Compositions containing basic metal salts and/or non-Newtonian colloidal disperse systems and vinyl aromatic containing polymers

• US 4,728,578 A
• Filed: 08/13/1986
• Issued: 03/01/1988
• Est. Priority Date: 08/13/1986
• Status: Expired due to Fees

• Current Assignee: The Lubrizol Corporation (Berkshire Hathaway Incorporated)
• Original Assignee: The Lubrizol Corporation (Berkshire Hathaway Incorporated)
• Inventors: Bretz, John, Higgins, William A.
• Primary Examiner(s): Page, Thurman K.
• Application Number:
  US06/896,544
• Time in Patent Office: 566 Days
• Field of Search: 427/388.2, 427/388.4, 427/388.5, 252/395, 252/396, 252/393, 428/462, 148/6.14 RR
• US Class Current: 428/462
• CPC Class Codes: C08K 13/02 Organic and inorganic ingredients
• CPC Class Codes: C08K 3/26 Carbonates; Bicarbonates
• CPC Class Codes: C08K 5/42 Sulfonic acids; Derivatives thereof
• CPC Class Codes: C08L 53/02 of vinyl-aromatic monomers and conjugated dienes
• CPC Class Codes: C09D 5/08 Anti-corrosive paints
• CPC Class Codes: Y10T 428/31696 Including polyene monomers [e.g., butadiene, etc.]

Abstract

The present invention relates to modified non-Newtonian colloidal disperse systems exhibiting improved thickening power, particularly when diluted. These compositions are useful as high-solids, thermosetting caulks, molding compositions, extruding compositions and the like, but are particularly suitable for use as high solids thermosetting coating compositions. These coating compositions are heat-stable and sag-resistant.

The compositions of this invention comprise a mixture of

(B) at least one non-Newtonian colloidal disperse system comprising

(B-1) solid metal-containing colloidal particles,

(B-2) a liquid dispersing medium, and

(B-3) at least one organic compound which is soluble in said dispersing medium, the molecules of said organic compound being characterized by a hydrophobic portion and at least one polar substituent; and

(C) at least one hydrogenated block copolymer of a vinyl aromatic monomer and an aliphatic conjugated diene.

Optionally, the compositions also contain (D) a substantially inert, normally liquid diluent.

The invention also relates to methods of coating metal surfaces with the compositions of the invention described above as well as compositions comprising mixtures of neutral and/or basic metal salts of organic acidic materials and the copolymers (C) described above.

Claims

1. A composition comprising a mixture of

(B) at least one non-Newtonian colloidal disperse system comprising

(B-1) solid metal-containing colloidal particles,

(B-2) a liquid dispersing medium, and

(B-3) at least one organic compound which is soluble in said dispersing medium, the molecules of said organic compound being characterized by a hydrophobic portion and at least one polar substituent;

and

(C) at least one hydrogenated block copolymer of a vinyl aromatic monomer and an aliphatic conjugated diene.

2. The composition of claim 1 comprising from about 50% to about 99% by weight of (B) and from about 1% to about 50% by weight of (C).

3. The composition of claim 1 wherein the solid metal-containing colloidal particles (B-1) comprise solid metal salts.

4. The composition of claim 1 wherein at least about 10% of the solid metal-containing colloidal particles (B-1) are characterized by having been formed in situ.

5. The composition of claim 1 wherein the solid metal-containing particles (B-1) are further characterized by having a unit particle size of from about 20 A to about 5000 A.

6. The composition of claim 1 wherein the solid metal-containing particles (B-1) are selected from alkali and alkaline earth metal salts.

7. The composition of claim 1 wherein (B-3) comprises an alkali or alkaline earth metal salt of an organic acid.

8. The composition of claim 7 wherein said organic acid is a sulfonic acid or a carboxylic acid.

9. The composition of claim 8 wherein said salt is an alkaline earth metal salt.

10. The composition of claim 1 wherein said solid metal-containing particles (B-1) comprise alkaline earth metal salts.

11. The composition of claim 1 wherein said solid metal-containing colloidal particles (B-1) comprise calcium carbonate.

12. The composition of claim 1 wherein (B-3) is represented by the formula ##STR13## wherein R is a hydrocarbyl group of about 12 to about 30 carbon atoms.

13. The composition of claim 1 wherein said disperse system (A) comprises

(A-1) solid calcium carbonate colloidal particles having a unit particle size in the range of about 50 A to about 4000 A,

(A-2) an organic solvent, and

(A-3) a third component represented by the formula ##STR14## wherein R is a hydrocarbyl group having an average of about 12 to about 30 carbon atoms.

