CN102972396B - Hydrolysis-resistant organic modified trisiloxane surfactants - Google Patents

Abstract

The present invention describes three classes of trisiloxane surfactants having the basic formula: MDM' in which the substituents on the different M and M' groups and the polyoxyalkylene side substituents on the D group are combined This makes the surfactant resistant to hydrolysis under alkaline or acidic conditions outside the pH range of 6.0-7.5. The composition can be used in agricultural, household and cosmetic applications.

Description

Organomodified Trisiloxane Surfactants Resistant to Hydrolysis

This application is a divisional application of an invention patent application with the filing date of March 8, 2007, the application number of 200780052767.7 (PCT/US2007/005905), and the title of "hydrolysis-resistant organically modified trisiloxane surfactant" .

field of invention

The present invention relates to trisiloxane surfactant compositions which exhibit resistance to hydrolysis over a broad pH range. More particularly, the present invention relates to such hydrolysis resistant trisiloxane surfactants having hydrolysis resistance between about pH 3 and about pH 12.

Background of the invention

Liquid compositions are topically applied to the surfaces of animate and inanimate objects to produce desired changes, including controlled wetting, spreading, foaming, cleaning, and the like. When used in aqueous solutions to improve the delivery of active ingredients to the surface being treated, it has been found that the use of trisiloxane-type compounds enables the control of these processes to achieve the desired effect. However, trisiloxane compounds are only available in a narrow pH range, ie from slightly acidic pH 6 to very mild alkaline pH 7.5. Outside this narrow pH range, trisiloxane compounds are not hydrolytically stable, undergoing rapid decomposition.

Brief description of the invention

The present invention provides an extreme environment composition for use as an agricultural composition, a personal care composition, a coating composition or a home care composition, said composition comprising a silicone composition comprising a surface active A trisiloxane compound or a combination thereof selected from trisiloxane compounds of formula I, II or III.

Trisiloxane compound I has the formula:

M ¹ D ¹ M ²

in

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

in

R ¹ is selected from branched or linear hydrocarbon groups of 2 to 4 carbon atoms, aryl groups, and alkyl hydrocarbon groups of 4 to 9 carbon atoms 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 a monovalent hydrocarbon group of 1 to 4 carbon atoms, an aryl group, and a hydrocarbon group of 4 to 9 carbon atoms containing an aryl group; Z is a An oxyalkylene group of the following 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 has 2, 3, 5, 6, 7, 8 or 9 carbon atoms straight chain or branched divalent hydrocarbon group; R ⁹ is selected from H, monovalent hydrocarbon group and acetyl group with 1 to 6 carbon atoms, subscript a, b and c are Zero or a positive number that satisfies the following relationship:

2≤a+b+c≤20, where a≥2.

When the subscript a satisfies the condition 2≦a≦5, it is recommended to use the co-surfactants listed below to obtain the benefits of the compositions of the present invention.

Trisiloxane compound II has the formula:

M ³ D ² M ⁴

in

M ³ =(R ¹⁰ )(R ¹¹ )(R ¹² )SiO _1/2 ;

M ⁴ =(R ¹³ )(R ¹⁴ )(R ¹⁵ )SiO _1/2 ; and

D ² =(R ¹⁶ )(Z')SiO _2/2

in

R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently selected from monovalent hydrocarbon groups with 1 to 4 carbon atoms, aryl groups, and aryl groups with 6 to 20 carbon atoms An alkyl hydrocarbon group of 4 to 9 carbon atoms as a substituent; Z' is an oxyalkylene group having the general formula: R ¹⁷ (C ₂ H ₄ O) _d (C ₃ H ₆ O) _e (C ₄ H ₈ O) _f R ¹⁸ , where R ¹⁷ is selected from the general formula: -C ₄ H ₈ O-(C ₂ H ₄ O)-branched or linear divalent hydrocarbon group; R ¹⁸ is selected from H, with 1～ Monovalent hydrocarbon group and acetyl group with 6 carbon atoms, the subscripts d, e and f are zero or positive numbers and satisfy the following relationship:

2≤d+e+f≤20, where d≥2.

When the subscript d satisfies the condition 2≦d≦5, it is recommended to use the co-surfactants listed below to achieve the benefits of the compositions of the present invention.

Trisiloxane compound III has the formula:

M ⁵ D ³ M ⁶

in

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

in

R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ are each independently selected from monovalent hydrocarbon groups with 1 to 4 carbon atoms, aryl groups, and aryl substituents with 6 to 20 carbon atoms An alkyl hydrocarbon group with 4 to 9 carbon atoms, R ²⁵ is a straight chain or branched hydrocarbon group with 2 to 4 carbon atoms; Z" is an oxyalkylene group with the following general formula: R ²⁶ (C ₂ H ₄ O ) _g (C ₃ H ₆ O) _h (C ₄ H ₈ O) _i R ²⁷ , where R ²⁶ is straight-chain or branched with 2, 3, 5, 6, 7, 8 or 9 carbon atoms Divalent hydrocarbon group; ^R27 is selected from H, monovalent hydrocarbon group and acetyl group with 1 to 6 carbon atoms, subscripts g, h and i are zero or positive numbers and satisfy the following relationship:

2≤g+h+i≤20, where g≥2.

When the subscript g satisfies the condition 2≦g≦5, it is recommended to use the co-surfactants listed below to achieve the benefits of the compositions of the present invention.

The present invention includes:

1. An agricultural composition comprising

a) Silicones having the formula:

M ¹ D ¹ M ²

in

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

in

R ^is selected from branched or linear hydrocarbon groups of 2 to 4 carbon atoms, aryl groups, and alkyl hydrocarbon groups of 4 to 9 carbon atoms containing aryl substituents of 6 to 20 carbon atoms. Hydrocarbyl; R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently selected from monovalent hydrocarbon groups with 1 to 4 carbon atoms, aryl groups, and aryl-containing 4 to 9 carbon atoms Hydrocarbyl; Z is an oxyalkylene group having 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 group with 2 , 3, 5, 6, 7, 8 or 9 carbon atoms straight chain or branched divalent hydrocarbon group; R ⁹ is selected from H, monovalent hydrocarbon group and acetyl group with 1 to 6 carbon atoms, subscript a , b and c are zero or positive numbers and satisfy the following relationship:

2≤a+b+c≤20, where a≥2; and

b) agriculturally active ingredients,

wherein said agricultural composition has improved resistance to hydrolysis.

2. The composition of item ¹ , wherein R and ^R are selected from propyl, isopropyl, butyl, sec-butyl, isobutyl and tert-butyl.

3. The composition according to item 1, wherein R ² , R ³ , R ⁵ , R ⁶ and R ⁷ are methyl groups.

4. The composition of item 1, wherein R ⁸ is a divalent hydrocarbon group having three carbon atoms.

5. The composition according to item 1, wherein the subscript a is 8-12.

6. The composition according to item 1, wherein the subscript b is 0-3.

7. The composition of item 1, wherein the subscript c is 0.

8. The composition of item 1, wherein ^R9 is selected from hydrogen and methyl.

9. The composition of item 2, wherein R ¹ and R ⁴ are selected from isopropyl and tert-butyl.

10. The composition of item 5, wherein the subscript a is 11.

11. The composition of item 8, wherein R ⁹ is hydrogen.

12. The composition according to item 9, wherein R ² , R ³ , R ⁵ , R ⁶ and R ⁷ are methyl groups.

13. The composition of item 12, wherein R ⁸ is a divalent hydrocarbon group having three carbon atoms.

14. The composition of item 13, wherein the subscript a is 11.

15. The composition of item 14, wherein the subscripts b and c are both zero.

16. The composition of item 15, wherein R ⁹ is hydrogen.

17. An agricultural composition comprising:

a) Silicones having the formula:

M ¹ D ¹ M ²

in

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

in

R ^is selected from branched or linear hydrocarbon groups of 2 to 4 carbon atoms, aryl groups, and alkyl hydrocarbon groups of 4 to 9 carbon atoms containing aryl substituents of 6 to 20 carbon atoms. Hydrocarbyl; R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently selected from monovalent hydrocarbon groups with 1 to 4 carbon atoms, aryl groups, and aryl-containing 4 to 9 carbon atoms Hydrocarbyl; Z is an oxyalkylene group having 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 group with 2 , 3, 5, 6, 7, 8 or 9 carbon atoms straight chain or branched divalent hydrocarbon group; R ⁹ is selected from H, monovalent hydrocarbon group and acetyl group with 1 to 6 carbon atoms, subscript a , b and c are zero or positive numbers and satisfy the following relationship:

2≤a+b+c≤20, where a≥2; and

b) Agricultural active ingredients selected from the group consisting of: aldimorph, clarizoline, mobendazim, dimethomorph; flusilazole, penconazole, cyconazole, econazole, furconazole, propiconazole, penconazole Coniferazole, carbendazim, thiophanate, benomyl, carbendazim, chlorothalonil, clonidamine, trifloxystrobin, fluoxastrobin, kyserostrobin, azoxystrobin, fenstrobin, propylchloride Ling, sulfamethanil, oxafefenone, captan, maneb, mancozeb, multi-antibacterial bacteria, Bacillus thuringiensis, Acetyl 105, abamectin, doramectin, lepimectin, pyrethrin, Carbaryl, pirimicarb, aldicarb, methoxam, chrysanthemum, boric acid, chlordimeform, diflubenzuron, ditriflubenzuron, dimeturon, diflubenzuron, mimaphid, Zinon, acephate, endosulfan, kelevan, dimethoate, azinphos-ethyl, azinphos-methyl, isoxazophos, chlorpyrifos, tetrafenazine, cyhalothrin, permethrin, fluorine Permethrin, Cypermethrin, Phenoxyacetic Acid, Phenoxypropionic Acid, Phenoxybutyric Acid, Benzoic Acid, Triazines and S-Triazines, Substituted Ureas, Uracil, Bentazone, Isobenad, Imazetam, Bendicon, Dacaozhi, Diquat, Clomazone, Fluoxazone, Dazamide, Dinitroaniline, Isalaline, Huangcaoxiao, Amoxazol, Amprofen, Trifluralin , glyphosate, glufosinate-ammonium, sulfonylurea, imidazolinone, pyridine carboxylic acid, clethodim, chloroform, fenoxaprop-p-p, fluoralifop-pyl, chloroxyfop-pyridine, grass Gram, sethoxydim, dichlorpyril, clomazone, bipyridylium compound, zinc sulfate, ferrous sulfate, ammonium sulfate, urea, urea ammonium nitrogen, ammonium thiosulfate, potassium sulfate, monoammonium phosphate, urea phosphate , calcium nitrate, boric acid, potassium salt of boric acid, sodium salt of boric acid, phosphoric acid, magnesium hydroxide, manganese carbonate, calcium polysulfide, copper sulfate, manganese sulfate, iron sulfate, calcium sulfate, sodium molybdate, and calcium chloride, wherein said agricultural composition has improved resistance to hydrolysis.

