Hydrolysis resistant organomodified trisiloxane ionic surfactants

Abstract

The present invention provides for a composition comprising a siloxane having the formula: M 1 DM 2 wherein M 1 =(R 1 )(R 2 )(R 3 )SiO 1/2 ; M 2 =(R 4 )(R 5 )(R 6 )SiO 1/2 and D=(R 7 )(Z)SiO 2/2 where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently selected from the group consisting of 1 to 4 carbon monovalent hydrocarbon radicals, aryl, and a hydrocarbon group of 4 to 9 carbons containing an aryl group; Z is a pendant hydrophilic ionic group selected from the group consisting of R 8 —R A , R 9 —R C , and R 10 —R Z ; R A being an anionic substituent, R C a cationic substituent or R Z a zwitterionic substituent on the D group wherein the composition is resistant to hydrolysis under either basic or acidic conditions.

1 . A composition comprising a siloxane having the formula:
   M 1 DM 2      
       wherein
 M 1 =(R 1 )(R 2 )(R 3 )SiO 1/2 ; 
 M 2 =(R 4 )(R 5 )(R 6 )SiO 1/2  and 
 D=(R 7 )(Z)SiO 2/2    
 
       where R 1 , R 2 , R 3 , R 4 , R 5 , R 6  and R 7  are each independently selected from the group consisting of 1 to 4 carbon monovalent hydrocarbon radicals, aryl, and a hydrocarbon group of 4 to 9 carbons containing an aryl group;
 Z is a hydrophilic substituent selected from the group consisting of R 8 —R A , R 9 —R C , and R 10 —R Z ; 
 R 8  is a monovalent radical 
 
       
         
           
           
               
               
           
         
       
       of
 R 11 (O) t (R 12 ) u (O) v , R 13 —CHCH 2 CH(OH)CH(O—)CH 2 CH 2 ; and 
 R 14 O(C 2 H 4 O) a (C 3 H 6 O) b (C 4 H 8 O) c ; 
 where R 11  and R 12  are each independently selected from the group consisting of a divalent hydrocarbon group of 1 to 4 carbon atoms, that may each be optionally substituted with one or more OH radicals; 
 R 13  is a divalent hydrocarbon group of 2 to 4 carbon atoms; 
 R 14  is a divalent hydrocarbon group of 1 to 6 carbons, that may each be optionally branched; subscripts t, u and v are zero or 1; t 
 the subscripts a, b and c are zero or positive and satisfy the following relationships:
   1 ≦a+b+c≦ 10 with a≧1; 
 
 R A  is a monovalent radical selected from the group consisting of SO 3 M K , —C(═O)CH 2 CH(R 15 )COOM K ; —PO 3 H M K ; COOM K ; where R 15  is H or SOM K ; 
 M K  is a cation selected from the group consisting of Na + , K + , Ca 2+ , NH 4   + , Li + , and monovalent ammonium ions derived from mono-, di- and trialkylamines of 2 to 4 carbons or mono-, di- and trialkanolamines of 2 to 4 carbons; 
 R 9  is a monovalent radical selected from the group consisting of R 16 (O) w (R 17 ) x  and R 18 O(C 2 H 4 O) d (C 3 H 6 O) e (C 4 H 8 O) f CH 2 CH(OH)CH 2 ; 
 where R 16  and R 17  are each independently selected from the group consisting of a divalent hydrocarbon group of 1 to 4 carbon atoms, that may each be optionally substituted with one or more OH radicals; 
 R 18  is a divalent hydrocarbon group of 2 to 4 carbon atoms; subscripts w and x are zero or 1; 
 the subscripts d, e and f are zero or positive and satisfy the following relationships:
   1 ≦d+e+f≦ 10 with d≧1; 
 
 R C  is selected from the group consisting of N(R 19 )(R 20 ), 
 
       
         
           
           
               
               
           
         
       
       where R 19  and R 20  are independently selected from the group consisting of H, a branched or linear monovalent hydrocarbon radical of 1 to 4 carbons; R 26 N(R 29 )(R 30 ), and —R 27 O(C 2 H 4 O) g (C 3 H 6 O) h (C 4 H 8 O) i R 28 ;
 the subscripts g, h and i are zero or positive and satisfy the following relationships:
   1 ≦g+h+i≦ 10 with g≧1. 
 