14. The composition of claim 1 wherein the molar ratio of (B-1) to (B-3) ranges from about 40:

1 to about 2;

1.

15. The composition of claim 1 wherein said system (B) is characterized by a neutralization base number of about 7 or less.

16. The composition of claim 1 wherein (C) comprises from about 2 to about 5 polymer blocks with at least one polymer block of said vinyl aromatic monomer and at least one polymer block of said aliphatic conjugated diene.

17. The composition of claim 16 wherein the vinyl aromatic monomer content in said copolymer is in the range of from about 20% to about 70% by weight, and the diene content is in the range of from about 30% to about 80% by weight.

18. The composition of claim 16 wherein the number average molecular weight of said copolymer (C) is in the range of from about 10,000 to about 500,000.

19. The composition of claim 16 wherein component (C) has 2 or 3 polymer blocks.

20. The composition of claim 1 wherein component (C) is a linear block copolymer.

21. The composition of claim 1 wherein component (C) is a radial block copolymer.

22. The composition of claim 1 wherein said vinyl aromatic compound is a styrene.

23. The composition of claim 1 wherein said conjugated diene is isoprene.

24. The composition of claim 1 wherein said conjugated diene is 1,3-butadiene.

25. The composition of claim 1 wherein the number average molecular weight for said copolymer (C) is in the range of about 30,000 to about 200,000.

26. The composition of claim 1 wherein the content of said vinyl aromatic monomer in said copolymer (C) is in the range of about 40% to about 60% by weight, and the content of said diene in said copolymer is in the range of about 40% to about 60% by weight.

27. The composition of claim 1 also containing

(D) at least one substantially inert, normally liquid organic diluent.

28. The composition of claim 27 containing from about 35% to about 98% by weight of the diluent (D).

29. A composition comprising a mixture of

(B) a non-Newtonian colloidal disperse system comprising

(B-1) solid metal-containing colloidal particles predispersed in

(B-2) a liquid dispersing medium, and

(B-3) at least one organic compound which is soluble in said dispersing medium, the molecules of said organic compound being characterized by a hydrophobic portion and at least one polar substituent, and

(C) at least one hydrogenated block copolymer of a styrene and an aliphatic conjugated diene, said copolymer having from 2 to about 5 polymer blocks with at least one polymer block of said styrene and at least one polymer block of said hydrogenated aliphatic conjugated diene, the content of said styrene in said copolymer being in the range of from about 20% to about 70% by weight and the content of said diene being in the range of from about 30% to about 80% by weight, the number average molecular weight of said copolymer being in the range of about 10,000 to about 500,000.

30. The composition of claim 29 also containing

(D) a substantially inert, normally liquid organic diluent.

31. The composition of claim 29 containing from about 1% to about 20% by weight of (C).

32. The composition of claim 29 wherein said solid metal-containing colloidal particles (B-1) comprise solid metal salts.

33. The composition of claim 29 wherein at least about 10% of the solid metal-containing colloidal particles (B-1) are characterized by having been formed in situ.

34. The composition of claim 29 wherein the solid metal-containing particles (B-1) are further characterized by having a unit particle size of from about 20 A to about 5000 A.

35. The composition of claim 29 wherein the solid metal-containing particles (B-1) are selected from alkali and alkaline earth metal salts.

36. The composition of claim 29 wherein said solid metal-containing particles (B-1) comprise alkaline earth metal salts.

37. The composition of claim 29 wherein said solid metal-containing colloidal particles (B-1) comprise calcium carbonate.

38. The composition of claim 29 wherein (B-3) comprises an alkali or alkaline earth metal salt of an organic acid.

39. The composition of claim 38 wherein said organic acid is a sulfonic acid or a carboxylic acid.

40. The composition of claim 39 wherein said salt is an alkaline earth metal salt.

41. The composition of claim 29 wherein (B-3) is represented by the formula ##STR15## wherein R is a hydrocarbyl group of about 12 to about 30 carbon atoms.

42. The composition of claim 29 therein said disperse system (B) comprises

(B-1) solid calcium carbonate colloidal particles having a unit particle size in the range of about 50 A to about 4000 A,

(B-2) an aromatic solvent;

and

(B-3) a third component represented by the formula ##STR16## wherein R is a hydrocarbyl group having an average of about 12 to about 30 carbon atoms.

43. The composition of claim 42 wherein the molar ratio of (B-1) to (B-3) ranges from about 40:

1 to about 2;

1.

44. The composition of claim 29 wherein said system (B) is characterized by a neutralization base number of about 7 or less.

