Fast-curing modified siloxane compositions

• US 20060058451A1
• Filed: 09/15/2004
• Published: 03/16/2006
• Est. Priority Date: 09/15/2004
• Status: Active Grant

• Current Assignee: PPG Industries Ohio Incorporated (Nouryon BV)
• Original Assignee: Ameron International Corporation (NOV, Inc.)
• Inventors: Mowrer, Norman R., Sakugawa, Haruji, Bavin, Michael Norman, Constable, Karen Tisha, Gommans, Louie Herman, Chu, Shu Yi
• Granted Patent: US 7,459,515 B2
• Time in Patent Office: Days
• US Class Current: 524/588
• CPC Class Codes: C08K 5/0025 Crosslinking or vulcanising agents; including accelerators
• CPC Class Codes: C08L 2666/04 Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: C08L 2666/14 Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
• CPC Class Codes: C08L 33/14 of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
• CPC Class Codes: C08L 63/00 Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• CPC Class Codes: C08L 83/10 Block- or graft-copolymers containing polysiloxane sequences obtained by polymerising a compound having a carbon-to-carbon double bond on to a polysiloxane C08L51/08, C08L53/00
• CPC Class Codes: C09D 183/04 Polysiloxanes
• CPC Class Codes: C09D 183/06 containing silicon bound to oxygen-containing groups C09D183/12 takes precedence

Abstract

Fast-curing modified siloxane compositions comprise; (1) an alkoxy- or silanol-functional silicone intermediate, (2) at least one amine reactive ingredient selected from the group consisting of acetoacetate-functional ingredients, acrylate-functional ingredients, and mixtures thereof, (3) an epoxy-functional ingredient, (4) a curing agent selected from the group consisting of amines, aminosilanes, ketimines, aldimines and mixtures thereof, and (5) water. Other ingredients useful in forming fast-curing modified siloxane compositions of this invention include silanes, organometallic catalysts, solvents, pigments, fillers and modifying agents. The above-identified ingredients are combined and reacted to form a fully cured protective film comprising a cross-linked enamine polysiloxane and/or acrylate polysiloxane chemical structure in a reduced amount of time when compared to conventional epoxy siloxane compositions.

Claims

1. A fast-curing modified siloxane composition comprising:

an alkoxy- or silanol-functional silicone intermediate;

at least one amine reactive ingredient selected from the group consisting of acetoacetate-functional ingredients, acrylate-functional ingredients, and mixtures thereof;

an epoxy-functional ingredient;

a curing agent selected from the group consisting of amines, aminosilanes, ketimines, aldimines and mixtures thereof; and

water.

2. The composition as recited in claim 1 further comprising a silane.

3. The composition as recited in claim 1 further comprising an organometallic catalyst.

4. The composition as recited in claim 2 wherein the silane has the general formula

5. The composition as recited in claim 2 including a compatiblizing composition formed by adducting an amount of the combined silane, acetoacetate-functional ingredient, epoxy-functional ingredient, and curing agent.

6. The composition as recited in claim 1 wherein the alkoxy- or silanol-functional silicone intermediate has the general formula

7. The composition as recited in claim 1 wherein the amine reactive ingredient is an acetoacetate-functional ingredient having the general chemical formula

R₂₀[OCOCH₂COCH₂]_aR₂₁

where R₂₀ is selected from the group consisting of acrylic, polyester, polyether, and urethane polymers and diluents, and any hydroxy-functional oligomer or polymer capable of being functionalized with [OCOCH₂COCH₂], where “

a”

is from 1 to 10, and where R₂₁ is selected from the group consisting of hydrogen, and carbon-containing groups having up to about 6 carbon atoms.

8. The composition as recited in claim 1 wherein the amine reactive ingredient is an acetoacetate-functional ingredient selected from the group consisting of acetoacetate-functional diluents, acetoacetate-functional oligomers, acetoacetate-functional polymers, and combinations thereof.

9. The composition as recited in claim 8 wherein the acetoacetate-functional polymers are selected from the group consisting of acrylic, polyester, polyether, and urethane polymers.

10. The composition as recited in claim 8 wherein the composition includes an acetoacetate-functional ingredient and the combined ingredients react to form a fully cross-linked enamine polysiloxane structure suitable for forming a protective film coating.