 R 21 , R 23 , R 24 , R 25  are independently selected from the groups consisting of H, a branched or linear monovalent hydrocarbon radical of 1 to 4 carbons; 
 R 22  is H, a branched or linear monovalent hydrocarbon radical of 1 to 4 carbons, or —R 31 O(C 2 H 4 O) j (C 3 H 6 O) k (C 4 H 8 O) l R 32 ; 
 the subscripts j, k and l are zero or positive and satisfy the following relationships:
   1 ≦j+k+l≦ 10 with j≧1; 
 
 R 26  is a divalent hydrocarbon radical of 1 to 6 carbons that may be optionally substituted with a heterocyclic group containing nitrogen, sulfur, oxygen or combinations thereof or R 33 O(C 2 H 4 O) m (C 3 H 6 O) n (C 4 H 8 O) o R 34 ; 
 the subscripts m, n and o are zero or positive and satisfy the following relationships:
   1 ≦m+n+o≧ 10 with m≧1; 
 
 R 29  and R 30  are independently selected from the group consisting of H or a branched or linear monovalent hydrocarbon radical of 1 to 4 carbons; 
 R 27 , R 31  and R 33  are divalent radicals independently selected from the group consisting of a divalent hydrocarbon group of 2 to 4 carbon atoms; 
 R 28  is H, a monovalent hydrocarbon radical of 1 to 6 carbons, or N(R 35 )(R 36 ); 
 R 32  and R 34  are independently selected from the group consisting of H, a branched or linear monovalent hydrocarbon radical of 1 to 4 carbons, and R 37 N(R 38 )(R 39 ); where R 37  is a divalent hydrocarbon radical of 1 to 6 carbons; R 35 , R 36 , R 38  and R 39  are independently selected from the group consisting of H and branched or linear monovalent hydrocarbon radicals of 1 to 4 carbons; 
 R 10  is a monovalent radical selected from the group consisting of R 40 (O) y  (R 41 ) z  and R 42 O(C 2 H 4 O) p (C 3 H 6 O) q (C 4 H 8 O) r CH 2 CH(OH)CH 2 ; 
 where R 40  and R 41  are each independently selected from the group consisting of a divalent hydrocarbon bridging group of 1 to 4 carbon atoms, that may be each optionally substituted with one or more OH radicals; 
 R 42  is a divalent hydrocarbon group of 2 to 4 carbon atoms; subscripts y and z are zero or 1; 
 the subscripts p, q and r are zero or positive and satisfy the following relationships:
   1 ≦p+q+r≦ 10 with p≧1. 
 
 R Z  is a monovalent radical selected from the group consisting of 
 N—(R 43 )(R 44 ) α R 45 SO 3 -(M K ) β , N—(R 46 )(R 47 ) γ R 48 COO-(M K ) δ , 
 N + -(R 49 )(R 50 )R 51 OP(═O)(A)(B) or, 
 (—C(═O)N(R 52 )R 53 N—(R 54 )(R 55 )) + -(R 56 OP(═O)(A)(B))(X) ε ; 
 where R 43 , R 44 , R 46 , R 47 , R 49 , R 50 , R 52 , R 54  and R 55  are independently selected from the group consisting of H, a branched or linear monovalent hydrocarbon radical of 1 to 4 carbons, and an alkanolamine group of 2 to 4 carbons; 
 R 45  is a divalent group of 3 to 4 carbons; 
 the subscripts α, β, γ, δ and ε are zero or 1 subject to the following relationships: α+β=1 and γ+δ=1; 
 R 48  and R 51  are independently a divalent group of 1 to 4 carbons; 
 R 53  and R 56  are each independently a divalent group of 2 to 4 carbons; 
 A and B are selected from the group consisting of O— and OM K ; 
 X is an anion selected from the group of anions consisting of Cl, Br, and I; 
 and the subscript ε is 0, 1 or 2. 
 
     
     