18. The composition of item 17, wherein R ^{and R} are selected from propyl, isopropyl, butyl, sec-butyl, isobutyl and tert-butyl.

19. The composition of item 17, wherein R ² , R ³ , R ⁵ , R ⁶ and R ⁷ are methyl.

20. The composition of item 17, wherein R ⁸ is a divalent hydrocarbon group having three carbon atoms.

21. The composition according to item 17, wherein the subscript a is 8-12.

22. The composition according to item 17, wherein the subscript b is 0-3.

23. The composition of item 17, wherein the subscript c is 0.

24. The composition of item 17, wherein ^R9 is selected from hydrogen and methyl.

25. The composition of item 18, wherein R ^{and R} are selected from isopropyl and tert-butyl.

26. The composition of item 21, wherein the subscript a is 11.

27. The composition of item 24, wherein R ⁹ is hydrogen.

28. The composition of item 25, wherein R ² , R ³ , R ⁵ , R ⁶ and R ⁷ are methyl.

29. The composition of item 28, wherein R ⁸ is a divalent hydrocarbon group having three carbon atoms.

30. The composition of item 29, wherein subscript a is 11.

31. The composition of item 30, wherein the subscripts b and c are both zero.

32. The composition of item 31, wherein R ⁹ is hydrogen.

33. An aqueous emulsion, wherein the discontinuous phase comprises water and the continuous phase comprises the composition of item 1.

34. An aqueous emulsion, wherein the discontinuous phase comprises water and the continuous phase comprises the composition of item 17.

35. An aqueous emulsion, wherein the continuous phase comprises water and the discontinuous phase comprises the composition of item 1.

36. An aqueous emulsion, wherein the continuous phase comprises water and the discontinuous phase comprises the composition of item 17.

37. A non-aqueous emulsion, wherein the discontinuous phase comprises a non-aqueous hydroxylic solvent and the continuous phase comprises the composition of item 1.

38. A non-aqueous emulsion, wherein the discontinuous phase comprises a non-aqueous hydroxylic solvent and the continuous phase comprises the composition of item 17.

39. A non-aqueous emulsion, wherein the continuous phase comprises a non-aqueous hydroxylic solvent and the discontinuous phase comprises the composition of item 1.

40. A non-aqueous emulsion, wherein the continuous phase comprises a non-aqueous hydroxylic solvent and the discontinuous phase comprises the composition of item 17.

41. An agricultural composition comprising

a) Silicones having the formula:

M ³ D ² M ⁴

in

M ³ =(R ¹⁰ )(R ¹¹ )(R ¹² )SiO _1/2 ;

M ⁴ =(R ¹³ )(R ¹⁴ )(R ¹⁵ )SiO _1/2 ; and

D ² =(R ¹⁶ )(Z')SiO _2/2

wherein R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently selected from monovalent hydrocarbon groups with 1 to 4 carbon atoms, aryl groups, and aromatic groups with 6 to 20 carbon atoms An alkyl hydrocarbon group of 4 to 9 carbon atoms as a substituent; Z' is an oxyalkylene group having the following formula: R ¹⁷ (C ₂ H ₄ O) _d (C ₃ H ₆ O) _e (C ₄ H ₈ O) _f R ¹⁸ , wherein R ¹⁷ has the chemical formula: -C ₄ H ₈ O-(C ₂ H ₄ O)-; R ¹⁸ is selected from H, monovalent hydrocarbon groups and acetyl groups with 1 to 6 carbon atoms , the subscripts d, e and f are zero or positive and satisfy the following relationship:

2≤d+e+f≤20, where d≥2; and

b) agriculturally active ingredients,

wherein said agricultural composition has improved resistance to hydrolysis.

42. The composition of item 41, wherein the subscript f is 0.

43. The composition according to item 41, wherein subscript e is 0-3.

44. The composition according to item 41, wherein the subscript d is 8-11.

45. The composition according to item 41, wherein R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are methyl groups.

46. The composition of item 41, wherein R ¹⁸ is methyl.

47. The composition of item 42, wherein subscript e is 0.

48. The composition of item 47, wherein the subscript d is 8.

49. The composition according to item 48, wherein R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are methyl groups.

50. The composition of item 49, wherein R ¹⁸ is methyl.

51. An agricultural composition comprising

a) Silicones having the formula:

M ³ D ² M ⁴

in

M ³ =(R ¹⁰ )(R ¹¹ )(R ¹² )SiO _1/2 ;

M ⁴ =(R ¹³ )(R ¹⁴ )(R ¹⁵ )SiO _1/2 ; and

D ² =(R ¹⁶ )(Z')SiO _2/2

in

R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently selected from monovalent hydrocarbon groups with 1 to 4 carbon atoms, aryl groups, and aryl groups with 6 to 20 carbon atoms An alkyl hydrocarbon group of 4 to 9 carbon atoms as a substituent; Z' is an oxyalkylene group having the formula: R ¹⁷ (C ₂ H ₄ O) _d (C ₃ H ₆ O) _e (C ₄ H ₈ O) _f R ¹⁸ , where R ¹⁷ has the chemical formula -C ₄ H ₈ O-(C ₂ H ₄ O)-; R ¹⁸ is selected from H, a monovalent hydrocarbon group having 1 to 6 carbon atoms and an acetyl group, the following The marks d, e and f are zero or positive numbers and satisfy the following relationship:

2≤d+e+f≤20, where d≥2; and

b) Agricultural active ingredients selected from the group consisting of: aldimorph, clarizoline, mobendazim, dimethomorph; flusilazole, penconazole, cyconazole, econazole, furconazole, propiconazole, penconazole Coniferazole, carbendazim, thiophanate, benomyl, carbendazim, chlorothalonil, clonidamine, trifloxystrobin, fluoxastrobin, kyserostrobin, azoxystrobin, fenstrobin, propylchloride Ling, sulfamethanil, oxafefenone, captan, maneb, mancozeb, multi-antibacterial bacteria, Bacillus thuringiensis, Acetyl 105, abamectin, doramectin, lepimectin, pyrethrin, Carbaryl, pirimicarb, aldicarb, methoxam, chrysanthemum, boric acid, chlordimeform, diflubenzuron, ditriflubenzuron, dimeturon, diflubenzuron, mimaphid, Zinon, acephate, endosulfan, kelevan, dimethoate, azinphos-ethyl, azinphos-methyl, isoxazophos, chlorpyrifos, tetrafenazine, cyhalothrin, permethrin, fluorine Permethrin, Cypermethrin, Phenoxyacetic Acid, Phenoxypropionic Acid, Phenoxybutyric Acid, Benzoic Acid, Triazines and S-Triazines, Substituted Ureas, Uracil, Bentazone, Isobenad, Imazetam, Bendicon, Dacaozhi, Diquat, Clomazone, Fluoxazone, Dazamide, Dinitroaniline, Isalaline, Huangcaoxiao, Amoxazol, Amprofen, Trifluralin , glyphosate, glufosinate-ammonium, sulfonylurea, imidazolinone, pyridine carboxylic acid, clethodim, chloroform, fenoxaprop-p-p, fluoralifop-pyl, chloroxyfop-pyridine, grass Gram, sethoxydim, dichlorpyril, clomazone, bipyridylium compound, zinc sulfate, ferrous sulfate, ammonium sulfate, urea, urea ammonium nitrogen, ammonium thiosulfate, potassium sulfate, monoammonium phosphate, urea phosphate , calcium nitrate, boric acid, potassium salt of boric acid, sodium salt of boric acid, phosphoric acid, magnesium hydroxide, manganese carbonate, calcium polysulfide, copper sulfate, manganese sulfate, iron sulfate, calcium sulfate, sodium molybdate, and calcium chloride, wherein said agricultural composition has improved resistance to hydrolysis.

52. The composition of item 51, wherein the subscript f is 0.

53. The composition according to item 51, wherein subscript e is 0-3.

54. The composition according to item 51, wherein subscript d is 8-11.

55. The composition according to item 51, wherein R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are methyl groups.

56. The composition of item 51, wherein R ¹⁸ is methyl.

57. The composition of item 52, wherein subscript e is 0.

58. The composition of item 57, wherein the subscript d is 8.

59. The composition according to item 58, wherein R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are methyl groups.

60. The composition of item 59, wherein R ¹⁸ is methyl.

61. An aqueous emulsion, wherein the discontinuous phase comprises water and the continuous phase comprises the composition of item 41.

62. An aqueous emulsion, wherein the discontinuous phase comprises water and the continuous phase comprises the composition of item 51.

63. An aqueous emulsion, wherein the continuous phase comprises water and the discontinuous phase comprises the composition of item 41.

64. An aqueous emulsion, wherein the continuous phase comprises water and the discontinuous phase comprises the composition of item 51.

65. A non-aqueous emulsion, wherein the discontinuous phase comprises a non-aqueous hydroxylic solvent and the continuous phase comprises the composition of item 41.

66. A non-aqueous emulsion, wherein the discontinuous phase comprises a non-aqueous hydroxylic solvent and the continuous phase comprises the composition of item 51.

67. A non-aqueous emulsion, wherein the continuous phase comprises a non-aqueous hydroxylic solvent and the discontinuous phase comprises the composition of item 41.

68. A non-aqueous emulsion, wherein the continuous phase comprises a non-aqueous hydroxylic solvent and the discontinuous phase comprises the composition of item 51.

69. An agricultural composition comprising:

a) Silicones having the formula:

M ⁵ D ³ M ⁶

in

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

in

R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ are each independently selected from monovalent hydrocarbon groups with 1 to 4 carbon atoms, aryl groups, and aryl substituents with 6 to 20 carbon atoms An alkyl hydrocarbon group with 4 to 9 carbon atoms, R ²⁵ is a branched or straight chain hydrocarbon group with 2 to 4 carbon atoms; Z" is an oxyalkylene group with the following general formula: R ²⁶ (C ₂ H ₄ O ) _g (C ₃ H ₆ O) _h (C ₄ H ₈ O) _i R ²⁷ , where R ²⁶ is straight-chain or branched with 2, 3, 5, 6, 7, 8 or 9 carbon atoms Divalent hydrocarbon group; ^R27 is selected from H, monovalent hydrocarbon group and acetyl group with 1 to 6 carbon atoms, subscripts g, h and i are zero or positive numbers and satisfy the following relationship:

2≤g+h+i≤20, where g≥2; and

b) agriculturally active ingredients,

wherein said agricultural composition has improved resistance to hydrolysis.

