Hydrolysis resistant organomodified trisiloxane surfactants
Three types of trisiloxane surfactants having the basic formula: MDM′ are described wherein the substituents on the differing M and M′ groups in conjunction with a pendant polyalkylene oxide substituents on the D group to render the surfactant resistant to hydrolysis under either basic or acidic conditions.
1. A silicone composition comprising a silicone having the formula:
M 1 D 1 M 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 1 =(R 7 )(Z)SiO 2/2
where
R 1 is selected from the group of monovalent hydrocarbon radicals consisting of branched or linear hydrocarbon group consisting of 2 to 4 carbons, aryl, and an alkyl hydrocarbon group of 4 to 9 carbons containing aryl substituents of 6 to 20 carbon atoms;
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 an alkyleneoxide group of the general formula:
R 8 (C 2 H 4 O) a (C 3 H 6 O) b (C 4 H 8 O) c R 9 ,
where
R 8 is a linear or branched divalent hydrocarbon radical of 3 carbon atoms;
R 9 is selected from the group consisting of H, monovalent hydrocarbon radicals of from 1 to 6 carbon atoms and acetyl, and the subscripts a, b and c are zero or positive and satisfy the following relationships:
2a+b+c, 20 with a 2.
2. A silicone composition comprising a silicone having the formula:
M 1 D 1 M 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 1 =(R 7 )(Z)SiO 2/2
where
R 1 is selected from the group of monovalent hydrocarbon radicals consisting of branched or linear hydrocarbon group consisting of 2 to 4 carbons, aryl, and an alkyl hydrocarbon group of 4 to 9 carbons containing aryl substituents of 6 to 20 carbon atoms;
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 an alkyleneoxide group of the general formula:
R 8 (C 2 H 4 O) a (C 3 H 6 O) b (C 4 H 8 O) c R 9 ,
where
R 8 is a linear or branched divalent hydrocarbon radical of 2, 3, 5, 6, 7, 8, or 9 carbon atoms;
R 9 is selected from the group consisting of H, monovalent hydrocarbon radicals of from 1 to 6 carbon atoms and acetyl, and the subscripts a, b and c are zero or positive and satisfy the following relationships:
2a+b+c 20 with a 2
where R 1 and R 4 are selected from the group consisting of propyl, iso-propyl, butyl, sec-butyl, iso-butyl and tert-butyl.
3. The composition of claim 1 where R 2 , R 3 , R 5 , R 6 and R 7 are methyl.
4. The composition of claim 1 where the subscript a ranges from 8 to 12.
5. The composition of claim 1 where the subscript b ranges from 0 to 3.
6. The composition of claim 1 where the subscript c is 0.
7. The composition of claim 1 where R 9 is selected from the group consisting of hydrogen and methyl.
8. The composition of claim 2 where R 1 and R 4 are selected from the group consisting of iso-propyl and tert-butyl.
9. A silicone composition comprising a silicone having the formula:
M 1 D 1 M 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 1 =(R 7 )(Z)SiO 2/2
where
R 1 is selected from the group of monovalent hydrocarbon radicals consisting of branched or linear hydrocarbon group consisting of 2 to 4 carbons, aryl, and an alkyl hydrocarbon group of 4 to 9 carbons containing aryl substituents of 6 to 20 carbon atoms;
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 an alkyleneoxide group of the general formula:
R 8 (C 2 H 4 O) a (C 3 H 6 O) b (C 4 H 8 O) c R 9 ,
where
R 8 is a linear or branched divalent hydrocarbon radical of 2, 3, 5, 6, 7, 8, or 9 carbon atoms;
R 9 is selected from the group consisting of H, monovalent hydrocarbon radicals of from 1 to 6 carbon atoms and acetyl, and the subscripts a, b and c are zero or positive and satisfy the following relationships:
2a+b+c 20 with a 2
where the subscript a is 11.
10. The composition of claim 7 where R 9 is hydrogen.
11. The composition of claim 8 where R 2 , R 3 , R 5 , R 6 and R 7 are methyl.
12. The composition of claim 11 where R 8 is a divalent hydrocarbon radical having three carbon atoms.
13. The composition of claim 12 where the subscript a is 11.
14. The composition of claim 13 where the subscripts b and c are both zero.
15. The composition of claim 14 where R 9 is hydrogen.
16. A silicone composition comprising a silicone having the formula:
M 1 D 1 M 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 1 =(R 7 )(Z)SiO 2/2
where
R 1 is selected from the group of monovalent hydrocarbon radicals consisting of branched or linear hydrocarbon group consisting of 2 to 4 carbons, aryl, and an alkyl hydrocarbon group of 4 to 9 carbons containing aryl substituents of 6 to 20 carbon atoms;
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 an alkyleneoxide group of the general formula:
R 8 (C 2 H 4 O) a (C 3 H 6 O) b (C 4 H 8 O) c R 9 ,
where
R 8 is a linear or branched divalent hydrocarbon radical of 3 carbon atoms;
R 9 is selected from the group consisting of H, monovalent hydrocarbon radicals of from 1 to 6 carbon atoms and acetyl, and the subscripts a, b and c are zero or positive and satisfy the following relationships:
2a+b+c 20 with a 2
wherein said silicone composition has an enhanced resistance to hydrolysis.
