Selective 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 . 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 tris-substituted rhodium choloride 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 reactant 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 6  
   
       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 . (canceled) 
     
     
         6 . (canceled) 
     
     
         7 . (canceled) 
     
     
         8 . (canceled) 
     
     
         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 . (canceled) 
     
     
         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 . 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 unsaturated polyalkylene oxide. 
     
     
         15 . (canceled) 
     
     
         16 . (canceled) 
     
     
         17 . (canceled) 
     
     
         18 . (canceled) 
     
     
         19 . (canceled) 
     
     
         20 . The method of  claim 1 , wherein a first step precious metal hydrosilylation catalyst is tris(dibutylsulfide) rhodium chloride. 
     
     
         21 . The method of  claim 1 , wherein a first step precious metal hydrosilylation 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 - 81 . (canceled) 
     
     
         82 . The method of  claim 1 , further comprising incorporating the asymmetric organosiloxane as a hydrolysis resistant-imparting agent into a composition in need of hydrolysis resistance. 
     
     
         83 . The method of  claim 1 , comprising incorporating the asymmetrically substituted organosiloxane as a wetting agent or surfactant into a coating composition. 
     
     
         84 . The method of  claim 1 , comprising incorporating the asymmetrically substituted organosiloxane as an adjuvant into an agricultural or horticultural formulation, comprising a pesticide 
     
     
         85 . The method of  claim 1 , further comprising incorporating the asymmetrically substituted organosiloxane into a fungicide composition, comprising at least one active fungicide. 
     
     
         86 . The method of  claim 1 , further comprising incorporating the asymmetrically substituted organosiloxane into a pesticidal composition, comprising at least one active pesticide. 
     
     
         87 . A method to make an asymmetrically substituted organosiloxane comprising in a first step, reacting a molar excess up to less than 4:1 of a dihydridosiloxane under hydrosilylation conditions in the presence of a tris(triphenylphosphine) rhodium chloride catalyst with 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 asymmetrically substituted organosiloxane contains at least one polyalkylene oxide group. 
     
     
         88 . The method of  claim 82 , wherein the second and different hydrocarbon or heterocarbon compound 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, wherein a, b and c are zero or positive, where the subscript d may be 0 or 1; and R 16  is H, a monofunctional hydrocarbon radical of 1 to 6 carbons, or acetyl. 
     
     
         89 . The method of  claim 82 , wherein the second and different hydrocarbon or heterocarbon compound 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 - wherein a, b and c are zero or positive. 
     
     
         90 . The method of  claim 82 , wherein the second and different hydrocarbon or heterocarbon compound 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. 
     
     
         91 . The method of  claim 82 , comprising reacting the dihydridosiloxane with a vinylsilane. 
     
     
         92 . The method of  claim 82 , 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. 
     
     
         93 . The method of  claim 82 , further comprising incorporating the asymmetrically substituted organosiloxane as a hydrolysis resistant-imparting agent into a composition in need of hydrolysis resistance.