70. The composition of item 69, wherein R ²⁷ is selected from hydrogen and methyl.

71. The composition of item 69, wherein subscript i is 0.

72. The composition of item 69, wherein the subscript h is 0-3.

73. The composition of item 69, wherein the subscript g is 8-11.

74. The composition of item 69, wherein R ²⁵ is selected from monovalent hydrocarbon groups of 3 and 4 carbon atoms.

75. The composition of item 69, wherein R ²⁶ is a monovalent hydrocarbon group of 3 carbon atoms.

76. The composition according to item 69, wherein R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ are methyl.

77. The composition of item 76, wherein R ²⁵ is a monovalent hydrocarbon group of 4 carbon atoms.

78. The composition of item 77, wherein R ²⁵ is a monovalent hydrocarbon group of 4 carbon atoms.

79. The composition according to item 78, wherein R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ are methyl.

80. The composition of item 79, wherein the subscript g is 8.

81. The composition of item 80, wherein the subscript h is 0.

82. The composition of item 81, wherein subscript i is 0.

83. An agricultural composition comprising:

a) Silicones having the formula:

M ⁵ D ³ M ⁶

in

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

in

R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ are each independently selected from monovalent hydrocarbon groups with 1 to 4 carbon atoms, aryl groups, and aryl substituents with 6 to 20 carbon atoms An alkyl hydrocarbon group with 4 to 9 carbon atoms, R ²⁵ is a branched or straight chain hydrocarbon group with 2 to 4 carbon atoms; Z" is an oxyalkylene group with the following general formula: R ²⁶ (C ₂ H ₄ O ) _g (C ₃ H ₆ O) _h (C ₄ H ₈ O) _i R ²⁷ , where R ²⁶ is straight-chain or branched with 2, 3, 5, 6, 7, 8 or 9 carbon atoms Divalent hydrocarbon group; ^R27 is selected from H, monovalent hydrocarbon group and acetyl group with 1 to 6 carbon atoms, subscripts g, h and i are zero or positive numbers and satisfy the following relationship:

2≤g+h+i≤20, where g≥2; and

b) Agricultural active ingredients selected from the group consisting of: aldimorph, clarizoline, mobendazim, dimethomorph; flusilazole, penconazole, cyconazole, econazole, furconazole, propiconazole, penconazole Coniferazole, carbendazim, thiophanate, benomyl, carbendazim, chlorothalonil, clonidamine, trifloxystrobin, fluoxastrobin, kyserostrobin, azoxystrobin, fenstrobin, propylchloride Ling, sulfamethanil, oxafefenone, captan, maneb, mancozeb, multi-antibacterial bacteria, Bacillus thuringiensis, Acetyl 105, abamectin, doramectin, lepimectin, pyrethrin, Carbaryl, pirimicarb, aldicarb, methoxam, chrysanthemum, boric acid, chlordimeform, diflubenzuron, ditriflubenzuron, dimeturon, diflubenzuron, mimaphid, Zinon, acephate, endosulfan, kelevan, dimethoate, azinphos-ethyl, azinphos-methyl, isoxazophos, chlorpyrifos, tetrafenazine, cyhalothrin, permethrin, fluoride Permethrin, Cypermethrin, Phenoxyacetic Acid, Phenoxypropionic Acid, Phenoxybutyric Acid, Benzoic Acid, Triazines and S-Triazines, Substituted Ureas, Uracil, Bentazone, Isobenad, Imazetam, Bendicon, Dacaozhi, Diquat, Clomazone, Fluoxazone, Dazamide, Dinitroaniline, Isalaline, Huangcaoxiao, Amoxazol, Amprofen, Trifluralin , glyphosate, glufosinate-ammonium, sulfonylurea, imidazolinone, pyridine carboxylic acid, clethodim, chloroform, fenoxaprop-p-p, fluoralifop-pyl, chloroxyfop-pyridine, grass Gram, sethoxydim, dichlorpyril, clomazone, bipyridylium compound, zinc sulfate, ferrous sulfate, ammonium sulfate, urea, urea ammonium nitrogen, ammonium thiosulfate, potassium sulfate, monoammonium phosphate, urea phosphate , calcium nitrate, boric acid, potassium salt of boric acid, sodium salt of boric acid, phosphoric acid, magnesium hydroxide, manganese carbonate, calcium polysulfide, copper sulfate, manganese sulfate, iron sulfate, calcium sulfate, sodium molybdate, and calcium chloride, wherein said agricultural composition has improved resistance to hydrolysis.

84. The composition of item 83, wherein R ²⁷ is selected from hydrogen and methyl.

85. The composition of item 83, wherein subscript i is 0.

86. The composition according to item 83, wherein the subscript h is 0-3.

87. The composition according to item 83, wherein the subscript g is 8-11.

88. The composition of item 83, wherein R ²⁵ is selected from monovalent hydrocarbon groups of 3 and 4 carbon atoms.

89. The composition of item 83, wherein R ²⁶ is a monovalent hydrocarbon group of 3 carbon atoms.

90. The composition according to item 83, wherein R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ are methyl.

91. The composition of item 90, wherein R ²⁵ is a monovalent hydrocarbon group of 4 carbon atoms.

92. The composition of item 91, wherein R ²⁵ is a monovalent hydrocarbon group of 4 carbon atoms.

93. The composition according to item 92, wherein R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ are methyl.

94. The composition of item 93, wherein the subscript g is 8.

95. The composition of item 94, wherein the subscript h is 0.

96. The composition of item 95, wherein subscript i is 0.

97. An aqueous emulsion, wherein the discontinuous phase comprises water and the continuous phase comprises the composition of item 69.

98. An aqueous emulsion, wherein the discontinuous phase comprises water and the continuous phase comprises the composition of item 83.

99. An aqueous emulsion, wherein the continuous phase comprises water and the discontinuous phase comprises the composition of item 69.

100. An aqueous emulsion, wherein the continuous phase comprises water and the discontinuous phase comprises the composition of item 83.

101. A non-aqueous emulsion, wherein the discontinuous phase comprises a non-aqueous hydroxylic solvent and the continuous phase comprises the composition of item 69.

102. A non-aqueous emulsion, wherein the discontinuous phase comprises a non-aqueous hydroxylic solvent and the continuous phase comprises the composition of item 83.

103. A non-aqueous emulsion, wherein the continuous phase comprises a non-aqueous hydroxylic solvent and the discontinuous phase comprises the composition of item 69.

104. A non-aqueous emulsion, wherein the continuous phase comprises a non-aqueous hydroxylic solvent and the discontinuous phase comprises the composition of item 83.

105. A personal care composition comprising: a) the composition of item 1; and b) a personal care ingredient, wherein the cosmetic composition has improved resistance to hydrolysis.

106. A human care composition comprising: a) the composition of item 41; and b) a personal care ingredient, wherein the personal care composition has improved resistance to hydrolysis.

107. A personal care composition comprising: a) the composition of item 69; and b) a personal care ingredient, wherein the personal care composition has improved resistance to hydrolysis.

108. A home care composition comprising: a) the composition of item 1; and b) a surfactant selected from hydrocarbon-based surfactants and fluorocarbon-based surfactants, wherein the home care composition Has improved hydrolysis resistance.

109. A home care composition comprising: a) the composition of item 41; and b) a surfactant selected from hydrocarbon-based surfactants and fluorocarbon-based surfactants, wherein the home care composition Has improved hydrolysis resistance.

110. A home care composition comprising: a) the composition of item 69; and b) a surfactant selected from hydrocarbon-based surfactants and fluorocarbon-based surfactants, wherein the home care composition Has improved hydrolysis resistance.

111. A coating composition comprising: a) the composition of item 1; and b) a resin selected from polyesters, alkyd resins, acrylic resins, polyurethanes and epoxy resins, wherein the coating composition has improved Hydrolysis resistance.

112. A coating composition comprising: a) the composition of item 41; and b) a resin selected from polyesters, alkyd resins, acrylic resins, polyurethanes and epoxy resins, wherein the coating composition has improved Hydrolysis resistance.

113. A coating composition comprising: a) the composition of item 69; and b) a resin selected from polyesters, alkyd resins, acrylic resins, polyurethanes and epoxy resins, wherein the coating composition has improved Hydrolysis resistance.

114. An agricultural composition comprising

a) Silicones having the formula:

M ³ D ² M ⁴

in

M ³ =(R ¹⁰ )(R ¹¹ )(R ¹² )SiO _1/2 ;

M ⁴ =(R ¹³ )(R ¹⁴ )(R ¹⁵ )SiO _1/2 ; and

D ² =(R ¹⁶ )(Z')SiO _2/2

in

R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently selected from monovalent hydrocarbon groups with 1 to 4 carbon atoms, aryl groups, and aryl groups with 6 to 20 carbon atoms An alkyl hydrocarbon group of 4 to 9 carbon atoms as a substituent; Z' is an oxyalkylene group having the formula: R ¹⁷ (C ₂ H ₄ O) _d (C ₃ H ₆ O) _e (C ₄ H ₈ O) _f R ¹⁸ , where R ¹⁷ has the chemical formula -C ₄ H ₈ O-(C ₂ H ₄ O)-; R ¹⁸ is selected from H, a monovalent hydrocarbon group having 1 to 6 carbon atoms and an acetyl group, the following The marks d, e and f are zero or positive numbers and satisfy the following relationship:

2≤d+e+f≤20, wherein d≥2; the proviso is that when R ¹⁸ is methyl, d is 2～5 or 8～20; and

b) agriculturally active ingredients,

wherein said agricultural composition has improved resistance to hydrolysis.