17. A silicone composition comprising a silicone having the formula:
M 1 D 1 M 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 1 =(R 7 )(Z)SiO 2/2
where
R 1 is selected from the group of monovalent hydrocarbon radicals consisting of branched or linear hydrocarbon group consisting of 2 to 4 carbons, aryl, and an alkyl hydrocarbon group of 4 to 9 carbons containing aryl substituents of 6 to 20 carbon atoms;
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 an alkyleneoxide group of the general formula:
R 8 (C 2 H 4 O) a (C 3 H 6 O) b (C 4 H 8 O) c R 9 ,
where
R 8 is a linear or branched divalent hydrocarbon radical of 2, 3, 5, 6, 7, 8, or 9 carbon atoms;
R 9 is selected from the group consisting of H, monovalent hydrocarbon radicals of from 1 to 6 carbon atoms and acetyl, and the subscripts a, b and c are zero or positive and satisfy the following relationships:
2a+b+c20 with a2
where R 1 and R 4 are selected from the group consisting of propyl, iso-propyl, butyl, sec-butyl, iso-butyl and tert-butyl.
18. The composition of claim 16 where R 2 , R 3 , R 5 , R 6 and R 7 are methyl.
19. The composition of claim 16 where the subscript a ranges from 8 to 12.
20. The composition of claim 16 where the subscript b ranges from 0 to 3.
21. The composition of claim 16 where the subscript c is 0.
22. The composition of claim 16 where R 9 is selected from the group consisting of hydrogen and methyl.
23. The composition of claim 17 where R 1 and R 4 are selected from the group consisting of iso-propyl and tert-butyl.
24. A silicone composition comprising a silicone having the formula:
M 1 D 1 M 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 1 =(R 7 )(Z)SiO 2/2
where
R 1 is selected from the group of monovalent hydrocarbon radicals consisting of branched or linear hydrocarbon group consisting of 2 to 4 carbons, aryl, and an alkyl hydrocarbon group of 4 to 9 carbons containing aryl substituents of 6 to 20 carbon atoms;
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 an alkyleneoxide group of the general formula:
R 8 (C 2 H 4 O) a (C 3 H 6 O) b (C 4 H 8 O) c R 9 ,
where
R 8 is a linear or branched divalent hydrocarbon radical of 2, 3, 5, 6, 7, 8, or 9 carbon atoms;
R 9 is selected from the group consisting of H, monovalent hydrocarbon radicals of from 1 to 6 carbon atoms and acetyl, and the subscripts a, b and c are zero or positive and satisfy the following relationships:
2a+b+c 20 with a 2
where the subscript a is 11.
25. The composition of claim 22 where R 9 is hydrogen.
26. The composition of claim 23 where R 2 , R 3 , R 5 , R 6 and R 7 are methyl.
27. The composition of claim 26 where R 8 is a divalent hydrocarbon radical having three carbon atoms.
28. The composition of claim 27 where the subscript a is 11.
29. The composition of claim 28 where the subscripts b and c are both zero.
30. The composition of claim 29 where R 9 is hydrogen.
31. An aqueous emulsion wherein the discontinuous phase comprises water and the continuous phase comprises the composition of claim 1 .
32. An aqueous emulsion wherein the discontinuous phase comprises water and the continuous phase comprises the composition of claim 16 .
33. An aqueous emulsion wherein the continuous phase comprises water and the discontinuous phase comprises the composition of claim 1 .
34. An aqueous emulsion wherein the continuous phase comprises water and the discontinuous phase comprises the composition of claim 16 .
35. A non-aqueous emulsion wherein the discontinuous phase comprises a non-aqueous hydroxylic solvent and the continuous phase comprises the composition of claim 1 .
36. A non-aqueous emulsion wherein the discontinuous phase comprises a non-aqueous hydroxylic solvent and the continuous phase comprises the composition of claim 16 .
37. A non-aqueous emulsion wherein the continuous phase comprises a non-aqueous hydroxylic solvent and the discontinuous phase comprises the composition of claim 1 .
38. A non-aqueous emulsion wherein the continuous phase comprises a non-aqueous hydroxylic solvent and the discontinuous phase comprises the composition of claim 16 .