11. The composition as recited in claim 10 wherein the ingredients react at ambient temperature to form the fully cross-linked enamine polysiloxane structure.

12. The composition as recited in claim 1 wherein the amine reactive ingredient is an acrylate-functional ingredients having the general chemical formula

R₂₂[OCOCHCH]_bR₂₃

where R₂₂ is selected from the group consisting of acrylic, polyester, polyether, and urethane polymers and diluents, and any hydroxy-functional polymer that is capable of being functionalized with [OCOCHCH], where “

b”

is from 1 to 10, and where R₂₃ is selected from the group consisting of hydrogen, and carbon-containing groups having up to about 6 carbon atoms.

13. The composition as recited in claim 1 wherein the amine reactive ingredient is an acrylate-functional ingredient selected from the group consisting of acrylate-functional diluents, acrylate-functional oligomers, acrylate-functional polymers, and combinations thereof.

14. The composition as recited in claim 13 wherein the acrylate-functional polymers are selected from the group consisting of acrylic, polyester, polyether, and urethane polymers.

15. The composition as recited in claim 13 wherein the combined ingredients react to form a fully cross-linked acrylate polysiloxane structure suitable for forming a protective film coating.

16. The composition as recited in claim 15 wherein the combined ingredients react at ambient temperature to form the fully cross-linked acrylate polysiloxane structure

17. The composition as recited in claim 1 wherein the epoxy-functional ingredient is selected from the group consisting of epoxy-functional polymers and epoxy-functional diluents.

18. The composition as recited in claim 1 comprising two amine reactive ingredients, wherein each such amine reactive ingredient has a different rate of reaction with the curing agent.

19. The composition as recited in claim 1 comprising an acetoacetate-functional ingredient and an acrylate-functional ingredient.

20. The composition as recited in claim 1 comprising in the range of from about 5 to 50 percent by weight of the alkoxy- or silanol-functional silicone intermediate, 5 to 30 percent by weight of the amine reactive ingredient, 1 to 50 percent by weight of the epoxy-functional ingredient, and 1 to 30 percent by weight of the curing agent based on the total weight of the composition.

21. The composition as recited in claim 1 further comprising ingredients selected from the group consisting of pigments, fillers, solvents, rheological modifiers, plasticizers, antifoam agents, thixotropic agents, wetting agents, antisettling agents, light stabilizers, air release agents, dispensing aids, and combinations thereof.

22. A fast-curing modified siloxane composition comprising:

an alkoxy- or silanol-functional silicone intermediate;

at least one amine reactive ingredient selected from the group consisting of acetoacetate-functional ingredients, acrylate-functional ingredients, and mixtures thereof;

an epoxy-functional ingredient; and

a curing agent selected from the group consisting of amines, aminosilanes, ketimines, aldimines and mixtures thereof;

an organometallic catalyst; and

water;

wherein upon combination of the alkoxy-functional silicone intermediate, the at least one amine reactive ingredient, the epoxy-functional ingredient, the curing agent, and water, the combined ingredients react in the presence of the organometallic catalyst at ambient temperature to form a fully cross-linked polysiloxane structure suitable for forming a protective film coating; and

wherein when the amine reactive ingredient is an acetoacetate-functional ingredient the fully cross-linked polysiloxane structure is an enamine polysiloxane, and when the amine reactive ingredient is an acrylate-functional ingredient, the fully cross-linked polysiloxane structure is an acrylate polysiloxane.

23. A fast-curing modified siloxane composition prepared by combining in the presence of water:

an alkoxy- or silanol-functional silicone intermediate;

with

an acetoacetate-functional ingredient;

an epoxy-functional ingredient; and

a curing agent selected from the group consisting of amines, aminosilanes, ketimines, aldimines and mixtures thereof;

wherein upon combining the ingredients, the acetoacetate-functional ingredient and the epoxy-functional ingredient react with the curing agent and the alkoxy- or silanol-functional silicone intermediate to form a fully cured protective film having a fully cross-linked enamine polysiloxane chemical structure.