115. An agricultural composition comprising

a) Silicones having the formula:

M ³ D ² M ⁴

in

M ³ =(R ¹⁰ )(R ¹¹ )(R ¹² )SiO _1/2 ;

M ⁴ =(R ¹³ )(R ¹⁴ )(R ¹⁵ )SiO _1/2 ; and

D ² =(R ¹⁶ )(Z')SiO _2/2

in

R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently selected from monovalent hydrocarbon groups with 1 to 4 carbon atoms, aryl groups, and aryl groups with 6 to 20 carbon atoms An alkyl hydrocarbon group of 4 to 9 carbon atoms as a substituent; Z' is an oxyalkylene group having the formula: R ¹⁷ (C ₂ H ₄ O) _d (C ₃ H ₆ O) _e (C ₄ H ₈ O) _f R ¹⁸ , where R ¹⁷ has the chemical formula -C ₄ H ₈ O-(C ₂ H ₄ O)-; R ¹⁸ is selected from H, a monovalent hydrocarbon group having 1 to 6 carbon atoms and an acetyl group, the following The marks d, e and f are zero or positive numbers and satisfy the following relationship:

2≤d+e+f≤20, wherein d≥2; the proviso is that when R ¹⁸ is methyl, d is 2～5 or 8～20; and

b) Agricultural active ingredients selected from the group consisting of: aldimorph, clarizoline, mobendazim, dimethomorph; flusilazole, penconazole, cyconazole, econazole, furconazole, propiconazole, penconazole Coniferazole, carbendazim, thiophanate, benomyl, carbendazim, chlorothalonil, clonidamine, trifloxystrobin, fluoxastrobin, kyserostrobin, azoxystrobin, fenstrobin, propylchloride Ling, sulfamethanil, oxafefenone, captan, maneb, mancozeb, multi-antibacterial bacteria, Bacillus thuringiensis, Acetyl 105, abamectin, doramectin, lepimectin, pyrethrin, Carbaryl, pirimicarb, aldicarb, methoxam, chrysanthemum, boric acid, chlordimeform, diflubenzuron, ditriflubenzuron, dimeturon, diflubenzuron, mimaphid, Zinon, acephate, endosulfan, kelevan, dimethoate, azinphos-ethyl, azinphos-methyl, isoxazophos, chlorpyrifos, tetrafenazine, cyhalothrin, permethrin, fluoride Permethrin, Cypermethrin, Phenoxyacetic Acid, Phenoxypropionic Acid, Phenoxybutyric Acid, Benzoic Acid, Triazines and S-Triazines, Substituted Ureas, Uracil, Bentazone, Isobenad, Imazetam, Bendicon, Dacaozhi, Diquat, Clomazone, Fluoxazone, Dazamide, Dinitroaniline, Isalaline, Huangcaoxiao, Amoxazol, Amprofen, Trifluralin , glyphosate, glufosinate-ammonium, sulfonylurea, imidazolinone, pyridine carboxylic acid, clethodim, chloroform, fenoxaprop-p-p, fluoralifop-pyl, chloroxyfop-pyridine, grass Gram, sethoxydim, dichlorpyril, clomazone, bipyridylium compound, zinc sulfate, ferrous sulfate, ammonium sulfate, urea, urea ammonium nitrogen, ammonium thiosulfate, potassium sulfate, monoammonium phosphate, urea phosphate , calcium nitrate, boric acid, potassium salt of boric acid, sodium salt of boric acid, phosphoric acid, magnesium hydroxide, manganese carbonate, calcium polysulfide, copper sulfate, manganese sulfate, iron sulfate, calcium sulfate, sodium molybdate, and calcium chloride, wherein said agricultural composition has improved resistance to hydrolysis.

116. The composition according to item 41, wherein R ¹⁸ is methyl and subscript d is 6-8.

117. The composition according to item 51, wherein R ¹⁸ is methyl and subscript d is 6-8.

Detailed description of the invention

As used herein, integer values of stoichiometric subscripts refer to molecular species, and non-integer values of stoichiometric subscripts refer to mixtures of molecular species on a molecular weight average basis, number average basis, or mole fraction basis. In the case of mixtures of compounds of the invention, it should be readily seen that the stoichiometric subscripts of the mixture will have the average values of these tables below, compared to the pure compounds, and that the average subscript values will be integer or non-integer .

The present invention provides an extreme environment composition for use as an agricultural composition, a personal care composition, a coating composition or a home care composition, said composition comprising a silicone composition comprising a surface active A trisiloxane compound or a combination thereof selected from trisiloxane compounds of formula I, II or III.

Trisiloxane compound I has the formula:

M ¹ D ¹ M ²

in

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

in

R ¹ is selected from branched or linear hydrocarbon groups of 2 to 4 carbon atoms, aryl groups, and alkyl hydrocarbon groups of 4 to 9 carbon atoms 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 a monovalent hydrocarbon group of 1 to 4 carbon atoms, an aryl group, and a hydrocarbon group of 4 to 9 carbon atoms containing an aryl group; Z is a An oxyalkylene group of the following 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 has 2, 3, 5, 6, 7, 8 or 9 carbon atoms straight chain or branched divalent hydrocarbon group; R ⁹ is selected from H, monovalent hydrocarbon group and acetyl group with 1 to 6 carbon atoms, subscript a, b and c are Zero or a positive number that satisfies the following relationship:

2≤a+b+c≤20, where a≥2.

When the subscript a satisfies the condition 2≦a≦5, it is recommended to use the co-surfactants listed below to achieve the benefits of the composition of the present invention.

Trisiloxane compound II has the formula:

M ³ D ² M ⁴

in

M ³ =(R ¹⁰ )(R ¹¹ )(R ¹² )SiO _1/2 ;

M ⁴ =(R ¹³ )(R ¹⁴ )(R ¹⁵ )SiO _1/2 ; and

D ² =(R ¹⁶ )(Z')SiO _2/2

in

R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently selected from monovalent hydrocarbon groups with 1 to 4 carbon atoms, aryl groups, and aryl groups with 6 to 20 carbon atoms An alkyl hydrocarbon group of 4 to 9 carbon atoms as a substituent; Z' is an oxyalkylene group having the general formula: R ¹⁷ (C ₂ H ₄ O) _d (C ₃ H ₆ O) _e (C ₄ H ₈ O) _f R ¹⁸ , wherein R ¹⁷ has the following formula: -C ₄ H ₈ O-(C ₂ H ₄ O)-; R ¹⁸ is selected from H, a monovalent hydrocarbon group having 1 to 6 carbon atoms, and acetyl base, the subscripts d, e and f are zero or positive numbers and satisfy the following relationship:

2≤d+e+f≤20, where d≥2.

Trisiloxane compound II may also have the following formula:

M ³ D ² M ⁴

in

M ³ =(R ¹⁰ )(R ¹¹ )(R ¹² )SiO _1/2 ;

M ⁴ =(R ¹³ )(R ¹⁴ )(R ¹⁵ )SiO _1/2 ; and

D ² =(R ¹⁶ )(Z')SiO _2/2

in

R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently selected from monovalent hydrocarbon groups with 1 to 4 carbon atoms, aryl groups, and aryl groups with 6 to 20 carbon atoms An alkyl hydrocarbon group of 4 to 9 carbon atoms as a substituent; Z' is an oxyalkylene group having the formula: R ¹⁷ (C ₂ H ₄ O) _d (C ₃ H ₆ O) _e (C ₄ H ₈ O) _f R ¹⁸ , wherein R ¹⁷ has the following formula: -C ₄ H ₈ O-(C ₂ H ₄ O)-; R ¹⁸ is selected from H, monovalent hydrocarbon groups and acetyl groups having 1 to 6 carbon atoms , the subscripts d, e and f are zero or positive and satisfy the following relationship:

2≤d+e+f≤20, wherein d≥2, provided that when R ¹⁸ is methyl, d is 2-5 or 8-20.

When the subscript d satisfies the condition 2≦d≦5, it is recommended to use the co-surfactants listed below to achieve the benefits of the compositions of the present invention.

Trisiloxane compound III has the formula:

M ⁵ D ³ M ⁶

in

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

in

R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ are each independently selected from monovalent hydrocarbon groups with 1 to 4 carbon atoms, aryl groups, and aryl substituents with 6 to 20 carbon atoms An alkyl hydrocarbon group with 4 to 9 carbon atoms, R ²⁵ is a branched or straight chain hydrocarbon group with 2 to 4 carbon atoms; Z" is an oxyalkylene group with the following general formula: R ²⁶ (C ₂ H ₄ O ) _g (C ₃ H ₆ O) _h (C ₄ H ₈ O) _i R ²⁷ , where R ²⁶ is straight-chain or branched with 2, 3, 5, 6, 7, 8 or 9 carbon atoms Divalent hydrocarbon group; ^R27 is selected from H, monovalent hydrocarbon group and acetyl group with 1 to 6 carbon atoms, subscripts g, h and i are zero or positive numbers and satisfy the following relationship:

2≤g+h+i≤20, where g≥2.

When the subscript g satisfies the condition 2≦g≦5, it is recommended to use the co-surfactants listed below to achieve the benefits of the compositions of the present invention.

One method of preparing the compositions of the present invention is to react a molecule of the formula with an olefinically modified polyalkylene oxide under hydrosilylation conditions:

MD ^H M

In the formula, D ^H is the hydride precursor of the D' structural unit in the composition of the present invention, wherein its definition and relationship are defined below, and consistent with the definition made above, said olefin-modified polyoxyalkylene such as Allyloxypolyethylene glycol, or methallyloxypolyoxyalkylene, these compounds are cited in this application as examples, not meant to limit other possible olefin-modified oxyalkylene components. As used herein, the phrase "olefin-modified polyoxyalkylene" is defined as a molecule having one or more oxyalkylene groups containing one or more terminal carbon-carbon double bonds or pendant carbon-carbon double bonds . Polyethers (precursors of substituted moieties Z, Z' or Z") are olefin-modified polyoxyalkylenes (hereinafter "polyethers") represented by the general formula:

CH ₂ =CH(R ²⁸ )(R ²⁹ ) _j O(R ³⁰ ) _k (C ₂ H ₄ O) _m (C ₃ H ₆ O) _n (C ₄ H ₈ O) _p R ³¹

In the formula

R ²⁸ is H or methyl; R ²⁹ is a divalent alkyl group with 1 to 6 carbon atoms, wherein the subscript j can be 0 or 1; R ³⁰ is -C ₂ H ₄ O-, wherein the subscript k is 0 or 1; R ³¹ is H, a monofunctional hydrocarbon group with 1 to 6 carbon atoms, or an acetyl group, and the subscripts m, n and p are zero or positive numbers and satisfy the relationship: 2≤m+n+p≤ 20, where m≥2. When the polyether is composed of mixed oxyalkylene oxide groups (ie ethylene oxide, propylene oxide and butylene oxide), the units can be block or randomly distributed. Those skilled in the art will appreciate the benefits of using block or random configurations. Illustrative examples of block configurations are: - (ethylene oxide) _a (propylene oxide) _b ; - (butylene oxide) _c (ethylene oxide) _a -; and - (propylene oxide) _b (ethylene oxide) _a (oxy butene) _c- .

