Method and composition for sealing components and components sealed thereby

• US 20040166333A1
• Filed: 12/19/2003
• Published: 08/26/2004
• Est. Priority Date: 06/07/2002
• Status: Active Grant

• Current Assignee: The Boeing Co.
• Original Assignee: The Boeing Co.
• Inventors: Byrd, Norman R., Keener, Steven G.
• Granted Patent: US 7,202,321 B2
• Time in Patent Office: Days
• US Class Current: 428/447
• CPC Class Codes: C08G 18/61 Polysiloxanes
• CPC Class Codes: C08G 77/455 containing polyamide, polyesteramide or polyimide sequences
• CPC Class Codes: C08L 83/00 Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
• 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 175/04 Polyurethanes
• CPC Class Codes: C09D 183/04 Polysiloxanes
• CPC Class Codes: C09D 183/14 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms C09D183/10 takes precedence
• CPC Class Codes: C25D 11/24 Chemical after-treatment
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane

Abstract

The present invention is directed to a method for applying to a substrate, in the form of a seal, a polysiloxane-containing coating, preferably a polysiloxane(amide-ureide) coating capable of inhibiting corrosion as well as the accumulation of ice. One embodiment of the present invention is directed to a polysiloxane(amide-ureide) that forms a durable, long lasting, anti-corrosive and anti-ice coating when applied to a substrate as a seal.

Claims

1. A corrosion-resistant, moisture-resistant sealant material for use as a seal for a component surface, said sealant material made from a polysiloxane(amide-ureide) having the formula:

2. The sealant material of claim 1, wherein the seal is selected from the group consisting of a fillet seal and a void pack seal.

3. The sealant material of claim 1, wherein the component surface further comprises a component assembly interface.

7. The sealant material of claim 2, wherein the seal exists on at least one component surface.

8. The sealant material of claim 2, wherein the seal exists at adjacent component surfaces.

4. A sealant material comprising a material made from a coating comprising a polymer comprising Component A and Component B, wherein Component A is a compound comprising the formula:

5. The sealant material of claim 4, wherein the diisocyanate is selected from the group consisting of alkyl diisocyanate, wherein the alkyl portion is from C₁ to C₁₀;

non-linear aryl diisocyanate; and

non-linear heterocyclic diisocyanate.

6. The sealant material of claim 4, wherein at least a portion of the substituted dicarboxylic acid is selected from the group consisting of fumaryl halides, succinyl halides, phthalyl halides, terephthalyl halides, and maleiyl halides.

9. A substrate comprising a seal, said seal comprising a polymer, said polymer comprising a Component A and a Component B, wherein Component A is a compound comprising the formula:

10. The substrate of claim 9, wherein the diisocyanate is selected from the group consisting of alkyl diisocyanate, wherein the alkyl portion is from C₁ to C₁₀;

non-linear aryl diisocyanate; and

non-linear heterocyclic diisocyanate.

11. The substrate of claim 9, wherein at least a portion of the substituted dicarboxylic acid is selected from the group consisting of fumaryl halides, succinyl halides, phthalyl halides, terephthalyl halides, and maleiyl halides.

12. The substrate of claim 9 wherein the polymer comprises a dicarboxylic component selected from fumaryl moieties, maleiyl moieties, saturated C₁ to C₁₀ dicarboxylic moieties, and partially-saturated C₃ to C₁₀ dicarboxylic moieties.

13. The substrate of claim 9, wherein greater than approximately 50% of the dicarboxylic component of the polymer comprises fumaryl moieties.

14. The substrate of claim 9, wherein greater than approximately 80% of the dicarboxylic component of the polymer comprises fumaryl moieties.

15. The substrate of claim 9, wherein R₁ and R₂ are independently selected from the group consisting of methyl, ethyl, propyl, butyl, phenyl, and hydrogen moieties.

16. The substrate of claim 9, wherein at least one of R₁ and R₂ are selected from the group consisting of halogenated alkyls and halogenated aryls.

17. The substrate of claim 9, wherein A₁ and A₂ are independently selected from the group consisting of methyl, ethyl, propyl, butyl, and phenyl moieties.

18. The substrate of claim 9, wherein at least one of A₁, A₂, R₁, and R₂ are selected from the group consisting of halogenated alkyls, halogenated aryls, halogenated alkylaryls, halogentated cycloaliphatics, and halogenated heterocycles.