24. The composition as recited in claim 23 further comprising an organometallic catalyst.

25. The composition as recited in claim 24 wherein the acetoacetate-functional ingredient and the epoxy-functional ingredient react with the curing agent at ambient temperature to provide the fully cross-linked enamine polysiloxane chemical structure.

26. The composition as recited in claim 23 wherein the acetoacetate-functional ingredient has the general chemical formula

R₂₀[OCOCH₂COCH₂]_aR₂₁

where R₂₀ is selected from the group consisting of acrylic, polyester, polyether, and urethane polymers and diluents, and any hydroxy-functional oligomer or polymer capable of being functionalized with [OCOCH₂COCH₂], where “

a”

is from 1 to 10, and where R₂₁ is selected from the group consisting of hydrogen, and carbon-containing groups having up to about 6 carbon atoms.

27. The composition as recited in claim 23 wherein the acetoacetate-functional ingredient is selected from the group consisting of acetoacetate-functional diluents, acetoacetate-functional oligomers, acetoacetate-functional polymers, and combinations thereof.

28. The composition as recited in claim 27 wherein the acetoacetate-functional polymers are selected from the group consisting of acrylic, polyester, polyether, and urethane polymers.

29. The composition as recited in claim 28 wherein the acetoacetate-functional polymer is an acrylic polymer, and wherein the chemical structure comprises a fully cross-linked acrylic epoxy enamine polysiloxane.

30. The composition as recited in claim 23 wherein the epoxy-functional ingredient is selected from the group consisting of epoxy-functional polymers and epoxy-functional diluents.

31. The composition as recited in claim 23 wherein the curing agent is an aminosilane having the general formula

Y—

Si—

(O—

X)₃

where Y is H(HNR), and where “

c”

is an integer of from 1 to 6, each R is a difunctional organic radical independently selected from the group consisting of aryl, alkyl, dialkylaryl, alkoxyalkyl, and cycloalkyl radicals, where R can vary within each Y molecule, each X can be the same or different, and is limited to alkyl, hydroxyalkyl, alkoxyalkyl and hydroxyalkoxyalkyl groups, containing less than about six carbon atoms.

32. The composition as recited in claim 31 wherein the curing agent further includes a secondary amine.

33. The composition as recited in claim 23 further comprising a silane.

34. The composition as recited in claim 33 wherein an amount of each of the acetoacetate-functional ingredient, the silane, the epoxy-functional ingredient, and the curing agent is combined together prior to combination with the remaining ingredients to form an enamine epoxy siloxane that acts to compatablize the remaining ingredients.

35. The composition as recited in claim 33 wherein upon combination of the acetoacetate-functional ingredient with the one or more of the alkoxy- or silanol-functional silicone intermediate, the silane, and the epoxy-functional ingredient, an adduct having acetoacetate functionality is formed, wherein the adduct reacts with the curing agent to form the fully cross-linked enamine polysiloxane chemical structure.

36. The composition as recited in claim 23 wherein the acetoacetate-functional ingredient is combined with the alkoxy- or silanol-functional silicone intermediate to form an adduct having acetoacetate functionality, wherein the curing agent is combined with the epoxy-functional ingredient to form an epoxy-silane adduct, and wherein the adducts and the remaining ingredients are combined together to form the fully cross-linked enamine polysiloxane chemical structure.

37. The composition as recited in claim 23 wherein the acetoacetate-functional ingredient and epoxy-functional ingredient are disposed within a first container, and the curing agent is disposed within a second container, and wherein the contents of the first and second containers are combined together to form the composition and undergo cure reactions to form the filly cross-linked enamine polysiloxane chemical structure.

38. The composition as recited in claim 37 further comprising a compatiblizing compound in the first container that is formed by combining a silane with an amount of each of the acetoacetate-functional ingredient, the epoxy-functional ingredient, and the curing agent.

39. The composition as recited in claim 23 comprising two acetoacetate-functional ingredients, one of which includes an acrylic polymer.

40. The composition as recited in claim 23 wherein the alkoxy- or silanol-functional silicone intermediate, acetoacetate-functional ingredient, and epoxy-functional ingredient are disposed within a first container, and the curing agent is disposed within a second container, and wherein the contents of the first and second containers are combined together to form the fully cross-linked enamine polysiloxane chemical structure.

