Assembly for hydrosylilation, method for preparing same and silicone compositions incorporating same

Abstract

Process for preparing catalyst assemblies by mixing a metal catalyst capable of catalyzing a hydrosilylation reaction and an organophosphorus inhibitor of the formula (I) or of formula (VIII) P(OR) 3 , either by mixing the inhibitor into a solution of catalyst in an unsaturated silane or siloxane or by mixing the inhibitor into a gum or oil at a temperature greater than the melting temperature or softening temperature of the organophosphorus compound, then mixing the catalyst. Catalyst assemblies, process for preparing one-component silicone compositions, and resultant compositions.

1 - 38 . (canceled)  
     
     
         39 . A process for preparing a hydrosilylation-crosslinkable one-component silicone composition comprising at least one polyorganosiloxane (POS) A bearing ethylenic and/or acetylenic unsaturation(s), at least one polyorganohydrosiloxane (POS) B, a hydrosilylation catalyst and an inhibitor which is an organophosphorus compound inhibiting the action of the catalyst at room temperature, said process comprising premixing said hydrosilylation catalyst and said inhibitor to form a catalyst/inhibitor additive and then combining said additive with said at least one polyorganosiloxane (POS) A bearing ethylenic and/or acetylenic unsaturation(s) and said at least one polyorganohydrosiloxane (POS) B, wherein said inhibitor is of the following formula (I):  
       
         
           
           
               
               
           
         
       
       in which: 
 R, R 1 , R 2 , R 3  and R 4 , which are identical or different, represent a linear, branched or cyclic alkyl radical or an aryl radical which is substituted or unsubstituted, especially:  
 i. a linear or branched alkyl radical having particularly 2 to 30 carbon (C) atoms, preferably 2 to 12 C,  
 ii. an alkyl radical containing one or more rings, especially 1 or 2, it being possible in particular for one ring to have 4 to 14 C, preferably 5 to 8 C, or  
 iii. an aryl or alkylaryl radical containing one or more fused or unfused aromatic rings, especially 1 or 2 rings, it being possible for one ring to contain 4 to 14 C, preferably 6 to 8 C, which is or are optionally substituted by 1 or more, especially 1 to 2, linear or branched alkyl(s), especially having 1 to 12 C, preferably 4 to 12 C; or wherein the inhibitor is of formula (VIII) P(OR) 3  in which R is an alkylaryl radical having in particular 7 to 31 carbon atoms, preferably substituted phenyl radicals.  
 
     
     
         40 . The process according to  claim 39 , wherein in the formula (I), R is a cyclic alkyl radical or an aryl radical, preferably biphenyl.  
     
     
         41 . The process according to  claim 39 , wherein in the formula (I), R 1 , R 2 , R 3  and R 4  are cyclic alkyl radicals, aryl radicals or alkylaryl radicals, preferably substituted phenyl radicals.  
     
     
         42 . The process according to  claim 39 , wherein the inhibitor is of the formula (II):  
       
         
           
           
               
               
           
         
       
       in which the radicals R 5 , which are identical or different, preferably identical, are linear or branched alkyls having in particular 1 to 12 C, preferably 4 to 12 C, and preferably represent t-Bu.  
     
     
         43 . The process according to  claim 39 , wherein the inhibitor is of the formula (IX):  
       
         
           
           
               
               
           
         
       
       in which R 1 , R 2 , R 3 , R 4  and R 5 , which are identical or different, represent H, a linear or branched aliphatic radical, saturated, of formula C n H 2n+1 , or unsaturated, of formula C m H 2m−1 , or a radical of formula C n F 2n+1 , with n=1 to 15 and m=3 to 15, it not being possible for all of these radicals together to represent H.  
     
     
         44 . The process according to  claim 39 , wherein the inhibitor is:  
       
         
           
           
               
               
           
         
       
     
     
         45 . The process according to  claim 39 , wherein the catalyst is a platinum/unsaturated siloxane complex, especially a platinum/vinylsiloxane complex, preferably a Karstedt complex.  
     
     
         46 . The process according to  claim 39 , wherein the additive is obtained by dispersing the inhibitor in a solution of the catalyst in an unsaturated silane or siloxane, preferably vinylsiloxane.  
     
     
         47 . The process according to  claim 46 , wherein the additive is obtained by dispersing the inhibitor in a platinum/unsaturated siloxane catalyst solution, in particular a platinum/vinylsiloxane catalyst solution, preferably Karstedt solution.  
     
     
         48 . The process according to  claim 39 , wherein the additive is obtained by mixing the inhibitor in a silicone gum or oil at a temperature greater than the melting temperature or softening temperature of the inhibitor, followed by addition of the catalyst.  
     