         2 . The composition of  claim 1  where
 R 1  and R 4  are propyl, isopropyl, butyl, sec-butyl, iso-butyl, or tert-butyl;   R 2 , R 3 , R 5 , R 6 , R 7  is methyl;   R 11  is —CH 2 CH 2 CH 2 —; R 12  is —CH 2 CH(OH)CH 2 —;   R 13  is —H 2 CH 2 —; R 14  is —CH 2 CH 2 CH 2 —, —CH(CH 3 )CH 2 CH 2 —, or —CH 2 CH(CH 3 )CH 2 —;   R 15 =H;   R 16  is —H 2 CH 2 CH 2 —;   R 17  is CH 2 CH(OH)CH 2 —;   R 18  is —CH 2 CH 2 CH 2 —;   R 19  and R 20  is H, methyl, ethyl, propyl, isopropyl or   —R 27 O(C 2 H 4 O) g (C 3 H 6 O) h (C 4 H 8 O) i R 28 ;   R 27  is —CH 2 CH 2 CH 2 —, H or methyl;   R 21  and R 23  are H;   R 22 =H, methyl or —R 31 O(C 2 H 4 O) j (C 3 H 6 O) k (C 4 H 8 O) l R 32 ;   R 31  is —CH 2 CH 2 CH 2 —; j is 1-5, k and l=0;   R 32  is H or methyl; R 24  and R 25  are H;   R 40  is —CH 2 CH 2 CH 2 —; R 41  is —H 2 CH(CH 3 )CH 2 —;   R 42  is —CH 2 CH 2 CH 2 —;   R 43  and R 44  are H or methyl;   R 45  is —CH 2 CH 2 CH 2 — or —CH 2 CH 2 CH 2 CH 2 —;   R 46  and R 47  are H or methyl;   R 48  is —CH 2 CH 2 CH 2 — or —CH 2 CH 2 CH 2 CH 2 —;   R 49  and R 50  are H or methyl; and   R 52 , R 54  and R 55  are H or methyl.   
     
     
         3 . The composition of  claim 2  wherein Z is R 8 —R A . 
     
     
         4 . The composition of  claim 2  wherein Z is R 9 —R C . 
     
     
         5 . The composition of  claim 2  wherein Z is R 10 —R Z . 
     
     
         6 . An aqueous emulsion where the discontinuous phase comprises water and the continuous phase comprises the composition of  claim 1 . 
     
     
         7 . An aqueous emulsion where the discontinuous phase comprises water and the continuous phase comprises the composition of  claim 2 . 
     
     
         8 . An aqueous emulsion where the discontinuous phase comprises water and the continuous phase comprises the composition of  claim 3 . 
     
     
         9 . An aqueous emulsion where the discontinuous phase comprises water and the continuous phase comprises the composition of  claim 4 . 
     
     
         10 . An aqueous emulsion where the discontinuous phase comprises water and the continuous phase comprises the composition of  claim 5 . 
     
     
         11 . An aqueous emulsion where the discontinuous phase comprises the composition of  claim 1  and the continuous phase comprises water. 
     
     
         12 . An aqueous emulsion where the discontinuous phase comprises the composition of  claim 2  and the continuous phase comprises water. 
     
     
         13 . An aqueous emulsion where the discontinuous phase comprises the composition of  claim 3  and the continuous phase comprises water. 
     
     
         14 . An aqueous emulsion where the discontinuous phase comprises the composition of  claim 4  and the continuous phase comprises water. 
     
     
         15 . An aqueous emulsion where the discontinuous phase comprises the composition of  claim 5  and the continuous phase comprises water. 
     
     
         16 . A non-aqueous emulsion where the discontinuous phase comprises a non-aqueous hydroxylic solvent and the continuous phase comprises the composition of  claim 1 . 
     
     
         17 . A non-aqueous emulsion where the discontinuous phase comprises a non-aqueous hydroxylic solvent and the continuous phase comprises the composition of  claim 2 . 
     
     
         18 . A non-aqueous emulsion where the discontinuous phase comprises a non-aqueous hydroxylic solvent and the continuous phase comprises the composition of  claim 3 . 
     
     
         19 . A non-aqueous emulsion where the discontinuous phase comprises a non-aqueous hydroxylic solvent and the continuous phase comprises the composition of  claim 4 . 
     
     
         20 . A non-aqueous emulsion where the discontinuous phase comprises a non-aqueous hydroxylic solvent and the continuous phase comprises the composition of  claim 5 . 
     
     
         21 . A non-aqueous emulsion where the continuous phase comprises a non-aqueous hydroxylic organic solvent and the discontinuous phase comprises the composition of  claim 1 . 
     
     
         22 . A non-aqueous emulsion where the continuous phase comprises a non-aqueous hydroxylic organic solvent and the discontinuous phase comprises the composition of  claim 2 . 
     
     
         23 . A non-aqueous emulsion where the continuous phase comprises a non-aqueous hydroxylic organic solvent and the discontinuous phase comprises the composition of  claim 3 . 
     
     
         24 . A non-aqueous emulsion where the continuous phase comprises a non-aqueous hydroxylic organic solvent and the discontinuous phase comprises the composition of  claim 4 . 
     
     
         25 . A non-aqueous emulsion where the continuous phase comprises a non-aqueous hydroxylic organic solvent and the discontinuous phase comprises the composition of  claim 5 .