Organosilicone compositions and methods for preparing them

Abstract

Disclosed herein is a composition comprising a structure (M 1 ) a (M E ) b )D 1 ) c (D 2 ) d (T) e (Q) f , wherein M 1 =R 1 R 2 R 3 SiO 1/2 ; M E =R 4 R 5 R E SiO 1/2 ; D 1 =R 6 R 7 SiO 2/2 ; D 2 =R 8 R 9 SiO 2/2 ; T=R 10 SiO 3/2 ; and Q=SiO 4/2 ; wherein each R E is independently a monovalent hydrocarbon radical containing an epoxy group; R 9 comprises a structure -L 1 -Si(R 11 ) g (OR 12 ) 3-g or L 2 (D 3 ) h (M 2 ) i -L 3 -Si(R 13 ) g′ (OR 14 ) 3-g′ , wherein L 1 , L 2 , and L 3 are independently divalent linking groups; g and g′ independently have a value from 0 to 2; M 2 =R 15 R 16 R 17 SiO 1/2 ; D 3 =R 18 R 19 SiO 2/2 ; wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 are independently monovalent hydrocarbon radicals; wherein a, b, c, d, e, f, h, and i are stoichiometric subscripts that are zero or positive subject to the following limitations: b has a value of 2; d is greater than or equal to 1; when (a+c+e+f) is equal to zero, (b+d) is greater than or equal to 3; and when i=0, h is at least 1.

1 . A composition comprising a structure:
   (M 1 ) a (M E ) b (D 1 ) c (D 2 ) d (T) e (Q) f      wherein M 1 =R 1 R 2 R 3 SiO 1/2 ; M E =R 4 R 5 R E SiO 1/2 ; D 1 =R 6 R 7 SiO 2/2 ; D 2 =R 8 R 9 SiO 2/2 ; T=R 10 SiO 3/2 ; and Q=SiO 4/2 ;   wherein each R E  is independently a monovalent hydrocarbon radical containing an epoxy group; R 9  comprises -L 1 -Si(R 11 ) g (OR 12 ) 3-g  or L 2 (D 3 ) h (M 2 ) i -L 3 -Si(R 13 ) g′ (OR 14 ) 3-g′ , wherein L 1 , L 2 , and L 3  are independently divalent linking groups; g and g′ independently have a value from 0 to 2; M 2 =R 15 R 16 R 17 SiO 1/2 ; D 3 =R 18 R 19 SiO 2/2 ;   wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and R 19  are independently monovalent hydrocarbon radicals;   wherein a, b, c, d, e, f, h, and i are stoichiometric subscripts that are zero or positive subject to the following limitations: b has a value of 2; d is greater than or equal to 1; when (a+c+e+f) is equal to zero, (b+d) is greater than or equal to 3; when i=0, h is at least 1.   
     
     
         2 . The composition of  claim 1 , wherein R E  has a structure: 
       
         
           
           
               
               
           
         
         wherein R 29 , R 30 , R 31 , R 32 , R 33 , and R 34  are independently selected from the group consisting of hydrogen atom and monovalent hydrocarbon radicals having from one to sixty carbon atoms, W 1  is a divalent or a trivalent hydrocarbon radical having from one to sixty carbon atoms, W 2  is a divalent hydrocarbon radical having from one to sixty carbon atoms, and subscripts p and q are independently zero or one subject to the limitation that when W 1  is trivalent, one of R 29  or R 31  is a hydrogen atom. 
       
     
     
         3 . The composition of  claim 1 , wherein R E  is selected from the group consisting of 
       
         
           
           
               
               
           
         
       
       ; or combinations thereof;
 wherein r has a value from 2 to 20. 
 
     
     
         4 . The composition of  claim 2 , wherein R 29 , R 30 , R 31 , R 32 , R 33 , and R 34  are hydrogen; and p and q are zero. 
     
     
         5 . The composition of  claim 1 , wherein L 1 , L 2 , and L 3  are independently derived from monovalent alkenyl groups. 
     
     
         6 . The composition of  claim 5 , wherein L 1 , L 2 , and L 3  are independently selected from the group consisting of 1-ethenyl, 1-propenyl, 1-butenyl, 1-pentenyl, and styrenyl. 
     
     
         7  . The composition of  claim 1 , wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and R 19  are independently selected from the group consisting of methyl, ethyl, sec-butyl, tert-butyl, octyl, decyl, butoxy, dodecyl, cetyl, hydroxypropyl, butoxy, 2,5,8-trioxadecyl, triacontyl, and 3,3,3-trifluoropropyl. 
     