     
         49 . A process for preparing a catalyst additive or assembly comprising a metallic hydrosilylation catalyst and an organophosphorus compound which inhibits the catalytic action of the catalyst at room temperature, said process comprising adding said organophosphorus compound to a silicone gum or oil and dispersing said organophosphorus compound in said silicone gum or oil at a temperature greater than the melting temperature or softening temperature of said organophosphorus compound, and then mixing said catalyst into the composition thus obtained.  
     
     
         50 . The process according to  claim 49 , comprising first dispersing said organophosphorus compound in said oil or gum and then heating the resultant mixture to a temperature greater than the melting temperature or softening temperature of the organophosphorus compound.  
     
     
         51 . The process according to  claim 49 , wherein the composition formed from the silicone gum or oil and the organophosphorus inhibitor is cooled, in particular at room temperature, prior to mixing said composition with said catalyst.  
     
     
         52 . A process for preparing a catalyst additive or assembly comprising a metallic hydrosilylation catalyst and an organophosphorus compound which inhibits the catalytic activity of the catalyst at room temperature, comprising mixing a solution or dispersion of said metal catalyst in an unsaturated silane or siloxane, preferably vinylsiloxane, with said organophosphorus compound.  
     
     
         53 . The process according to  claim 49 , wherein the catalyst is a platinum/unsaturated silane or platinum/unsaturated siloxane solution, in particular a platinum/vinylsiloxane solution and preferably a Karstedt solution.  
     
     
         54 . The process according to  claim 49 , wherein the organophosphorus compound is selected from organophosphorus compounds of formula (I):  
       
         
           
           
               
               
           
         
       
       in which: 
 R, R 1 , R 2 , R 3  and R 4 , which are identical or different, represent a linear, branched or cyclic alkyl radical or an aryl radical which is substituted or unsubstituted, especially:  
 iv. a linear or branched alkyl radical having particularly 2 to 30 carbon (C) atoms, preferably 2 to 12 C,  
 v. an alkyl radical containing one or more rings, especially 1 or 2, it being possible in particular for one ring to have 4 to 14 C, preferably 5 to 8 C, or  
 vi. an aryl or alkylaryl radical containing one or more fused or unfused aromatic rings, especially 1 or 2 rings, it being possible for one ring to contain 4 to 14 C, preferably 6 to 8 C, which is or are optionally substituted by 1 or more, especially 1 to 2, linear or branched alkyl(s), especially having 1 to 12 C, preferably 4 to 12 C, or wherein the inhibitor is of the formula (VIII) P(OR) 3  in which R is an alkylaryl radical having in particular 7 to 31 carbon atoms, preferably substituted phenyl radicals.  
 
     
     
         55 . The process according to  claim 54 , wherein the inhibitor is of the following formula (IX):  
       
         
           
           
               
               
           
         
       
       in which R 1 , R 2 , R 3 , R 4  and R 5 , which are identical or different, represent H, a linear or branched aliphatic radical, saturated, of formula C n H 2n+1 , or unsaturated, of formula C m H 2m−1 , or a radical of formula C n F 2n+1 , with n=1 to 15 and m=3 to 15, it not being possible for all of these radicals together to represent H.  
     
     
         56 . The process according to  claim 54 , wherein the inhibitor is of the following formula (X):  
       
         
           
           
               
               
           
         
       
     
     
         57 . An additive comprising a hydrosilylation catalyst and an organophosphorus compound which inhibits the catalytic action of the catalyst at room temperature, obtainable by the process according to  claim 49 .  
     
     
         58 . A catalyst assembly comprising, in an organosilicone solvent such as an unsaturated silane, an unsaturated siloxane, a silicone oil or a silicone gum, a metal catalyst capable of catalyzing a hydrosilylation reaction and an inhibitor of the following formula (I):  
       
         
           
           
               
               
           
         
       
       in which: 
 R, R 1 , R 2 , R 3  and R 4 , which are identical or different, represent a linear, branched or cyclic alkyl radical or an aryl radical which is substituted or unsubstituted, especially:  
 i. a linear or branched alkyl radical having particularly 2 to 30 carbon (C) atoms, preferably 2 to 12 C,  
 ii. an alkyl radical containing one or more rings, especially 1 or 2, it being possible in particular for one ring to have 4 to 14 C, preferably 5 to 8 C, or  
 iii. an aryl or alkylaryl radical containing one or more fused or unfused aromatic rings, especially 1 or 2 rings, it being possible for one ring to contain 4 to 14 C, preferably 6 to 8 C, which is or are optionally substituted by 1 or more, especially 1 to 2, linear or branched alkyl(s), especially having 1 to 12 C, preferably 4 to 12 C, wherein the inhibitor inhibits the catalytic action of the catalyst at room temperature.  
 
     
     
         59 . The catalyst assembly according to  claim 58 , wherein R is a cyclic alkyl radical or an aryl radical, preferably biphenyl.  
     