19. The substrate of claim 9, wherein the diisocyanate component comprises an aromatic diisocyante.

20. The substrate of claim 9, wherein the diisocyanate component comprises toluene-2,4-diisocyanate.

21. The substrate of claim 9, wherein the diisocyanate component comprises a saturated aliphatic diisocyanate.

22. The substrate of claim 9, wherein x is a number from 1 to about 1000.

23. The substrate of claim 9, wherein x is a number from about 200 to about 500.

24. An aircraft component comprising the substrate of claim 9.

25. The substrate of claim 9, wherein the surface comprises a faying surface.

26. The substrate of claim 9, wherein the seal is selected from the group consisting of fillet seals and void pack seals.

27. The substrate of claim 9, wherein the seal inhibits the ability of ice to adhere to a surface of the substrate.

28. The substrate of claim 9, wherein the seal inhibits the ability of moisture to adhere to a surface of the substrate.

29. The substrate of claim 9, wherein the substrate further comprises a subsequent coating applied to the seal.

30. The substrate of claim 9, wherein the substrate further comprises a pre-treatment applied to the substrate surface.

31. The substrate of claim 30, wherein the pre-treatment is selected from the group consisting of ZnNi pre-treatment, Cd flash pre-treatment, and an anodizing pre-treatment.

32. The substrate of claim 9, wherein the substrate further comprises a first coating applied to the substrate, with the polymer applied as a secondary coating to the first coating.

33. The substrate of claim 32, wherein the first coating comprises a curable organic coating material selected from the group consisting of phenolics, urethanes, epoxies, and melamines.

34. The substrate of claim 32, wherein the first coating comprises a curable organic coating material selected from the group consisting of polyurethanes, polyvinyl chlorides, silicones, epoxides, acrylates, polyimides, and phenolics.

35. The substrate of claim 9, wherein the substrate is made from a material selected from the group consisting of:

aluminum alloys, titanium alloys, ferrous alloys, and non-metallic materials.

36. The substrate of claim 35, wherein the non-metallic material is selected from the group consisting of ceramic-, epoxy-, glass-, wood-, and carbon-containing materials.

37. The substrate of claim 9, wherein the substrate is made from a material selected from the group consisting of Monel 400, Monel K-500, A-286, Inconel 600, stainless steels 302, 303, 304, 304, 410, 416, 430, Custom 450, and 17-4PH.

38. An aluminum-alloy aircraft component comprising the substrate of claim 9.

39. An aluminum-alloy aircraft component comprising the substrate of claim 32.

40. An aircraft comprising the substrate of claim 9.

41. An aircraft comprising the substrate of claim 32.

42. A method for sealing at least one component with a corrosion-inhibiting, moisture-inhibiting sealant material comprising the steps of:

providing a component having a surface requiring a seal;

providing a sealant material, said sealant material comprising a polymer comprising Component A and Component B, wherein Component A is a compound comprising the formula;

and wherein Component B comprises a compound comprising the formula;

or a compound comprises the formula;

wherein X is a prepolymer comprising the formula;

wherein R₁, R₃, and R₄ are independently selected from the group consisting of hydrogen;

C₁ to C₆ alkyls and aryls;

C₃ to C₆ cycloaliphatics; and

C₃ to C₆ heterocycles;

A₁ and A₂ are independently selected from the group consisting of C₁ to C₆ alkyls and aryls;

C₇ to C₁₂ alkylaryls;

C₃ to C₆ cycloaliphatics; and

C₃ to C₆ heterocycles;

R₂, R₅, and R₆ are independently selected from the group consisting of C₁ to C₁₀ alkyls;

aryls, and heterocycles;

m and x are each a number from 1 to about 10,000;

CYAN is a diisocyanate;

Z is a halide-substituted dicarboxylic acid; and

applying the polymer coating to the component surface to provide a seal.

43. The method of claim 42, wherein the polymer comprises a dicarboxylic component selected from fumaryl moieties, maleiyl moieties, saturated C₁ to C₁₀ dicarboxylic moieties, and partially-saturated C₃ to C₁₀ dicarboxylic moieties.

44. The method of claim 43, wherein greater than approximately 50% of the dicarboxylic component of the polymer comprises fumaryl moieties.