     
         8 . The composition of  claim 1 , wherein R 11  and R 12  are independently selected from the group consisting of methyl, ethyl, propyl, n-butyl, cyclohexyl, phenyl, benzyl, sec-butyl, tert-butyl, octyl, decyl, dodecyl, cetyl, hydroxypropyl, butoxy, 2,5,8-trioxadecyl, triacontyl, and 3,3,3-trifluoropropyl. 
     
     
         9 . The composition of  claim 1 , wherein R 9  is —(CH 2 ) 2 Si(OC 2 H 5 ) 3 . 
     
     
         10 . The composition of  claim 1 , wherein R 9  has a structure, 
       
         
           
           
               
               
           
         
       
       wherein a′ has a value from 1 to 500, and D=(CH 3 ) 2 SiO 1/2 . 
     
     
         11 . A polymer composition comprising the products of reaction of the composition of  claim 1  and a polymer having at least one reactive end-group. 
     
     
         12 . The polymer composition of  claim 11 , wherein the reactive end-group is a carboxylic acid group. 
     
     
         13 . The polymer composition of  claim 12 , wherein the polymer is selected from the group consisting of polyesters and polyamides. 
     
     
         14 . A polymer composition comprising the products of reaction of the composition of  claim 1  and a polyester end-capped with carboxylic acid groups. 
     
     
         15 . The polymer composition of  claim 14 , wherein the the polymer end-capped with carboxylic acid groups is selected from the group consisting of polyesters and polyamides. 
     
     
         16 . A coating composition comprising the polymer composition of  claim 11 . 
     
     
         17 . A coating composition comprising the polymer composition of  claim 15 . 
     
     
         18 . The coating composition of  claim 16 , comprising a coating for metal, a coating for plastic, a coating for fabric, or a coating for paper. 
     
     
         19 . The coating composition of  claim 17 , comprising a coating for metal, a coating for plastic, a coating for fabric, or a coating for paper. 
     
     
         20 . A composition comprising a structure:
   (M E ) j (D 4 ) k (D 5 ) l ,   
       wherein M E =R 20 R 21 R E SiO 1/2 ; D 4 =R 22 R 23 SiO 2/2 ; and D 5 =R 24 R 25 SiO 2/2 ; wherein R 20 , R 21 , R 22 , R 23 , R 24 , and R 25  are independently monovalent hydrocarbon radicals; each R E  is independently a monovalent hydrocarbon radical containing an epoxy group, R 25 =-L 4 -Si(R 26 ) m (OR 27 ) 3-m , wherein L 4  is a divalent linking group, m has a value from 0 to 2, and R 26  and R 27  are independently monovalent hydrocarbon radicals; j has a value of 2; k is zero or greater than 1, and l is greater than or equal to 1. 
     
     
         21 . The composition of  claim 20 , wherein R 20 , R 21 , R 22 , R 23 , R 24 , and R 25  are independently selected from the group consisting of methyl, ethyl, sec-butyl, tert-butyl, octyl, decyl, dodecyl, cetyl, hydroxypropyl, butoxy, 2,5,8-trioxadecyl, triacontyl, and 3,3,3-trifluoropropyl. 
     
     
         22 . The composition of  claim 20 , wherein R 26  and R 27  are independently selected from the group consisting of methyl, ethyl, propyl, n-butyl, cyclohexyl, phenyl, benzyl, sec-butyl, tert-butyl, octyl, decyl, dodecyl, cetyl, hydroxypropyl, butoxy, 2,5,8-trioxadecyl, triacontyl, and 3,3,3-trifluoropropyl. 
     
     
         23 . The composition of  claim 20 , wherein R E  is 
       
         
           
           
               
               
           
         
       
     
     
         24 . A polymer composition comprising the products of reaction of the composition of  claim 22  and a polymer end-capped with carboxylic acid groups. 
     
     
         25 . A coating composition comprising the polymer composition of  claim 24 . 
     