     
         60 . The catalyst assembly according to  claim 58 , wherein R 1 , R 2 , R 3  and R 4  are cyclic alkyl radicals, aryl radicals or alkylaryl radicals, preferably substituted phenyl radicals.  
     
     
         61 . The catalyst assembly according to  claim 58 , wherein the inhibitor is of the formula (II):  
       
         
           
           
               
               
           
         
       
       in which the radicals R 5 , which are identical or different, preferably identical, are linear or branched alkyls having in particular 1 to 12 C, preferably 4 to 12 C.  
     
     
         62 . The catalyst assembly according to  claim 58 , wherein the inhibitor is of the formula (III):  
       
         
           
           
               
               
           
         
       
     
     
         63 . The catalyst assembly according to  claim 58 , wherein the molar ratios of the metal catalyst to inhibitor are between 1/0.5 and 1/10, preferably between 1/1 and 1/5.  
     
     
         64 . The catalyst assembly according to  claim 58 , wherein the metal catalyst is a platinum catalyst.  
     
     
         65 . The catalyst assembly according to  claim 64 , wherein the metal catalyst is a platinum/unsaturated siloxane complex, preferably a platinum/vinylsiloxane complex.  
     
     
         66 . The catalyst assembly according to  claim 64 , wherein the metal catalyst is a Karstedt complex.  
     
     
         67 . A catalyst assembly comprising the following chemical species:  
       
         
           
           
               
               
           
         
       
       in which: 
 R, R 1 , R 2 , R 3  and R 4 , which are identical or different, represent a linear, branched or cyclic alkyl radical or an aryl radical which is substituted or unsubstituted, especially:  
 iv. a linear or branched alkyl radical having particularly 2 to 30 carbon (C) atoms, preferably 2 to 12 C,  
 v. an alkyl radical containing one or more rings, especially 1 or 2, it being possible in particular for one ring to have 4 to 14 C, preferably 5 to 8 C, or  
 vi. an aryl or alkylaryl radical containing one or more fused or unfused aromatic rings, especially 1 or 2 rings, it being possible for one ring to contain 4 to 14 C, preferably 6 to 8 C, which is or are optionally substituted by 1 or more, especially 1 to 2, linear or branched alkyl(s), especially having 1 to 12 C, preferably 4 to 12 C.  
 
     
     
         68 . A catalyst assembly comprising the following chemical species:  
       
         
           
           
               
               
           
         
       
       in which the radicals R 5 , which are identical or different, preferably identical, are linear or branched alkyls, having in particular 1 to 12 C, preferably 4 to 12 C.  
     
     
         69 . A catalyst assembly comprising the following chemical species:  
       
         
           
           
               
               
           
         
       
     
     
         70 . A hydrosilylation-crosslinkable silicone composition comprising at least one polyorganosiloxane (POS) A bearing ethylenic and/or acetylenic unsaturation(s), at least one polyorganohydrosiloxane (POS) B, a hydrosilylation catalyst and an inhibitor of formula (I):  
       
         
           
           
               
               
           
         
       
       in which: 
 R, R 1 , R 2 , R 3  and R 4 , which are identical or different, represent a linear, branched or cyclic alkyl radical or an aryl radical which is substituted or unsubstituted, especially:  
 vii. a linear or branched alkyl radical having particularly 2 to 30 carbon (C) atoms, preferably 2 to 12 C,  
 viii. an alkyl radical containing one or more rings, especially 1 or 2, it being possible in particular for one ring to have 4 to 14 C, preferably 5 to 8 C, or  
 ix. an aryl or alkylaryl radical containing one or more fused or unfused aromatic rings, especially 1 or 2 rings, it being possible for one ring to contain 4 to 14 C, preferably 6 to 8 C, which is or are optionally substituted by 1 or more, especially 1 to 2, linear or branched alkyl(s), especially having 1 to 12 C, preferably 4 to 12 C.  
 
     
     
         71 . The composition according to  claim 70 , wherein the silicone composition is of the high-temperature-vulcanizable composition type or of the room-temperature-vulcanizable type.  
     
     
         72 . The composition according to  claim 70 , wherein the POS A has a viscosity of at least 5×10 5  mPa.s, preferably between 1×10 6  and 1×10 7  mPa.s, at 25° C.  
     
     
         73 . The composition according to  claim 70 , wherein the POS A has a viscosity of between 1×10 4  and 5×10 5  mPa.s.  
     
     
         74 . The composition according to  claim 70 , wherein the POS A has a viscosity of between 100 and 10 4  mpa.s, preferably between 1000 and 5000 mPa.s, at 25° C.  
     
     
         75 . The composition according to  claim 70 , wherein the POS B has a viscosity of between 10 and 10 000 mpa.s, preferably between 50 and 1000 mPa.s, at 25° C.