45. The composition of claim 29 wherein component (C) has 2 or 3 polymer blocks.

46. The composition of claim 29 wherein component (C) is a linear block copolymer.

47. The composition of claim 29 wherein component (C) is a radial block copolymer.

48. The composition of claim 29 wherein said styrene is styrene.

49. The composition of claim 29 wherein said conjugated diene is isoprene.

50. The composition of claim 29 wherein said conjugated diene is 1,3-butadiene.

51. The composition of claim 29 wherein the styrene content in said copolymer is in the range of about 40% to about 60% by weight, and the diene content in said copolymer is in the range of from about 40% to about 60% by weight.

95. The method of claim 38 wherein said organic acid is a sulfonic acid or a carboxylic acid.

96. The method of claim 39 wherein said salt is an alkaline earth metal salt.

52. A method of protecting metal from corrosion which comprises applying to said metal, a composition comprising a mixture of

(A) at least one neutral or basic metal salt of an acidic organic compound or mixtures of said neutral and/or basic metal salts, or

(B) at least one non-Newtonian colloidal disperse system comprising

(B-1) solid metal-containing colloidal particles,

(B-2) a liquid dispersing medium, and

(B-3) at least one organic compound which is soluble in said dispersing medium, the molecules of said organic compound being characterized by a hydrophobic portion and at least one polar subtituent;

and

(C) at least one hydrogenated block copolymer of a vinyl aromatic monomer and an aliphatic conjugated diene.

53. The method of claim 52 wherein (A) is an overbased salt having a metal ratio of at least about 2.0.

54. The method of claim 52 wherein the metal salt (A) is selected from alkali and alkaline earth metal salts.

55. The method of claim 52 wherein the metal salt is an alkali or alkaline earth metal salt of at least one sulfonic acid, carboxylic acid, organic phosphorus acid or phenol.

56. The method of claim 55 wherein the salt is an alkaline earth metal salt.

57. The method of claim 52 wherein the metal salt is an alkaline earth metal salt of an organic sulfonic acid.

58. The method of claim 52 wherein the mixture also contains

(D) at least one substantially inert, normally liquid organic diluent.

59. The method of claim 58 wherein the mixture contains from about 35% to about 98% by weight of the diluent (D).

60. The method of claim 52 wherein the mixture contains

(B) at least one non-Newtonian colloidal disperse system comprising

(B-1) solid metal-containing colloidal particles,

(B-2) a liquid dispersing medium, and

(B-3) at least one organic compound which is soluble in said dispersing medium, the molecules of said organic compound being characterized by a hydrophobic portion and at least one polar substituent, and

(C) at least one hydrogenated block copolymer of a vinyl aromatic monomer and an aliphatic conjugated diene.

61. The method of claim 60 wherein the mixture comprises from about 50% to about 99% by weight of (B) and from about 1% to about 50% by weight of (C).

62. The method of claim 60 wherein the solid metal-containing colloidal particles (B-1) comprise solid metal salts.

63. The method of claim 60 wherein at least about 10% of the solid metal-containing colloidal particles (B-1) are characterized by having been formed in situ.

64. The method of claim 60 wherein the solid metal-containing particles (B-1) are further charactrized by having a unit particle size of from about 20 A to about 5000 A.

65. The method of claim 60 wherein the solid metal-containing particles (B-1) are selected from alkali and alkaline earth metal salts.

66. The method of claim 60 wherein (B-3) comprises an alkali or alkaline earth metal salt of an organic acid.

67. The method of claim 66 wherein said organic acid is a sulfonic acid or a carboxylic acid.

68. The method of claim 66 wherein said salt is an alkaline earth metal salt.

69. The method of claim 60 wherein said solid metal-containing particles (B-1) comprise alkaline earth metal salts.

70. The method of claim 60 wherein said solid metal-containing colloidal particles (B-1) comprise calcium carbonate.

71. The method of claim 60 wherein (B-3) is represented by the formula ##STR17## wherein R is a hydrocarbyl group of about 12 to about 30 carbon atoms.

72. The method of claim 60 wherein said disperse system (B) comprises

(B-1) solid calcium carbonate colloidal particles having a unit particle size in the range of about 50 A to about 4000 A,

(B-2) an organic solvent, and

(B-3) a third component represented by the formula ##STR18## wherein R is a hydrocarbyl group having an average of about 12 to about 30 carbon atoms.

73. The method of claim 60 wherein the molar ratio of (B-1) to (B-3) ranges from about 40:

1 to about 2;

1.