     
         26 . A method for preparing a composition, comprising:
 reacting an organosilicon hydride having a structure (M 1 ) a (M H ) b (D 1 ) c (T) e (Q) f  with an epoxyolefin to form a first intermediate product having a structure (M 1 ) a (M E ) b (D 1 ) c (T) e (Q) f ; wherein M 1 =R 1 R 2 R 3 SiO 1/2 ; M H =R 4 R 5 HSiO 1/2 ; D 1 =R 6 R 7 SiO 2/2 ; T=R 10 SiO 3/2 ; Q=SiO 4/2 ; and M E =R 4 R 5 R E SiO 1/2 ; wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 10  are independently monovalent hydrocarbon radicals; each R E  is independently a monovalent hydrocarbon radical containing an epoxy group; and a, b, c, e, and f are stoichiometric subscripts that are zero or positive subject to the following limitations: b has a value such that 0≦b≦2; and when (a+c+e+f) is equal to zero, b is equal to 2;   reacting said first intermediate product with a cyclic siloxane having a structure (D 6 ) n  to form a second intermediate product having a structure (M 1 ) a (M E ) b (D 1 ) c (D 6 ) o (T) e (Q) f ; wherein D 6  is R 8 R 28 SiO 2/2 , wherein R 8  is a monovalent hydrocarbon radical, R 28  is a monovalent alkenyl group; a, b, c, e, f, n, and o are stoichiometric subscripts that are zero or positive subject to the following limitations: n is greater than or equal to 3; o is at least 1; b has a value of 2; and when (a+c+e+f) is equal to zero, (b+o) is greater than or equal to 3; and   reacting said second intermediate product with an (alkoxy)hydrosilane to form said composition having a structure (M 1 ) a (M E ) b (D 1 ) c (D 2 ) d (T) e (Q) f ; wherein M 1 =R 1 R 2 R 3 SiO 1/2 ; M E =R 4 R 5 R E SiO 1/2 ; D 1 =R 6 R 7 SiO 2/2 ; D 2 =R 8 R 9 SiO 2/2 ; T=R 10 SiO 3/2 ; and Q=SiO 4/2 ; wherein each R E  is independently a monovalent hydrocarbon radical containing an epoxy group; R 9  comprises a pendant functional organosilicon group comprising a structure -L 1 -Si(R 11 ) g (OR 12 ) 3-g  or L 2 (D 3 ) h (M 2 ) i -L 3 -Si(R 13 ) g′ (OR 14 ) 3-g′ , wherein L 1 , L 2 , and L 3  are independently divalent linking groups; g and g′ independently have a value from 0 to 2; M 2 =R 15 R 16 R 17 SiO 1/2 ; D 3 =R 18 R 19 SiO 2/2 ;   wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and R 19  are independently monovalent hydrocarbon radicals;   wherein a, b, c, d, e, f, h, and i are stoichiometric subscripts that are zero or positive subject to the following limitations: b has a value of 2; d is greater than or equal to 1; when (a+c+e+f) is equal to zero, (b+d) is greater than or equal to 3; and when i=0, h is at least 1.   
     
     
         27 . The method of  claim 26 , wherein said epoxyolefin has a structure:  
       
         
           
           
               
               
           
         
         wherein R 29 , R 30 , R 31 , R 32 , R 33 , and R 34  are independently selected from the group consisting of hydrogen atom and monovalent hydrocarbon radicals having from one to sixty carbon atoms, W 1  is a divalent or a trivalent hydrocarbon radical having from one to sixty carbon atoms, W 2  is a divalent hydrocarbon radical having from one to sixty carbon atoms, and the subscripts p and q are independently zero or one subject to the limitation that when W 1  is trivalent, one of R 29  or R 30  is a hydrogen atom. 
       
     
     
         28 . The method of  claim 27 , wherein said epoxyolefin is selected from the group consisting of limonene oxide, 1,2-epoxy-7-octene, 1,2-epoxy-9-decene, 1,2-epoxy-4-vinylcyclohexane, 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene, 3,4-epoxy-1-butene, allyl glycidyl ether, 1,2-epoxy-7-octene, 2,3-epoxy-5,6-norbornene, 2-(4-allyloxyphenyl)-2-(4-glycidyloxyphenyl)propane, and mixtures thereof. 
     
     
         29 . The method of  claim 26 , wherein e and f are zero, a is 1 or 2 with the limitation that (a+b)=2; and c has a value from 0-500. 
     
     
         30 . The method of  claim 28 , wherein R 8  is selected from the group consisting of methyl, ethyl, sec-butyl, tert-butyl, octyl, decyl, dodecyl, cetyl, butoxy, hydroxypropyl, 2,5,8-trioxadecyl, triacontyl, and 3,3,3-trifluoropropyl; R 28  is selected from the group consisting of 1-ethenyl, 1-propenyl, 1-butenyl, 1-pentenyl, and styrenyl; and n has a value of 3-6. 
     
     
         31 . The method of  claim 30 , wherein R 8  is methyl, R 28  is 1-ethenyl, and n is 4. 
     
     
         32 . The method of  claim 26 , wherein said (alkoxy)hydrosilane comprises triethoxysilane.