     
         83 . An asymmetric organosiloxane product of the method of  claim 1 .