74. The method of claim 60 wherein said system (B) is characterized by a neutralization base number of about 7 or less.

75. The method of claim 52 wherein (C) comprises from about 2 to about 5 polymer blocks with at least one polymer block of said vinyl aromatic monomer and at least one polymer block of said aliphatic conjugated diene.

76. The method of claim 75 wherein the vinyl aromatic monomer content in said copolymer is in the range of from about 20% to about 70% by weight, and the diene content is in the range of from about 30% to about 80% by weight.

77. The method of claim 75 wherein the number average molecular weight of said copolymer (C) is in the range of from about 10,000 to about 500,000.

78. The method of claim 75 wherein component (C) has 2 or 3 polymer blocks.

79. The method of claim 52 wherein component (C) is a linear block copolymer.

80. The method of claim 52 wherein component (C) is a radial block copolymer.

81. The method of claim 52 wherein said vinyl aromatic compound is a styrene.

82. The method of claim 52 wherein said conjugated diene is isoprene.

83. The method of claim 52 wherein said conjugated diene is 1,3-butadiene.

84. The method of claim 52 wherein the number average molecular weight for said copolymer (C) is in the range of about 30,000 to about 200,000.

85. The method of claim 52 wherein the content of said vinyl aromatic monomer in said copolymer (C) is in the range of about 40% to about 60% by weight, and the content of said diene in said copolymer is in the range of about 40% to about 60% by weight.

107. The metal surface treated in accordance with the method of claim 52.

86. A method of coating metal surfaces to retard corrosion thereof which comprises applying to the metal surface, a composition comprising a mixture of

(B) a non-Newtonian colloidal disperse system comprising

(B-1) solid metal-containing colloidal particles predispersed in

(B-2) a liquid dispersing medium, and

(B-3) at least one organic compound which is soluble in said dispersing medium, the molecules of said organic compound being characterized by a hydrophobic portion and at least one polar substituent, and

(C) at least one hydrogenated block copolymer of a styrene and an aliphatic conjugated diene, said copolymer having from 2 to about 5 polymer blocks with at least one polymer block of said styrene and at least one polymer block of said hydrogenated aliphatic conjugated diene, the content of said styrene in said copolymer being in the range of from about 20% to about 70% by weight and the content of said diene being in the range of from about 30% to about 80% by weight, the number average molecular weight of said copolymer being in the range of about 10,000 to about 500,000.

87. The method of claim 86 also containing

(D) a substantially inert, normally liquid organic diluent.

88. The method of claim 86 containing from about 1% to about 20% by weight of (C).

89. The method of claim 86 wherein said solid metal-containing colloidal particles (B-1) comprise solid metal salts.

90. The method of claim 86 wherein the solid metal-containing particles (B-1) are further characterized by having a unit particle size of from about 20 A to about 5000 A.

91. The method of claim 86 wherein the solid metal-containing particles (B-1) are selected from alkali and alkaline earth metal salts.

92. The method of claim 86 wherein said solid metal-containing particles (B-1) comprise alkaline earth metal salts.

93. The method of claim 86 wherein said solid metal-containing colloidal particles (B-1) comprise calcium carbonate.

94. The method of claim 86 wherein (B3) comprises an alkali or alkaline earth metal salt of an organic acid.

97. The method of claim 86 wherein (B-3) is represented by the formula ##STR19## wherein R is a hydrocarbyl group of about 12 to about 30 carbon atoms.

98. The method of claim 86 therein said disperse system (B) comprises

(B-1) solid calcium carbonate colloidal particles having a unit particle size in the range of about 50 A to about 4000 A,

(B-2) an aromatic solvent;

and

(B-3) a third component represented by the formula ##STR20## wherein R is a hydrocarbyl group having an average of about 12 to about 30 carbon atoms.

99. The method of claim 86 wherein the molar ratio of (B-1) to (B-3) ranges from about 40:

1 to about 2;

1.

100. The method of claim 86 wherein component (C) has 2 or 3 polymer blocks.

101. The method of claim 86 wherein component (C) is a linear block copolymer.

102. The method of claim 86 wherein component (C) is a radial block copolymer.

103. The method of claim 86 wherein said styrene is styrene.

104. The method of claim 86 wherein said conjugated diene is isoprene.

105. The method of claim 86 wherein said conjugated diene is 1,3-butadiene.

106. The method of claim 86 wherein the styrene content in said copolymer is in the range of about 40% to about 60% by weight, and the diene content in said copolymer is in the range of from about 40% to about 60% by weight.

108. The metal surface treated in accordance with the method of claim 86.