41. The composition as recited in claim 39 wherein the epoxy-functional ingredient has a reaction rate that is different than that of one of the acetoacetate-functional ingredients, the difference in reaction rates producing a fully cured protective film having a low degree of surface gloss.

42. The composition as recited in claim 23 wherein a first amount of the alkoxy- or silanol-functional silicone intermediate, acetoacetate-functional ingredient, and organometallic catalyst is disposed within a first container, and the epoxy-functional ingredient, curing agent, and a second amount of the alkoxy- or silanol-functional silicone intermediate is disposed within a second container, and wherein the contents of the first and second containers are combined together to form the fully cross-linked enamine polysiloxane chemical structure.

43. The composition as recited in claim 23 comprising in the range of from about 5 to 50 percent by weight of the alkoxy- or silanol-functional silicone intermediate, 5 to 30 percent by weight of the acetoacetate-functional ingredient, 1 to 50 percent by weight of the epoxy-functional ingredient, and 1 to 30 percent by weight of the curing agent based on the total weight of the composition.

44. The composition as recited in claim 23 further comprising ingredients selected from the group consisting of pigments, fillers, solvents, rheological modifiers, plasticizers, antifoam agents, thixotropic agents, wetting agents, antisettling agents, light stabilizers, air release agents, dispensing aids, and combinations thereof.

45. A fast-curing modified siloxane composition prepared by combining in the presence of water:

an alkoxy- or silanol-functional silicone intermediate;

with

an acrylate-functional ingredient;

an epoxy-functional ingredient; and

a curing agent selected from the group consisting of amines, aminosilanes, ketimines, aldimines and mixtures thereof;

wherein upon combining the ingredients, the acrylate-functional ingredient and the epoxy-functional ingredient react with the curing agent to form a fully cured protective film having a fully cross-linked acrylate polysiloxane chemical structure.

46. The composition as recited in claim 45 further comprising an organometallic catalyst.

47. The composition as recited in claim 46 wherein the acrylate-functional ingredient and the epoxy-functional ingredient react with the curing agent at ambient temperature to form the fully cross-linked acrylate polysiloxane chemical structure.

48. The composition as recited in claim 45 wherein the acrylate-functional ingredient has the general chemical formula

R₂₂[OCOCHCH]_bR₂₃

where R₂₂ is selected from the group consisting of acrylic, polyester, polyether, urethane polymers and diluents, and any hydroxy-functional polymer that is capable of being functionalized with [OCOCHCH], where “

b”

is from 1 to 10, and where R₂₃ is selected from the group consisting of hydrogen, and carbon-containing groups having up to about 6 carbon atoms.

49. The composition as recited in claim 45 wherein the acrylate-functional ingredient is selected from the group consisting of acrylate-functional diluents, acrylate-functional oligomers, acrylate-functional polymers, and combinations thereof.

50. The composition as recited in claim 49 wherein the acrylate-functional polymers are selected from the group consisting of acrylic, polyester, polyether, and urethane polymers.

51. The composition as recited in claim 45 comprising in the range of from about 5 to 50 percent by weight of the alkoxy- or silanol-functional silicone intermediate, 5 to 30 percent by weight of the acrylate-functional ingredient, 1 to 50 percent by weight of the epoxy-functional ingredient, and 1 to 30 percent by weight of the curing agent based on the total weight of the composition.

52. The composition as recited in claim 45 further comprising ingredients selected from the group consisting of pigments, fillers, solvents, rheological modifiers, plasticizers, antifoam agents, thixotropic agents, wetting agents, antisettling agents, light stabilizers, air release agents, dispensing aids, and combinations thereof.

57. The composition as recited in claim 45 further comprising ingredients selected from the group consisting of pigments, fillers, solvents, rheological modifiers, plasticizers, antifoam agents, thixotropic agents, wetting agents, antisettling agents, light stabilizers, air release agents, dispensing aids, and combinations thereof.