45. The method of claim 43 wherein greater than approximately 80% of the dicarboxylic component of the polymer comprises fumaryl moieties.

46. The method of claim 42, wherein R₁ and R₂ are independently selected from the group consisting of methyl, ethyl, propyl, butyl, phenyl, and hydrogen moieties.

47. The method of claim 42, wherein at least one of R₁ and R₂ are selected from the group consisting of halogenated alkyls and halogenated aryls.

48. The method of claim 42, wherein A₁ and A₂ are independently selected from the group consisting of methyl, ethyl, propyl, butyl, and phenyl moieties.

49. The method of claim 42, wherein at least one of A₁ , A₂, R₁, and R₂ are selected from the group consisting of halogenated alkyls, halogenated aryls, halogenated alkylaryls, halogentated cycloaliphatics, and halogenated heterocycles.

50. The method of claim 42, wherein the diisocyanate component comprises an aromatic diisocyante.

51. The method of claim 42, wherein the diisocyanate component comprises toluene-2,4-diisocyanate.

52. The method of claim 42, wherein the diisocyanate component comprises a saturated aliphatic diisocyanate.

53. The method of claim 42, wherein x is a number from 1 to about 1000.

54. The method according to claim 42, wherein x is a number from about 200 to about 500.

55. The method of claim 42, further comprising the steps of providing a first coating between the component surface and the sealant material.

56. The method of claim 55, wherein the first coating comprises a curable organic coating material selected from the group consisting of phenolics, urethanes, epoxies, and melamines.

57. The method of claim 55, wherein the first coating comprises a curable organic coating material selected from the group consisting of polyurethanes, polyvinyl chlorides, silicones, epoxides, acrylates, polyimides, and phenolics.

58. The method of claim 42, wherein the component comprises an aircraft component.

59. The method of claim 42, wherein the seal is selected from the group consisting of a fillet seal, and a void pack seal.

60. The method of claim 42, wherein the non-metallic material is selected from the group consisting of ceramic-, epoxy-, glass-, wood-, and carbon-containing materials.

61. The method of claim 42, wherein at least one component is made from a material selected from the group consisting of:

aluminum alloys, ferrous alloys, and non-metallic materials.

62. The method of claim 42, wherein at least one component is made from a material selected from the group consisting of Monel 400, Monel K-500, A-286, Inconel 600, stainless steels 302, 303, 304, 304, 410, 416, 430, Custom 450, and 17-4PH.

63. The method of claim 42, further comprising the step of applying a coating to the sealant material.

64. The method of claim 42, further comprising the step of applying a pre-treatment to the component surface.

65. The substrate of claim 42, wherein the pre-treatment is selected from the group consisting of a ZnNi pre-treatment and an anodizing pre-treatment.

66. The method of claim 42, wherein the component surface comprises a faying surface.

67. An aircraft comprising components comprising adjacent surfaces coated according to the method of claim 42.

68. An aircraft comprising components comprising adjacent surfaces sealed by the sealant material according to the method of claim 55.

69. The method of claim 42, wherein the sealant material inhibits the ability of ice and moisture to adhere to a component surface.

70. The method of claim 55, wherein the sealant material inhibits the ability of ice and moisture to adhere to an aircraft component surface.

71. A sealant material comprising a polymer formed from repeating units having the formula:

72. The sealant material of claim 71 wherein the dicarboxyl residue is selected from fumaryl moieties, maleiyl moieties, saturated C₁ to C₁₀ dicarboxyl moieties, and partially-saturated C₃ to C₁₀ dicarboxyl moieties.

73. The sealant material of claim 71, wherein at least one of R₁ and R₂ are selected from the group consisting of halogenated alkyls and halogenated aryls.

74. The sealant material of claim 71 wherein x is a number from about 200 to about 500.

75. A corrosion-resistant and moisture-resistant sealant material comprising a polymer formed from repeat units having the formula:

76. The sealant material of claim 75 wherein Z is selected from the group consisting of fumaryl moieties, maleiyl moieties, saturated C₁ to C₁₀ dicarboxyl moieties, and partially-saturated C₃ to C₁₀ dicarboxyl moieties.

77. The sealant material of claim 75, wherein at least one of R₁ and R₂ are selected from the group consisting of halogenated alkyls and halogenated aryls.

