Hydrolysis resistant organomodified disiloxane ionic surfactants

Abstract

An asymmetric organomodified disiloxane surfactant having the formula: MM′ wherein M comprises branched hydrocarbon substituents and M′ comprises a cationic, anionic or zwitterionic substituent and a polyether substituent that may be combined as one moiety, wherein the disiloxane surfactant has an enhanced resistance to hydrolysis between a pH of about 3 to about 12.

1 . A silicone composition comprising a silicone having the formula:
   MM′
   
       where
 M is selected from the group consisting of R 1 R 2 R 3 SiO 1/2 ; 
 M′ is selected from the group consisting of R 4 R 8 R 6 SiO 1/2 ; 
 
       with R 1  identical to
 R 7 , where R 7  is selected from the group consisting of
   R 8 R 9 R 10 SiR 12  and (R 4 R 5 R 6 )SiR 12 (Si(R 2 R 3 )SiO 1/2 ) 
 
 
       with R 8 , R 9 , and R 18  each independently selected from the group of monovalent hydrocarbon radicals having from 1 to 6 carbon atoms and monovalent aryl or alkaryl hydrocarbon radicals having from 6 to 13 carbon atoms and R 12  is a divalent hydrocarbon radical having from 1 to 3 carbon atoms;
 R 2  and R 3  are each independently selected from the group of from 1 to 6 carbon atom monovalent hydrocarbon radicals or R 1 , where R 4  is R 13 —R A , R 14 —R C , and R 15 —R Z ; 
 R 13  is selected from the group
                     R 18 —CHCH 2 CH(OH)CH(O—)CH 2 CH 2 ; and
 
   R 19 O(C 2 H 4 O) a (C 3 H 6 O) b (C 4 H 8 O) c —;
 
 
 
       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;
 R 19  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; 
 
       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 20 )COO − M K ; —PO 3 HM K ; —COOM K ; where R 20  is selected from the group consisting of H and —SO 3 M 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 14  is a monovalent radical selected from the group consisting of
   R 21 (O) w (R 22 ) x — and R 23 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 21  and R 22  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 23  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 24 )(R 25 ), 
 
       
         
           
           
               
               
           
         
       
       where R 24  and R 25  are independently selected from the group consisting of H, a branched or linear monovalent hydrocarbon radical of 1 to 4 carbons, R 31 N(R 34 )(R 35 ), and —R 32 O(C 2 H 4 O) g (C 3 H 6 O) h (C 4 H 8 O) i R 3 ; 
       the subscripts g, h and i are zero or positive and satisfy the following relationships:
   1≦ g+h+i≦ 10 with  g≧ 1.
 
 R 26 , R 28 , R 29 , R 30  are each independently selected from the groups consisting of H and a branched or linear monovalent hydrocarbon radical of 1 to 4 carbons; 
 R 27  is a monovalent radical selected from the group consisting of H, a branched or linear monovalent hydrocarbon radical of 1 to 4 carbons, and
   —R 36 O(C 2 H 4 O) j (C 3 H 6 O) k (C 4 H 8 O) l R 37 ;
 
 
 
       the subscripts j, k and l are zero or positive and satisfy the following relationships:
   1≦ j+k+ 1≦10 with  j≅ 1;
 
 R 31  is a divalent hydrocarbon radical of 1 to 6 carbons, optionally substituted with a heterocyclic group containing nitrogen, sulfur, oxygen or combinations thereof or R 38 O(C 2 H 4 O) m (C 3 H 6 O) n (C 4 H 8 O) o R 39 ; the subscripts m, n and o are zero or positive and satisfy the following relationships:
   1≦ m+n+o≦ 10 with  m≧ 1.
 
 
 R 34  and R 35  are independently selected from the group consisting of H and a branched or linear monovalent hydrocarbon radical of 1 to 4 carbons. 
 R 32 , R 36  and R 38  are independently selected from the group consisting of a divalent hydrocarbon group of 2 to 4 carbon atoms; 
 R 33  is a monovalent radical selected from the group consisting of H, a monovalent hydrocarbon radical of 1 to 6 carbons and N(R 40 )(R 41 ); 
 R 37  and R 39  are independently selected from the group consisting of H, a branched or linear monovalent hydrocarbon radical of 1 to 4 carbons, and R 42 N(R 43 )(R 44 ); where R 42  is a divalent hydrocarbon radical of 1 to 6 carbons. R 40 , R 41 , R 43  and R 44  are independently selected from the group consisting of H and branched or linear monovalent hydrocarbon radicals of 1 to 4 carbons; 
 R 15  is a monovalent radical selected from the group consisting of 
 R 45 (O) y (R 46 ) z — and R 47 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 45  and R 46  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 47  is a divalent hydrocarbon group of 2 to 4 carbon atoms; subscripts γ 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 —N—(R 48 )(R 49 ) α R 50 SO 3 (M K ) β , —N—(R 51 )(R 52 ) γ R 53 COO(M K ) δ , —N + —(R 54 )(R 55 )R 56 OP(═O)(A)(B) or, (—C(═O)N(R 57 )R 58 N—(R 59 )(R 60 )) + —(R 61 OP (is selected from the group consisting of O)(A)(B))(X − ) ε ; 
       where R 48 , R 49 , R 51 , R 52 , R 54 , R 55 , R 57 , R 59  and R 60  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 50  is a divalent bridging group of 3 to 4 carbons; subscripts α, β, γ and δ are zero or 1 subject to the following relationships: α+β=1 and γ+δ=1; 
 R 53  and R 56  are independently a divalent bridging group of 1 to 4 carbons; 
 R 58  and R 61  are each independently a divalent bridging group of 2 to 4 carbons; 
 A and B are selected from O −  and OM K ; X is an anion selected from the group of anions consisting of Cl, Br, and I; the subscript ε is 0, 1 or 2; and 
 R 58  and R 61  are each independently a divalent group of 2 to 4 carbons. 
 
     
     
         2 . (canceled) 
     
     
         3 . The composition of  claim 1  wherein Z is R 8 —R A . 
     
     
         4 . The composition of  claim 1  wherein Z is R 9 —R C . 
     
     
         5 . The composition of  claim 1  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 . (canceled) 
     
     
         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 . (canceled) 
     
     
         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 . (canceled) 
     
     
         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 . (canceled) 
     
     
         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 .