Illustrative examples of polyethers are provided below, but are not limited to these:

_CH2 = _CHCH2O ( _{CH2CH2O ) 8H} ; _{CH2 = CHCH2O} ( _CH2CH2O ) _{8CH3 ;}

_CH2 = _CHCH2O ( _CH2CH2O ) _{4 ( CH2CH} ( _CH3 )O) _5H ;

_CH2 =CHO( _CH2CH2O ) ₅ ( _CH2CH ( _{CH3 )} O) _5H ;

CH ₂ =C(CH ₃ )CH ₂ O(CH ₂ CH ₂ O) ₄ (CH ₂ CH(CH ₃ )O) ₅ C(=O)CH ₃ ;

CH ₂ =CHCH ₂ O(CH ₂ CH ₂ O) ₅ (CH ₂ CH(CH ₃ )O) ₂ (CH ₂ CH(CH ₂ CH ₃ )O) ₂ H

Olefin-modified (i.e. vinyl, allyl or methallyl) polyoxyalkylenes are grafted onto the trisiloxane hydride (SiH) intermediates of the invention in a conventional manner by using a hydrosilylation reaction In vivo to prepare polyether-modified siloxane.

In a preferred embodiment of the trisiloxane compound of formula I, ^R1 and ^R4 are selected from branched or linear hydrocarbon groups, aryl groups, and substituted aryl groups containing 6 to 20 carbon atoms. An alkyl hydrocarbon group of 4 to 9 carbon atoms; more preferably a branched or straight chain hydrocarbon group or an aryl group of 3 to 4 carbon atoms. R ² , R ³ , R ⁵ , R ⁶ and R ⁷ are each independently selected from monovalent hydrocarbon groups of 1 to 4 carbon atoms, aryl groups, and hydrocarbon groups of 4 to 9 carbon atoms containing aryl groups; more preferably 1 Monovalent hydrocarbon and aryl groups of ~2 carbon atoms; most preferably methyl. Z is an oxyalkylene group having 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 group having 2, 3 , a linear or branched divalent hydrocarbon group of 5, 6, 7, 8 or 9 carbon atoms, more preferably 3 to 7 carbon atoms, most preferably 3 to 6 carbon atoms. The subscripts a, b and c are zero or positive numbers and satisfy the following relationship: 2≤a+b+c≤20, where a≥2; preferably a is 5-20, more preferably 5-8; preferably b is 0 ~10, more preferably 0~5; preferably c is 0~8, more preferably 0~4. R ⁹ is selected from H, a monovalent hydrocarbon group having 1 to 6 carbon atoms, and an acetyl group.

In another preferred embodiment of the trisiloxane compound of formula I, R ¹ , R ⁴ and R ⁷ are selected from branched or linear hydrocarbon groups and aryl groups with 2 to 4 carbon atoms; more preferably 3 to 4 carbon atoms A branched or straight-chain hydrocarbon group of atoms. R ² , R ³ , R ⁵ and R ⁶ are each independently selected from a monovalent hydrocarbon group with 1 to 4 carbon atoms, and an aryl group; more preferably a monovalent hydrocarbon group with 1 to 2 carbon atoms; most preferably a methyl group. Z is as defined above.

In a preferred embodiment of the trisiloxane compound of formula II, R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently selected from monovalent hydrocarbon groups with 1 to 4 carbon atoms, and aryl; Z' is an oxyalkylene group of the general formula: R ¹⁷ (C ₂ H ₄ O) _d (C ₃ H ₆ O) _e (C ₄ H ₈ O) _f R ¹⁸ , where R ¹⁷ is selected from From the general formula -C ₄ H ₈ O-(C ₂ H ₄ O)-branched or linear divalent hydrocarbon groups; R ¹⁸ is selected from H, monovalent hydrocarbon groups and acetyl groups with 1 to 6 carbon atoms, More preferably H and a monovalent hydrocarbon group of 1 to 4 carbon atoms, the subscripts d, e and f are zero or positive numbers and satisfy the following relationship:

2≤d+e+f≤20, wherein d≥2; preferably d is 5-20, more preferably 5-8; preferably e is 0-10; more preferably 0-5; preferably f is 0-8, More preferably, it is 0-4.

In a preferred embodiment of the trisiloxane compound of formula III, R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , and R ²⁴ are each independently selected from monovalent hydrocarbon groups and aryl groups with 1 to 4 carbon atoms ; R ²⁵ is a linear or branched hydrocarbon group of 2 to 4 carbon atoms, most preferably 3 to 4 carbon atoms; Z" is an oxyalkylene group having the general formula: R ²⁶ (C ₂ H ₄ O) _g (C ₃ H ₆ O) _h (C ₄ H ₈ O) _i R ²⁷ , where R ²⁶ is a linear or branched di Valence hydrocarbon group, more preferably 3 to 7 carbon atoms, most preferably 3 to 6 carbon atoms;

R ^is selected from H, a monovalent hydrocarbon group having 1 to 6 carbon atoms and an acetyl group, more preferably H and a monovalent hydrocarbon group having 1 to 4 carbon atoms; subscripts g, h and i are zero or positive numbers and Satisfy the following relationship:

2≤g+h+i≤20, wherein g≥2; preferably g is 5-20, more preferably 5-8; preferably h is 0-10, more preferably 0-5; preferably i is 0-8, More preferably, it is 0-4.

Noble metal catalysts suitable for use in preparing polyether-substituted siloxanes are also well known in the art and include complexes of rhodium, ruthenium, palladium, osmium, iridium, and/or platinum. Many types of platinum catalysts are known for this SiH olefin addition reaction, and such platinum catalysts can be used to produce the compositions of the present invention. The platinum compound may be selected from those having the formula (PtCl ₂ olefin) and H(PtCl ₃ olefin), as described in US Patent 3,159,601, which is incorporated herein by reference. Additional platinum-containing species may be complexes of chloroplatinic acid with up to 2 moles per gram of platinum of a species selected from alcohols, ethers, aldehydes, and mixtures thereof, as described in US Pat. No. 3,220,972, which is incorporated herein by reference. Another class of platinum-containing materials useful in the present invention is described in US Patent Nos. 3,715,334; 3,775,452 and 3,814,730 (Karstedt). Additional background on the prior art can be found in JLSpier, "Homogeneous Catalysis of Hydrosilation by Transition Metals", Advances in Organometallic Chemistry, Vol. 17, pp. 407-447, edited by FGA Stone and R. West, Academic Press (New York, 1979) published. An effective amount of platinum catalyst can be readily determined by one skilled in the art. Typically, an effective amount is from about 0.1 to 50 ppm of the total organomodified trisiloxane composition.

The compositions of the present invention show increased resistance to hydrolysis outside the pH range of 6 to 7.5, ie under extreme environmental conditions as defined herein. Increased resistance to hydrolysis can be demonstrated by a variety of tests, but as used herein, increased resistance to hydrolysis means after 24 hours exposure to aqueous acidic conditions with a solution pH below 6 or after exposure to a solution pH greater than 7.5 After 24 hours under aqueous alkaline conditions, 50 mol% or more of the hydrolysis-resistant composition of the present invention remains unchanged or unreacted. Under acidic conditions, the composition of the present invention exhibits a survival rate (survival) of 50 mol% or greater of the initial concentration at a pH of 5 or below for a period of more than 48 hours; A pH of 5 or below for more than 2 weeks exhibited a residual rate of 50 mol % or more; more specifically, the composition of the present invention exhibited a pH of 5 or below for more than 1 month A residual rate of 50 mol% or greater; most specifically, the composition of the present invention exhibits a residual rate of 50 mol% or greater when maintained at a pH of 5 or below for a period of more than 6 months. Under alkaline conditions, the composition of the present invention exhibits a residual rate of 50 mol% or more when maintained at a pH of 8 or above for a period of more than 2 weeks; specifically, the composition of the present invention has a pH of 8 or above exhibits a residual rate of 50 mol% or greater when maintained over a period of 4 weeks; more specifically, a composition of the present invention exhibits a residual rate of 50 mol% when maintained at a pH of 8 or above over a period of 6 months or greater; most specifically, the compositions of the present invention exhibit a residual rate of 50 mol% or greater when maintained at a pH of 8 or above for a period of more than 1 year.

Uses of the composition of the present invention:

A. Pesticides - Agriculture, Horticulture, Turf, Ornamental and Forestry:

Many pesticide applications require that adjuvants be added to the spray mixture to provide wetting and spreading on the foliage. Adjuvants are often surfactants, which can serve various functions, such as increasing the retention of spray droplets on difficult-to-wet foliage surfaces, increasing spread to improve spray coverage, or providing penetration of herbicides into plant cuticles sex. These adjuvants are either provided as tank-side additives or used as components in pesticide formulations.

Typical applications for pesticides include agricultural, horticultural, turf, ornamental, home and garden, veterinary and forestry applications.

The pesticide composition of the present invention also includes at least one pesticide wherein the organomodified trisiloxane surfactant of the present invention is present as a concentrate or dilution in a tank mix in an amount sufficient to provide 0.005 % to 2% final use concentration. Optionally, the pesticidal composition may include excipients, co-surfactants, solvents, foam control agents, deposition aids, drift retardants, biological agents, micronutrients, fertilizers, and the like. The term pesticide refers to any compound used to destroy pests, such as rodenticides, insecticides, acaricides, fungicides and herbicides. Illustrative examples of pesticides that may be used include, but are not limited to, growth regulators, photosynthesis inhibitors, pigment inhibitors, mitotic disrupters, lipid biosynthesis inhibitors, cell wall inhibitors, and cell membrane disrupters. The amount of pesticide used in the compositions of the invention will vary with the type of pesticide used. More specific examples of pesticide compounds that can be used with the compositions of the present invention are, but not limited to, herbicides and growth regulators such as: phenoxyacetic acid, phenoxypropionic acid, phenoxybutyric acid, benzoic acid, triazine and s-triazines, substituted ureas, uracils, bentazone, isofendiazon, bemazad, benzadon, daquat, diquat, clomazone, fluridone, dacet Aquamide, dinitroaniline, isolaline, huangcaoxiao, ammonium, amiproflurine, trifluralin, glyphosate, glufosinate-ammonium, sulfonylurea, imidazolinone, pyridine carboxylic acid, olefin Oxaprop-methyl, chloralofop, fenoxaprop, fluazifop-p-p, haloxyfop, quizalofop, methoxydim, dichonil, oxapropen, and bipyridinium (bipyridylium) compound.

The fungicidal compositions that can be used in the present invention may include, but are not limited to, aldimorph, clarizolin, mobendazim, dimethomorph; azoles, propiconazole, tebuconazole, etc.; carbendazim, thiophanate, benomyl, carbendazim, chlorothialonil (chlorothialonil), nicloramine, trifloxystrobin (trifloxystrobin), fluoxastrobin (fluoxystrobin ), dimoxystrobin, azoxystrobin, furcaranil, prochloraz, sulfastrobin, famoxadone, captan, maneb, maneb Mancozeb, polyantibacterial, multifruit, and metalaxyl.