53. A fast-curing modified siloxane composition prepared by combining in the presence of water:

an alkoxy- or silanol-functional silicone intermediate;

with

an acetoacetate-functional ingredient;

an acrylate-functional ingredient;

an epoxy-functional ingredient; and

a curing agent selected from the group consisting of amines, aminosilanes, ketimines, aldimines and mixtures thereof,

wherein upon combining the ingredients, the acetoacetate-functional ingredient, acrylate-functional ingredient, and the epoxy-functional ingredient react with the curing agent and the alkoxy- or silanol-functional silicone intermediate to form fully cured protective film having a chemical structure comprising a fully cross-linked enamine polysiloxane.

54. The composition as recited in claim 53 further comprising an organometallic catalyst.

55. The composition as recited in claim 54 wherein the acetoacetate-functional ingredient, acrylate-functional ingredient, and the epoxy-functional ingredient react with the curing agend at ambient temperature to form the chemical structure comprising a fully cross-linked enamine polysiloxane.

56. The composition as recited in claim 54 comprising in the range of from about 5 to 50 percent by weight of the alkoxy- or silanol-functional silicone intermediate, 5 to 30 percent by weight of the combined acetoacetate-functional ingredient and acrylate-functional ingredient, 1 to 50 percent by weight of the epoxy-functional ingredient, and 1 to 30 percent by weight of the curing agent based on the total weight of the composition.

58. The composition as recited in claim 53 wherein the acetoacetate-functional ingredient has the general chemical formula

R₂₀[OCOCH₂COCH₂]_aR₂₁

where R₂₀ is selected from the group consisting of acrylic, polyester, polyether, and urethane polymers and diluents, and any hydroxy-functional oligomer or polymer capable of being functionalized with [OCOCH₂COCH₂], where “

a”

is from 1 to 10, and where R₂₁ is selected from the group consisting of hydrogen, and carbon-containing groups having up to about 6 carbon atoms.

59. The composition as recited in claim 53 wherein the acrylate-functional ingredient has the general chemical formula

R₂₂[OCOCHCH]_bR₂₃

where R₂₂ is selected from the group consisting of acrylic, polyester, polyether, urethane polymers and diluents, and any hydroxy-functional polymer that is capable of being functionalized with [OCOCHCH], where “

b”

is from 1 to 10, and where R₂₃ is selected from the group consisting of hydrogen, and carbon-containing groups having up to about 6 carbon atoms.

60. The composition as recited in claim 53 wherein the acetoacetate-functional ingredient and the acrylate-functional ingredient are each selected from the group consisting of acrylate-functional diluents, acrylate-functional oligomers, acrylate-functional polymers, and combinations thereof.

61. The composition as recited in claim 60 wherein the acetoacetate-functional ingredient and the acrylate-functional ingredients comprise polymers selected from the group consisting of acrylic, polyester, polyether, and urethane polymers.

62. A method of making a fully cross-linked modified epoxy polysiloxane comprising the steps of:

combining;

an alkoxy- or silanol-functional silicone intermediate;

with

an amine reactive ingredient selected from the group consisting acetoacetate-functional ingredients, acrylate-functional ingredients, and mixtures thereof; and

an epoxy-functional ingredient; and

curing the combined ingredients in the presence of water by adding to them;

a curing agent selected from the group consisting of amines, aminosilanes, ketimines, aldimines and mixtures thereof;

wherein during the curing step, the amine reactive ingredient and the epoxy-functional ingredient each react with the curing agent, and the silicone intermediate reacts with the amine reactive ingredient reaction product to provide the fully cross-linked modified epoxy polysiloxane.

63. The method as recited in claim 62 further comprising using an organometallic catalyst during the step of curing.

64. The method as recited in claim 62 wherein the curing step is carried out at ambient temperature.

65. The method as recited in claim 62 wherein the amine reactive ingredient comprises an acetoacetate-functional ingredient and the resulting polysiloxane is cross-linked modified epoxy enamine polysiloxane.

66. The method as recited in claim 62 wherein the amine reactive ingredient comprises an acrylate-functional ingredient and the resulting polysiloxane is a cross-linked modified epoxy acrylate polysiloxane.

67. The method as recited in claim 62 comprising in the range of from about 5 to 50 percent by weight of the alkoxy- or silanol-functional silicone intermediate, 5 to 30 percent by weight of the amine reactive ingredient, 1 to 50 percent by weight of the epoxy-functional ingredient, and 1 to 30 percent by weight of the curing agent based on the total weight of the composition.