Hydrolysis resistant organomodified disiloxane ionic surfactants
View Patent ↗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 5 R 6 SiO 1/2 ;
with R 1 selected from the group consisting of branched monovalent hydrocarbon radical of from 3 to 6 carbon atoms and R 7 , where R 7 is
R 8 R 9 R 10 SiR 12
with R 8 , R 9 , and R 10 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 consisting of
R 16 (O) t (R 17 ) u (O) y —,
and
R 19 O(C 2 H 4 O) a (C 3 H 6 O) b (C 4 H 8 O) c —;
where R 5 and R 6 are methyl,
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+l≦ 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 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 selected from the group consisting of —N—(R 48 )(R 49 ) α R 50 SO 3 (M K ) β ,
—N—(R 51 )(R 52 ) y R 53 COO(M K ) δ ,
—N + —(R 54 )(R 55 )R 56 OP(═O)(A)(B) and
—[—C(═O)N(R 57 )R 58 N + (R 59 )(R 60 R 61 OP(═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 is selected from O − and OM K ; B is OM K ; X is an anion selected from the group of anions consisting of Cl, Br, and I; the subscript ε is 0 or 1; and
R 58 and R 61 are each independently a divalent group of 2 to 4 carbons.
2. The composition of claim 1 where:
R 1 is selected from the group consisting of isopropyl, iso-butyl, tert-butyl and R 7 ;
where R 7 has the formula R 8 R 9 R 10 SiR 12 with R 8 , R 9 and R 10 each independently selected from the group consisting of methyl and R 12 is —CH 2 CH 2 ; R 2 , R 3 , are methyl; R 16 is —CH 2 CH 2 CH 2 —;
R 17 is —CH 2 CH(OH)CH 2 —; R 18 is —CH 2 CH 2 —;
R 19 is selected from the group consisting of —CH 2 CH 2 CH 2 —, —CH(CH 3 )CH 2 CH 2 —, and —CH 2 CH(CH 3 )CH 2 —;
R 20 is H; M K is selected from the group consisting of Na + , K + or NH 4 + ;
R 21 is selected from the group consisting of —CH 2 CH 2 CH 2 —; R 22 is CH 2 CH(OH)CH 2 —; R 23 is —CH 2 CH 2 CH 2 —;
R 24 and R 25 is selected from the group consisting of H, methyl, ethyl, propyl, isopropyl and —R 32 O(C 2 H 4 O) g (C 3 H 6 O) h (C 4 H 8 O) i R 33 ;
R 32 is —CH 2 CH 2 CH 2 —; R 33 is selected from the group consisting of H and methyl;
R 26 and R 28 is H; R 27 is selected from the group consisting of H, methyl and —R 36 O(C 2 H 4 O) j (C 3 H 6 O) k (C 4 H 8 O) l R 37 ; R 36 is selected from the group consisting of —CH 2 CH 2 CH 2 —;
R 37 is selected from the group consisting of H and methyl; R 29 and R 30 is selected from the group consisting of H;
R 45 is —CH 2 CH 2 CH 2 —; R 46 is —CH 2 CH(CH 3 )CH 2 —; y and z are 1; R 47 is
—CH 2 CH 2 CH 2 —;
R 48 and R 49 is selected from the group consisting of H and methyl;
R 50 is selected from the group consisting of —CH 2 CH 2 CH 2 — and —CH 2 CH 2 CH 2 CH 2 —;
R 51 and R 52 is each independently selected from the group consisting of H and methyl; R 53 is selected from the group consisting of —CH 2 CH 2 CH 2 — and
—CH 2 CH 2 CH 2 CH 2 —;
R 54 and R 55 are selected from the group consisting of H and methyl; R 57 , and R 59 and R 60 are selected from the group consisting of H and methyl.
3. The composition of claim 2 wherein R 4 is R 13 —R A .
4. The composition of claim 2 wherein R 4 is R 14 —R C .
5. The composition of claim 2 wherein R 4 is R 15 —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 .