78. The sealant material of claim 75 wherein x is a number from about 200 to about 500.

79. A substrate resistant to corrosion, ice formation and moisture penetration, comprising

a substrate having a seal on a substrate surface made from a polymer,

wherein the polymer is formed from repeat units having the formula:

wherein

for each repeat unit of the polymer, R₁ and R₂ are independently selected from the group consisting of C₁ to C₁₀ alkyls, aryls, and polyaryls;

for each repeat unit of the polymer, R₃ and R₄ are independently selected from the group consisting of hydrogen, C₁ to C₆ alkyls, aryls, C₃ to C₆ cycloaliphatics, and C₃ to C₆ heterocycles;

for each repeat unit of the polymer, A₁ and A₂ are independently selected from the group consisting of hydrogen, C₁ to C₆ alkyls, aryls, polyaryls, C₃ to C₆ cycloaliphatics, and C₃ to C₆ heterocycles;

for each repeat unit of the polymer, x is a number from 1 to about 10,000; and

for each repeat unit of the polymer, Y is selected from a dicarboxyl residue and a non-linear diisocyanate residue.

80. The substrate of claim 79, wherein at least one of R₁ and R₂ are selected from the group consisting of halogenated alkyls and halogenated aryls.

81. The substrate of claim 79, wherein x is a number from about 200 to about 500.

82. The substrate of claim 79, wherein the substrate is selected from the group consisting of as metal, carbon composites, wood, asphalt, resin matrices containing graphite, carbon, or glass fibers, or combinations thereof.

83. The substrate of claim 79, wherein the metal is selected from the group consisting of aluminum alloy, titanium alloy and ferrous alloy.

84. A vehicle comprising the substrate of claim 79.

85. An aircraft comprising the substrate of claim 79.

86. The substrate of claim 79, wherein the seal is selected from the group consisting of fillet seals and pack void seals.

87. The substrate of claim 79, wherein the polymer comprises a polymer formed from repeat units having the formula:

88. A method of imparting moisture penetration-inhibiting properties to a substrate seal, comprising

supplying a substrate having a surface, and

applying a sealant material made from a material comprising a polysiloxane(amide-ureide) polymer to at least a portion of the surface.

89. The method according to claim 88, wherein the seal is selected from the group consisting of a fillet seal and a void pack seal.

90. The method of claim 88, wherein the polymer is applied to the surface as a solution of the polymer in methylene chloride/toluene mixture (1:

1 ratio) onto the surface.

91. The method of claim 88, wherein the polymer coating is applied to the surface by

dissolving an amine-terminated polyamide intermediate of formula (V) in a methylene chloride/toluene mixture;

wherein

R₁ and R₂ are independently selected from the group consisting of C₁ to C₁₀ alkyls, aryls, and polyaryls;

R₃ and R₄ are independently selected from the group consisting of hydrogen, C₁ to C₆ alkyls, aryls, C₃ to C₆ cycloaliphatics, and C₃ to C₆ heterocycles;

A₁ and A₂ are independently selected from the group consisting of hydrogen, C₁ to C₆ alkyls, aryls, polyaryls, C₃ to C₆ cycloaliphatics, and C₃ to C₆ heterocycles; and

,

x is a number from 1 to about 10,000; and

dissolving an amount of isocyanate of formula (VII) in methylene chloride/toluene mixture;

X—

[NCO] 

 

(VII)

wherein n>

2; and

wherein X is selected from the group consisting of aliphatic and aromatic moieties and the isocyanate groups are bound to the X moiety so as to be positioned in a non-linear relationship with respect to one another;

combining the dissolved amine-terminated polyamide intermediate and dissolved diisocyanate just prior to or concurrent with application of the combination to the surface.

92. The method of claim 88, wherein at least one of the solutions contains solids prior to application to the surface of the substrate.

93. The method of claim 88, wherein the substrate is selected from the group consisting of metals, carbon composites, wood, asphalt, resin matrices containing graphite, carbon, or glass fibers, or combinations thereof.

94. The method of claim 88, wherein the metals are selected from the group consisting of aluminum alloys, titanium alloys and ferrous alloys.

95. A vehicle comprising the sealant material of claim 88.

96. An aircraft comprising the sealant material of claim 88.