Insecticide, larvicide, acaricide and ovacide compounds that can be used with the compositions of the present invention include, but are not limited to, Bacillus thuringiensis, Acetate 105 (spinosad), abamectin (abamectin), doramectin, lepimectin, pyrethrins, carbaryl, pirimicarb (pirimicarb), aldicarb, methoxam, chlorpyrifos, boric acid, chlordimeform, diflufenuron ( novaluron), bistrifluron (bistrifluron), triflumeron, hexamethonium, imidamid, diazinon, acephate, endosulfan, kelevan, dimethoate, azinphos-ethyl, gluten Thion, isoxafos (izoxathion), chlorpyrifos, tetrafenazine, cyhalothrin, permethrin, bifenthrin, cypermethrin, etc.

Pesticides can be liquid or solid. If solid, it is preferred that it is soluble in a solvent or organomodified trisiloxane of the present invention prior to application, the silicone may be used as a solvent, or a surfactant for such solubility, or another surface Active agents can accomplish this function.

Agricultural excipients:

Buffers, preservatives and other standard excipients known in the art can also be included in the composition.

Solvents may also be included in the compositions of the present invention. These solvents are liquid at room temperature. Examples include water, alcohols, aromatic solvents, oils (ie, mineral oils, vegetable oils, silicone oils, etc.), lower alkyl esters of vegetable oils, fatty acids, ketones, glycols, polyethylene glycols, glycols, paraffins, and the like. A particular solvent may be 2,2,4-trimethyl-1,3-pentanediol and its alkoxylated (especially ethoxylated) variants as described in US Patent 5,674,832, Or N-methyl-pyrrolidone (n-methyl-pyrrilidone), said US patent is incorporated herein by reference.

Co-surfactant:

Also useful are other co-surfactants that have short chain hydrophobic groups that do not interfere with superspreading, as described in U.S. Patent Nos. 5,558,806, 5,104,647, and 6,221,811, which are incorporated herein by reference .

Co-surfactants useful herein include nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, zwitterionic surfactants, polymeric surfactants, or any mixtures thereof. Surfactants are typically hydrocarbon-based, silicone-based or fluorocarbon-based.

Useful surfactants include alkoxylates, especially ethoxylates, containing block copolymers including copolymers of ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof ; Alkylarylalkoxylates, especially ethoxylates or propoxylates, and their derivatives, including alkylphenol ethoxylates; Arylarylalkoxylates, especially ethoxylates Alkylates or propoxylates, and their derivatives; Amine alkoxylates, especially amine ethoxylates; Fatty acid alkoxylates; Fatty alcohol alkoxylates; Alkyl sulfonates; Alkylbenzene and alkylnaphthalene sulfonates; sulfated fatty alcohols, amines or amides; acid esters of sodium isethionate; esters of sodium sulfosuccinate; sulfated or sulfonated fatty acid esters; Petroleum sulfonates; N-acyl sarcosinates; alkyl polyglycosides; alkyl ethoxylated amines;

Specific examples include alkylacetylene glycols (SURFONYL-Air Products), pyrrilodone-based surfactants (e.g., SURFADONE-LP100-ISP), 2-ethylhexyl sulfate, isodecyl alcohol ethoxy Compounds (eg, RHODASURF DA530-Rhodia), Ethylenediamine Alkoxylates (TETRONICS-BASF), Ethylene Oxide/Propylene Oxide Copolymers (PLURONICS-BASF), Gemini-type Surfactants (Rhodia).

Preferred surfactants include ethylene oxide/propylene oxide copolymers (EO/PO); amine ethoxylates; alkyl polyglycosides; oxy-tridecyl alcohol ethoxylates, and the like.

In a preferred embodiment, the agrochemical composition of the present invention further includes one or more agrochemical ingredients. Suitable agrochemical ingredients include, but are not limited to, herbicides, insecticides, growth regulators, fungicides, miticides, acaricides, fertilizers, biologicals, plant nutrients, Micronutrients, biocides, paraffinic mineral oils, methylated seed oils (i.e. methylsoyate or methylcanolate), vegetable oils (e.g. soybean oil and rapeseed oil), water conditioners such as (Loveland Industries, Greeley, CO) and Quest (Helena Chemical, Collierville, TN), modified clays such as (Englehard Corp.,), foam control agents, surfactants, wetting agents, dispersants, emulsifiers, deposition aids, antidrift components, and water.

Suitable agrochemical compositions are prepared in a manner known in the art by combining, for example, by mixing one or more of the aforementioned components with the organomodified trisiloxanes according to the invention, as a tank mix, Or as a "can" preparation. The term "tank mix" refers to the addition of at least one agrochemical to a spray medium, such as water or oil, immediately before use. The term "can" refers to a formulation or concentrate containing at least one agrochemical component. The "in-pot" formulation can then be diluted to the use concentration just before use, usually into a tank mix, or it can be used undiluted.

B. Paint:

Coating formulations often require wetting agents or surfactants for the purposes of emulsification, compatibilization of components, leveling, flow, and reduction of surface defects. In addition, these additives can bring improvements to the cured or dried film, such as improved abrasion resistance, anti-blocking properties, hydrophilicity and hydrophobicity. Coating formulations can exist as solventborne coatings, aqueous coatings and powder coatings.

Coating components can be used as: architectural coatings; OEM product coatings such as automotive coatings and coil coatings; specialty coatings such as industrial maintenance coatings and marine coatings;

Typical resin types include: polyesters, alkyds, acrylics, polyurethanes and epoxies.

C. Personal care products

In a preferred embodiment, based on per 100 parts by weight ("pbw") of the personal care composition, the organomodified trisiloxane surfactant of the present invention comprises 0.1 to 99 pbw, more preferably 0.5 to 30 pbw, Still more preferably 1 to 15 pbw of organomodified trisiloxane surfactant, and 1 pbw to 99.9 pbw, more preferably 70 pbw to 99.5 pbw, still more preferably 85 pbw to 99 pbw of personal care composition.

The organomodified trisiloxane surfactant compositions of the present invention can be used in the form of personal care emulsions such as lotions and creams. As is generally known, emulsions comprise at least two immiscible phases, one of which is continuous and the other is discontinuous. Additional emulsions may be liquid or solid with varying viscosities. Furthermore, the particle size of the emulsion can be such that the emulsion is a microemulsion, and when small enough, the microemulsion can be transparent. It is also possible to prepare emulsions of emulsions, which are often referred to as multiple emulsions. These lotions are available as:

1) an aqueous emulsion, wherein the discontinuous phase comprises water, and the continuous phase comprises the organomodified trisiloxane surfactant of the present invention;

2) an aqueous emulsion, wherein the continuous phase comprises the organomodified trisiloxane surfactant of the present invention, and the discontinuous phase comprises water;

3) a non-aqueous emulsion, wherein the discontinuous phase comprises a non-aqueous hydroxyl solvent and the continuous phase comprises the organomodified trisiloxane surfactant of the present invention; and

4) A non-aqueous emulsion wherein the continuous phase comprises a non-aqueous hydroxylic organic solvent and the discontinuous phase comprises the organomodified trisiloxane surfactant of the present invention.

Non-aqueous emulsions comprising a silicone phase are described in US Patent 6,060,546 and US Patent 6,271,295, the contents of which are specifically incorporated herein by reference.

As used herein, the term "non-aqueous hydroxyl organic compound" refers to a hydroxyl-containing organic compound that is liquid at room temperature, such as about 25°C and about 1 atmosphere, exemplified by alcohols, glycols, polyols, and polyglycols and its mixture. The non-aqueous organic hydroxylic solvent is selected from hydroxyl-containing organic compounds that are liquid at room temperature, eg, about 25°C and about 1 atmosphere pressure, including alcohols, glycols, polyols, and polyglycols, and mixtures thereof. Preferably, the non-aqueous hydroxylic organic solvent is selected from the group consisting of ethylene glycol, ethanol, propanol, isopropanol, propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, iso-butylene glycol, methylpropanediol , glycerin, sorbitol, polyethylene glycol, polypropylene glycol monoalkyl ether, polyoxyalkylene copolymer and mixtures thereof.

Once the desired form is obtained, whether as a single phase of silicone, an anhydrous mixture including a silicone phase, an aqueous mixture including a silicone phase, a water-in-oil emulsion, an oil-in-water emulsion, or any of two non-aqueous emulsions Either one or a variant thereof, the resulting substances are often creams or lotions with improved deposition properties and good touch properties. It can be blended into formulations of hair care products, skin care products, antiperspirants, sunscreens, cosmetics, color cosmetics, insect repellants, vitamin and hormone carriers, fragrance carriers, and the like.

Personal care applications in which the organomodified trisiloxane surfactants of the present invention and the silicone compositions of the present invention derived therefrom may be used include, but are not limited to, deodorants, antiperspirants, antiperspirants /Deodorants, shaving products, skin lotions, moisturizers, toners, bathroom products, cleaning products, hair care products such as shampoos, conditioners, mousses, hair styling sprays, hair sprays, hair dyes, hair coloring products, Hair bleaches, perm products, hair straighteners, manicure products such as nail polish, nail polish removers, nail creams and lotions, cuticle softeners, protective creams such as sunscreens, insect repellants and anti-aging products, color cosmetics Such as lipsticks, foundations, face powders, eyeliners, eye shadows, rouges, cosmetics, mascaras and other personal care formulations to which silicone components have generally been added, as well as for topical application of medical compositions to be applied to the skin. Drug delivery system.

In preferred embodiments, the personal care compositions of the present invention further comprise one or more personal care ingredients. Suitable personal care ingredients include, for example, emollients, humectants, humectants, pigments, including pearlescent pigments such as bismuth oxychloride and titanium dioxide coated mica, colorants, fragrances, biocides, preservatives, antioxidants , antimicrobials, antifungals, antiperspirants, exfoliants, hormones, enzymes, pharmaceutical compounds, vitamins, salts, electrolytes, alcohols, polyols, UV absorbers, plant extracts, surface Active agents, silicone oils, organic oils, waxes, film formers, thickeners such as fumed or hydrated silica, particulate fillers such as talc, kaolin, starch, modified starch, mica, nylon, clay Examples include bentonite and organically modified clays.

Suitable personal care compositions are prepared by combining in a manner known in the art, for example, by admixing one or more of the above components with the organomodified trisiloxane surfactant described . Suitable personal care compositions can be in the form of a single phase or in the form of an emulsion including oil-in-water, water-in-oil and anhydrous emulsions where the silicone phase can be a discontinuous or continuous phase, as well as multiple Emulsions, for example, oil-in-water-in-oil emulsions and water-in-oil-in-water emulsions.