39. A silicone composition comprising a silicone having the formula:
M 5 D 3 M 6
wherein
M 5 =(R 19 )(R 20 )(R 21 )SiO 1/2 ;
M 6 =(R 22 )(R 23 )(R 24 )SiO 1/2 ; and
D 3 =(R 25 )(Z″)SiO 2/2
where
R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 are each independently selected from the group consisting of 1 to 4 carbon monovalent hydrocarbon radicals, aryl, and an alkyl hydrocarbon group of 4 to 9 carbons containing an aryl substituents of 6 to 20 carbon atoms,
R 25 is a linear or branched monovalent hydrocarbon radical of 3 or 4 carbons;
Z″ is an alkylene oxide group of the general formula:
R 26 (C 2 H 4 O) g (C 3 H 6 O) h (C 2 H 4 O) i R 27 ,
where
R 26 is a linear or branched divalent hydrocarbon radical of 2, 3, 5, 6, 7, 8, or 9 carbon atoms;
R 27 is selected from the group consisting of H, monovalent hydrocarbon radicals of from 1 to 6 carbon atoms and acetyl and the subscripts g, h and i are zero or positive and satisfy the following relationships:
2 g+h+i 20 with g 2.
40. The composition of claim 39 where R 27 is selected from the group consisting of hydrogen and methyl.
41. The composition of claim 39 where the subscript i is 0.
42. The composition of claim 39 where the subscript h ranges from 0 to 3.
43. The composition of claim 39 where the subscript g ranges from 8 to 11.
44. The composition of claim 39 where R 26 is a 3 carbon monovalent hydrocarbon radical.
45. The composition of claim 39 where R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 are methyl.
46. The composition of claim 39 where R 25 is a 4 carbon monovalent hydrocarbon radical.
47. The composition of claim 46 where R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 are methyl.
48. The composition of claim 47 where the subscript g is 8.
49. The composition of claim 48 where the subscript h is 0.
50. The composition of claim 49 where the subscript i is 0.
51. A silicone composition comprising a silicone having the formula:
M 5 D 3 M 6
wherein
M 5 =(R 19 )(R 20 )(R 21 )SiO 1/2 ;
M 6 =(R 22 )(R 23 )(R 24 )SiO 1/2 ; and
D 3 =(R 25 )(Z″)SiO 2/2
where
R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 are each independently selected from the group consisting of 1 to 4 carbon monovalent hydrocarbon radicals, aryl, and an alkyl hydrocarbon group of 4 to 9 carbons containing an aryl substituents of 6 to 20 carbon atoms,
R 25 is a linear or branched monovalent hydrocarbon radical of 3 or 4 carbons;
Z″ is an alkylene oxide group of the general formula:
R 26 (C 2 H 4 O) g (C 3 H 6 O) h (C 2 H 4 O) i R 27 ,
where
R 26 is a linear or branched divalent hydrocarbon radical of 2, 3, 5, 6, 7, 8, or 9 carbon atoms;
R 27 is selected from the group consisting of H, monovalent hydrocarbon radicals of from 1 to 6 carbon atoms and acetyl and the subscripts g, h and i are zero or positive and satisfy the following relationships:
2 g+h+i 20 with g 2
wherein said silicone composition has an enhanced resistance to hydrolysis.
52. The composition of claim 51 where R 27 is selected from the group consisting of hydrogen and methyl.
53. The composition of claim 51 where the subscript i is 0.
54. The composition of claim 51 where the subscript h ranges from 0 to 3.
55. The composition of claim 51 where the subscript g ranges from 8 to 11.
56. The composition of claim 51 where R 26 is a 3 carbon monovalent hydrocarbon radical.
57. The composition of claim 51 where R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 are methyl.
58. The composition of claim 51 where R 25 is a 4 carbon monovalent hydrocarbon radical.
59. The composition of claim 58 where R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 are methyl.
60. The composition of claim 59 where the subscript g is 8.
61. The composition of claim 60 where the subscript h is 0.
62. The composition of claim 61 where the subscript i is 0.
63. An aqueous emulsion wherein the discontinuous phase comprises water and the continuous phase comprises the composition of claim 39 .
64. An aqueous emulsion wherein the discontinuous phase comprises water and the continuous phase comprises the composition of claim 51 .
65. An aqueous emulsion wherein the continuous phase comprises water and the discontinuous phase comprises the composition of claim 39 .
66. An aqueous emulsion wherein the continuous phase comprises water and the discontinuous phase comprises the composition of claim 51 .
67. A non-aqueous emulsion wherein the discontinuous phase comprises a non-aqueous hydroxylic solvent and the continuous phase comprises the composition of claim 39 .
68. A non-aqueous emulsion wherein the discontinuous phase comprises a non-aqueous hydroxylic solvent and the continuous phase comprises the composition of claim 51 .
69. A non-aqueous emulsion wherein the continuous phase comprises a non-aqueous hydroxylic solvent and the discontinuous phase comprises the composition of claim 39 .
70. A non-aqueous emulsion wherein the continuous phase comprises a non-aqueous hydroxylic solvent and the discontinuous phase comprises the composition of claim 51 .