In one useful embodiment, an antiperspirant composition comprises an organomodified trisiloxane surfactant of the present invention and one or more active antiperspirant agents. Suitable antiperspirants include, for example, the Class I active antiperspirant ingredients listed in the U.S. Food and Drug Administration's October 10, 1993 Monograph on antiperspirant drug products for over-the-counter human use, such as aluminum halides, aluminum hydroxyhalides (aluminum hydroxyhalides, such as aluminum chlorohydrate, and complexes or mixtures thereof with zirconyl oxyhalides and zirconyl hydroxyhalides, for example, aluminum-zirconium chlorohydrate, Aluminum zirconium glycine complexes such as aluminum zirconium tetrachlorohydrex gly.

In another useful embodiment, a skin care composition includes an organomodified trisiloxane surfactant and a carrier such as a silicone or organic oil. The skin care composition may optionally further comprise emollients, such as triglycerides, wax esters (wax esters), alkyl or alkenyl esters of fatty acids, or polyol esters, and one or more Known components in the composition, such as pigments, vitamins such as vitamin A, vitamin C and vitamin E, sunscreens or sunblock compounds such as titanium dioxide, zinc oxide, 2-hydroxy-4-methoxy-diphenyl Methanone, octyl methoxycinnamate, butyl methoxydibenzoylmethane, p-aminobenzoic acid, and octyldimethyl-p-aminobenzoic acid.

In another useful embodiment, a color-adding cosmetic composition such as a lipstick, make-up, or mascara composition includes an organomodified trisiloxane surfactant, and a colorant, such as a pigment, a water-soluble dye, or an oil-soluble dye. dye.

In another useful embodiment, the compositions of the present invention are used in combination with perfume substances. These fragrance materials may be fragrance compounds, encapsulated fragrance compounds or aroma releasing compounds, which may be pure compounds or encapsulated. Particularly compatible with the compositions of the present invention are aroma-releasing silicone-containing compounds as disclosed in US Patent Nos. 6,046,156, 6,054,547, 6,075,111, 6,077,923, 6,083,901 and 6,153,578; all of which are specifically incorporated herein by reference.

The use of the compositions of the present invention is not limited to personal care compositions, other products such as waxes, polishes and textiles treated with the compositions of the present invention are also envisioned.

D. Home care products

Home care applications include laundry detergents and fabric softeners, dishwashing liquids, wood and furniture polishes, floor waxes, tub and tile cleaners, toilet bowl cleaners, hard surface cleaners, window cleaners, anti-fog agents, Drain cleaners, automatic dish and linen detergents, carpet cleaners, prewash spotters, rust and scale removers.

experiment

The hydride intermediates used in the organomodified trisiloxane surfactant compositions of the present invention, as well as comparative compositions, were prepared as described in the Examples below.

Preparation Example 1

1,5-Di-tert-butyl-1,1,3,5,5,pentamethyltrisiloxane (Figure 1, Structure 1).

100 g of tBuMe ₂ SiCl and 46 g of MeHSiCl ₂ were dissolved in 150 ml of isopropyl ether (IPE) and placed in an addition funnel. Charge 150 g of water and 250 ml of IPE into a 1 L round bottom flask equipped with a mechanical stirrer, reflux condenser, and N _inlet . Chlorosilane was added dropwise via addition funnel at room temperature (23° C.) over 1 h. After the addition was complete, the temperature was adjusted to 70 °C and the reaction was carried out at reflux temperature for 20 h, the progress was monitored by GC (88% yield at 20 h). At the end of the reaction, the water was drained through a separatory funnel. The liquid was washed three times with 100 g of water each time. 25 g of _NaHCO3 was mixed with 100 g of water and slowly added to the mixture and stirred for 30 min. The water was drained again and dried over sodium sulfate. After filtration, the IPE was stripped off in a rotary evaporator and the crude product was further fractionated under reduced pressure to yield 63 _gtBuMe2SiOMe (H) _SiOSiMe2tBu (97% pure by GC).

Figure 1 - Reaction formula for the preparation of hydride intermediates

Preparation Example 2

1,5-bis(isopropyl)-1,1,3,5,5,pentamethyltrisiloxane (Figure 2, structure 2).

25g _iPrMe2SiCl (0.183 moles) and 13.1g _MeHSiCl2 (0.114 moles) were dissolved in 80ml isopropyl ether (IPE) and placed in an addition funnel. Charge 50 g of water and 100 ml of IPE into a 500 ml round bottom flask equipped with a mechanical stirrer, reflux condenser, and N _inlet . The chlorosilane was added dropwise via the addition funnel at room temperature (23° C.) over 40 minutes. After the addition was complete, the temperature was adjusted to 80 °C and the reaction was carried out at reflux temperature for 4 h, the progress was monitored by GC (75% yield at 4 h). At the end of the reaction, the water was drained through a separatory funnel. The liquid was washed three times with 80 g of water each time. 25 g of _NaHCO3 was mixed with 100 g of water and slowly added to the mixture and stirred for 30 min. The water was drained again and dried over sodium sulfate. After filtration, the IPE was stripped off in a rotary evaporator and the crude product was further fractionated under reduced pressure to yield 10 g of iPrMe ₂ SiOMe(H)SiOSiMe ₂ iPr (93% pure by GC).

Figure 2 - Reaction formula for the preparation of hydride intermediates

Preparation Example 3

The hydride intermediates of Examples 1-2 were further modified with various allyl polyoxyalkylenes to obtain organomodified trisiloxane surfactant compositions of the present invention (Table 1), as well as comparative trisilicon Oxylkane surfactants (from Table 2).

The organomodified trisiloxane surfactant compositions of the present invention are prepared by the conventional method of platinum-mediated hydrosilylation reactions, as described in US Patent 3,299,112 to Bailey, which is incorporated herein by reference.

Table 1 provides a description of the compositions of the present invention. Some of these compositions are described by the following structures:

M*D'M*

Where M*=R ¹ Si(CH ₃ ) ₂ O _0.5 ;

D'=OSi(CH ₃ )CH ₂ CH(R ³² )CH ₂ O-(CH ₂ CH ₂ O) _r -(CH ₂ CH ₂ O) _s R ³³

Wherein R ¹ , R ³² , R ³³ , subscripts r and s are as described in Table 1.

Table 1 - Description of organomodified trisiloxane surfactant compositions

Table 2 provides a description of comparative trisiloxanes and organosilicone polyether-based surfactants having the general structure:

MDxD'' _Y M

where M=(CH ₃ ) ₃ SiO _0.5 ; D=OSi(CH ₃ ) ₂ ; and

D''=OSi(CH ₃ )CH ₂ CH ₂ CHO-(CH ₂ CH ₂ O) _d R ⁹

Table 2 - Composition of Comparative Silicone Polyether Surfactants

In addition, the comparative sample OPE (octylphenol ethoxylate, containing 10 polyethylene oxide units) is a non-silicone organic surfactant. This product can be X-100 was obtained from Dow Chemical Company, Midland, MI.

Example 4

This example demonstrates the ability of the organomodified trisiloxane compositions of the present invention to lower the surface tension of water, thereby exhibiting utility as surfactants. Surface tension was measured using a Kruss tensiometer using a sandblasted platinum blade as a sensor. Solutions of the various components were prepared in deionized aqueous solution of 0.005 M NaCl at a concentration of 0.1 wt % as equilibration aids.

Table 3 shows that solutions of these unique compositions resulted in significant reductions in surface tension relative to conventional surfactants.

The compositions of the invention also provided spreading properties similar to the comparative trisiloxane surfactants (A, B). Furthermore, the organomodified trisiloxane surfactants of the present invention provide improved spreading relative to conventional silicone polyethers (C) and conventional organic surfactant products OPE.

Spreading is determined as follows: At 50-70% relative humidity (at 22-25° C.), a 10 μL droplet of surfactant solution is applied to a polyacetate film (USI, “Crystal Clear Writeon Film”) , and measure the spread diameter (mm) after 30 seconds. Apply the solution using an automatic pipette so that the volume of the droplet is reproducible. Surfactant solutions were prepared using deionized water that was further purified with a microfiltration system.

Table 3 - Surface Tension and Spreading Properties

Example 5

Hydrolytic stability was determined on representative compositions of the invention using HPLC. Solutions of various compositions were prepared at a concentration of 0.5 wt% within a pH range of pH 4 to pH 11, and their decomposition over time was monitored by HPLC.

Analytical method:

Samples were analyzed by reversed-phase chromatographic techniques using the experimental conditions listed in Table 4.

Table 4 - Solvent gradient for HPLC method

Detector: ELSD/LTA (Evaporative Light Scattering with Low Temperature Adapter)

Conditions: 30°C, 1.95SLPM _N2

Column: Phenomenex LUNA C18 end cap, 5 micron, 75x4.6mm

Flow rate: 1.0mL/min

Injection volume (Inj.Volume): 10 microliters

Sample: 0.050g/mL in methanol

Tables 5-8 demonstrate that the compositions of the present invention provide improved hydrolysis resistance relative to the standard comparative silicone-based surfactant Silicone A under similar pH conditions.

The comparative silicone A showed rapid hydrolysis at pH<5 and pH>7, while the organomodified trisiloxane surfactant of the present invention showed higher hydrolysis resistance under the same conditions.

Table 5 - Hydrolytic Stability of Silicone-Based Surfactants Determined by HPLC

Table 6 - Hydrolytic Stability of Silicone-Based Surfactants Determined by HPLC

Table 7 - Hydrolytic Stability of Silicone-Based Surfactants Determined by HPLC

Table 8 - Hydrolytic stability of comparative silicone-based surfactants as determined by HPLC

Example 6

Unlike conventional silicone-based surfactants that undergo rapid hydrolysis under acidic and basic conditions (pH<5 and pH>9), the In other words, the organomodified trisiloxane surfactants of the present invention provide increased resistance to hydrolysis. Hydrolysis products were observed as the spreadability decreased over time. Accordingly, solutions of the organomodified trisiloxane surfactants of the present invention, as well as comparative surfactants, were prepared at desired use concentrations and pHs. Spreading versus time was measured to illustrate hydrolysis resistance.

Table 9 is an illustrative example of an organomodified trisiloxane surfactant, wherein the No. 3 product superspreading surfactant is relative to a conventional trisiloxane ethoxylate surfactant (Product A), in The pH3-pH10 range has improved hydrolysis resistance. As mentioned above, resistance to hydrolysis was observed by monitoring the spreading properties over time. Here, 0.4 wt% solutions were prepared at pH 3, 4, 5 and 10. Spreading was determined according to the procedure of Example 4.

Table 9 - Effect of pH on Spreading Properties vs. Time

Example 7

The effect of other ingredients on spreading was determined by mixing the organosilicondisiloxane surfactants of the present invention with conventional organic-based co-surfactants. Co-surfactants are described in Table 10.

The blends were prepared as physical mixtures in which the weight fraction of silicone was indicated by α, indicating that the co-surfactant made up the balance of the blend ratio. For example when α=0, this indicates that the composition contains 0% silicone component, and 100% co-surfactant, while α=1.0 indicates that the composition contains 100% silicone, no (0%) co-surfactant Surfactant. A mixture of these two components is represented by a weight fraction α, where α varies within the following range: 0≤α≤1.0. For example, when α = 0.25, this indicates that the surfactant mixture consists of 25% silicone and 75% co-surfactant. These blends were then diluted in water to the desired concentration for spreading evaluation.

Spreading was determined as described in Example 4 at 0.2 wt% total surfactant.

Table 11 demonstrates that representative examples of co-surfactants of the present invention provide favorable spreading results, and in some cases, unexpected synergistic increases in which the spreading diameter of the mixture exceeds that of the individual components.

Table 10 - Description of Conventional Cosurfactants

Table 11 - Effect of co-surfactants on blend spreading properties

The foregoing embodiments are merely illustrative of the present invention, used to illustrate only some of the features of the present invention. The appended claims are intended to claim the broadest possible invention, and the examples of the application described illustrate selected embodiments from a wide variety of all possible embodiments. Accordingly, it is the applicant's intent that the appended items not be limited by the embodiments chosen to illustrate the features of the invention. The term "comprising" and its grammatical variants used in the clause logically also mean and include expressions of various degrees, such as, but not limited to, "consisting essentially of" and "consisting of". Where necessary, ranges have been provided; those ranges include all subranges between them. This range can be regarded as a Markush group or a plurality of Markush groups composed of different pairs of numerical boundaries, and the said Markush group or a plurality of Markush groups are completely defined by its lower limit and delimited by the upper bound, increasing numerically from the lower bound to the upper bound in the normal manner. Variations in these ranges are expected to occur to those skilled in the art and, if not committed to the public, should be understood to the extent possible to be covered by the appended items. It is also expected that scientific and technological advances will enable equivalent substitutions which are not presently contemplated due to the imprecision of language, and such variations should also be understood to be covered, as far as possible, by the appended clauses. All US patents (and patent applications) referenced in this application are hereby incorporated by reference in their entirety as if fully set forth in this application.

Claims (39)

1. Silicones having the formula: M ⁵ D ³ M ⁶ in 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 in R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ are each independently selected from a monovalent hydrocarbon group with 1 to 4 carbon atoms, and R ²⁵ is a branched or straight chain hydrocarbon group with 2 to 4 carbon atoms; Z" is an oxyalkylene group having the general formula: R ²⁶ (C ₂ H ₄ O) _g (C ₃ H ₆ O) _h (C ₄ H ₈ O) _i R ²⁷ , where R ²⁶ is a group having 2, 3, 5, 6, 7, 8 or 9 straight chain or branched divalent hydrocarbon groups of carbon atoms; ^R27 is selected from H, monovalent hydrocarbon groups and acetyl groups with 1 to 6 carbon atoms, and the subscript g is greater than or equal to 2, the subscripts h and i are zero or positive and satisfy the following relationship: 2≤g+h+i≤20, where g≥2; Therein the silicone has improved resistance to hydrolysis. 2. The silicone of claim 1, wherein ^R27 is selected from hydrogen and methyl. 3. The silicone of claim 1, wherein the subscript i is zero. 4. The silicone of claim 1, wherein the subscript h is 0-3. 5. The silicone of claim 1, wherein the subscript g is 8-11. 6. The silicone of claim 1, wherein ^R25 is selected from monovalent hydrocarbon groups of 3 and 4 carbon atoms. 7. The silicone of claim 1, wherein R ²⁶ is a monovalent hydrocarbon group of 3 carbon atoms. 8. The silicone of claim 1, wherein R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ are methyl groups. 9. The silicone of claim 8, wherein R ²⁵ is a monovalent hydrocarbon group of 4 carbon atoms. 10. The silicone of claim 9, wherein R ²⁵ is a monovalent hydrocarbon group of 4 carbon atoms. 11. The silicone of claim 10, wherein R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ are methyl groups. 12. The silicone of claim 11, wherein the subscript g is 8. 13. The silicone of claim 12, wherein the subscript h is zero. 14. The silicone of claim 13, wherein the subscript i is zero. 15. An agricultural composition comprising: a) Silicones having the formula: M ⁵ D ³ M ⁶ in 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 in R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ are each independently selected from a monovalent hydrocarbon group with 1 to 4 carbon atoms, and R ²⁵ is a branched or straight chain hydrocarbon group with 2 to 4 carbon atoms; Z" is an oxyalkylene group having the general formula: R ²⁶ (C ₂ H ₄ O) _g (C ₃ H ₆ O) _h (C ₄ H ₈ O) _i R ²⁷ , where R ²⁶ is a group having 2, 3, 5, 6, 7, 8 or 9 straight chain or branched divalent hydrocarbon groups of carbon atoms; ^R27 is selected from H, monovalent hydrocarbon groups and acetyl groups with 1 to 6 carbon atoms, and the subscript g is greater than or equal to 2, the subscripts h and i are zero or positive and satisfy the following relationship: 2≤g+h+i≤20, where g≥2; and b) Agricultural active ingredients selected from the group consisting of: aldimorph, clarizoline, mobendazim, dimethomorph; flusilazole, penconazole, cyconazole, econazole, furconazole, propiconazole, penconazole Coniferazole, carbendazim, thiophanate, benomyl, carbendazim, chlorothalonil, clonidamine, trifloxystrobin, fluoxastrobin, kyserostrobin, azoxystrobin, fenstrobin, propylchloride Ling, sulfamethanil, oxafefenone, captan, maneb, mancozeb, multi-antibacterial bacteria, Bacillus thuringiensis, Acetyl 105, abamectin, doramectin, lepimectin, pyrethrin, Carbaryl, pirimicarb, aldicarb, methoxam, chrysanthemum, boric acid, chlordimeform, diflubenzuron, ditriflubenzuron, dimeturon, diflubenzuron, mimaphid, Zinon, acephate, endosulfan, kelevan, dimethoate, azinphos-ethyl, azinphos-methyl, isoxazophos, chlorpyrifos, tetrafenazine, cyhalothrin, permethrin, fluorine Permethrin, Cypermethrin, Phenoxyacetic Acid, Phenoxypropionic Acid, Phenoxybutyric Acid, Benzoic Acid, Triazines and S-Triazines, Substituted Ureas, Uracil, Bentazone, Isobenad, Imazetam, Bendicon, Dacaozhi, Diquat, Clomazone, Fluoxazone, Dazamide, Dinitroaniline, Isalaline, Huangcaoxiao, Amoxazol, Amprofen, Trifluralin , glyphosate, glufosinate-ammonium, sulfonylurea, imidazolinone, pyridine carboxylic acid, clethodim, chloroform, fenoxaprop-p-p, fluoralifop-pyl, chloroxyfop-pyridine, grass Gram, sethoxydim, dichlorpyril, clomazone, bipyridylium compound, zinc sulfate, ferrous sulfate, ammonium sulfate, urea, urea ammonium nitrogen, ammonium thiosulfate, potassium sulfate, monoammonium phosphate, urea phosphate , calcium nitrate, boric acid, potassium salt of boric acid, sodium salt of boric acid, phosphoric acid, magnesium hydroxide, manganese carbonate, calcium polysulfide, copper sulfate, manganese sulfate, iron sulfate, calcium sulfate, sodium molybdate, and calcium chloride, wherein said agricultural composition has improved resistance to hydrolysis. 16. The composition of claim 15, wherein ^R27 is selected from hydrogen and methyl. 17. The composition of claim 15, wherein subscript i is zero. 18. The composition of claim 15, wherein subscript h is 0-3. 19. The composition of claim 15, wherein subscript g is 8-11. 20. The composition of claim 15, wherein ^R25 is selected from monovalent hydrocarbon groups of 3 and 4 carbon atoms. 21. The composition of claim 15, wherein ^R26 is a monovalent hydrocarbon group of 3 carbon atoms. 22. The composition of claim 15, wherein ^R19 , ^R20 , ^R21 , ^R22 , ^R23 , and ^R24 are methyl. 23. The composition of claim 22, wherein R ²⁵ is a monovalent hydrocarbon group of 4 carbon atoms. 24. The composition of claim 23, wherein R ²⁵ is a monovalent hydrocarbon group of 4 carbon atoms. 25. The composition of claim 24, wherein ^R19 , ^R20 , ^R21 , ^R22 , ^R23 , and ^R24 are methyl. 26. The composition of claim 25, wherein the subscript g is 8. 27. The composition of claim 26, wherein the subscript h is zero. 28. The composition of claim 27, wherein subscript i is zero. 29. An aqueous emulsion wherein the discontinuous phase comprises water and the continuous phase comprises the silicone of claim 1. 30. An aqueous emulsion wherein the discontinuous phase comprises water and the continuous phase comprises the composition of claim 15. 31. An aqueous emulsion wherein the continuous phase comprises water and the discontinuous phase comprises the silicone of claim 1. 32. An aqueous emulsion wherein the continuous phase comprises water and the discontinuous phase comprises the composition of claim 15. 33. A non-aqueous emulsion wherein the discontinuous phase comprises a non-aqueous hydroxylic solvent and the continuous phase comprises the silicone of claim 1. 34. A non-aqueous emulsion wherein the discontinuous phase comprises a non-aqueous hydroxylic solvent and the continuous phase comprises the composition of claim 15. 35. A non-aqueous emulsion wherein the continuous phase comprises a non-aqueous hydroxylic solvent and the discontinuous phase comprises the silicone of claim 1. 36. A non-aqueous emulsion wherein the continuous phase comprises a non-aqueous hydroxylic solvent and the discontinuous phase comprises the composition of claim 15. 37. A personal care composition comprising: a) the silicone of claim 1; and b) personal care ingredients, wherein said personal care composition has improved resistance to hydrolysis. 38. A home care composition comprising: a) the silicone of claim 1; and b) surfactants selected from hydrocarbon-based surfactants and fluorocarbon-based surfactants, wherein said home care composition has improved resistance to hydrolysis. 39. A coating composition comprising: a) the silicone of claim 1; and b) resins selected from polyester, alkyd, acrylic, polyurethane and epoxy resins, Therein the coating composition has improved hydrolysis resistance.