Polycaprolactone derivatives and coating compositions thereof

• US 4,096,125 A
• Filed: 05/26/1976
• Issued: 06/20/1978
• Est. Priority Date: 05/26/1976
• Status: Expired due to Term

• Current Assignee: Union Carbide Corporation (Dow, Inc.)
• Original Assignee: Union Carbide Corporation (Dow, Inc.)
• Inventors: Smith, Oliver Wendell, Koleske, Joseph Victor
• Primary Examiner(s): Phynes, Lucille M.
• Application Number:
  US05/690,353
• Time in Patent Office: 755 Days
• Field of Search: 260/75 R, 260/75 N, 260/78.41
• US Class Current: 528/289
• CPC Class Codes: C08G 63/08 Lactones or lactides
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 33/26 Homopolymers or copolymers of acrylamide or methacrylamide
• CPC Class Codes: C08L 61/20 Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen with aminophenols C08L61/04
• CPC Class Codes: C08L 67/04 Polyesters derived from hydroxycarboxylic acids, e.g. lactones C08L67/06 takes precedence
• CPC Class Codes: C09D 167/04 Polyesters derived from hydroxycarboxylic acids, e.g. lactones C09D167/06 takes precedence

Abstract

Water insoluble adducts are produced comprising the reaction product of a polycaprolactone polyol and an anhydride of a polycarboxylic acid. The polycaprolactone polyol reacted with the anhydride of the polycarboxylic acid has an average of at least two hydroxyl groups in the molecule, a hydroxyl number of from about 15 to 600 and an average molecular weight of from about 290 to about 6,000. The carboxylic acid anhydride has at least one intramolecular carboxylic anhydride group. These water insoluble adducts on reaction with an inorganic or organic base produce water soluble, carboxyl modified oligomer addition reaction products which are eminently suitable for the production of aqueous coatings compositions. Exceptionally good coatings compositions are obtained when a crosslinker is present in the coating composition.

Claims

1. A water insoluble adduct comprising the reaction product of a polycaprolactone polyol and an intramolecular anhydride of a polycarboxylic acid, wherein said polycaprolactone polyol has at least two hydroxyl groups in the molecule, a hydroxyl number of from 15 to 600 and an average molecular weight of from 290 to about 6,000, and wherein said anhydride has at least one intramolecular carboxylic anhydride group.

2. A water insoluble adduct as claimed in claim 1, wherein said polycaprolactone polyol has from 2 to 6 hydroxyl groups.

3. A water insoluble adduct as claimed in claim 1, wherein said polycaprolactone polyol has from 2 to 4 hydroxyl groups.

4. A water insoluble adduct as claimed in claim 1, wherein said polycaprolactone polyol has an average molecular weight of from 290 to 3,000.

5. A water insoluble adduct as claimed in claim 1, wherein said polycaprolactone polyol is a diol having an average molecular weight of from 290 to about 500.

6. A water insoluble adduct as claimed in claim 1, wherein said polycaprolactone polyol is a triol having an average molecular weight of from about 300 to about 1,000.

7. A water insoluble adduct as claimed in claim 1, wherein said polycaprolactone polyol is a mixture of polycaprolactone polyols.

8. A water insoluble adduct as claimed in claim 1, wherein said anhydride is phthalic anhydride.

9. A water insoluble adduct as claimed in claim 1, wherein said anhydride is hexahydrophthalic anhydride.

10. A water insoluble adduct as claimed in claim 1, wherein said anhydride is maleic anhydride.

11. A water insoluble adduct as claimed in claim 1, wherein said anhydride is trimellitic anhydride.

12. A water insoluble adduct as claimed in claim 1, wherein said anhydride is succinic anhydride.

13. A water insoluble adduct as claimed in claim 1, wherein said anhydride is isatoic anhydride.

14. A water insoluble adduct as claimed in claim 1, wherein from 0.1 to 1 anhydride equivalent per hydroxyl equivalent is initially charged and reacted.

15. A water insoluble adduct as claimed in claim 1, wherein from 0.1 to 0.4 anhydride equivalent per hydroxyl equivalent is initially charged and reacted.

16. A water insoluble adduct as claimed in claim 1, wherein said polycaprolactone polyol is a triol having an average molecular weight of about 540 and an average hydroxyl number of about 310 and said anhydride is phthalic anhydride.

17. A water insoluble adduct as claimed in claim 1, wherein said polycaprolactone polyol is a triol having an average molecular weight of about 540 and an average hydroxyl number of about 310 and said anhydride is hexahydrophthalic anhydride.

18. A water insoluble adduct as claimed in claim 1, wherein said polycaprolactone polyol is a triol having an average molecular weight of about 540 and an average hydroxyl number of about 310 and said anhydride is maleic anhydride.

19. A water insoluble adduct as claimed in claim 1, wherein said polycaprolactone polyol is a triol having an average molecular weight of about 300 and an average hydroxyl number of about 560 and said anhydride is maleic anhydride.

20. A water insoluble adduct as claimed in claim 1, wherein said polycaprolactone polyol is a diol having an average molecular weight of about 530 and an average hydroxyl number of about 212 and said anhydride is succinic anhydride.

21. A water insoluble adduct as claimed in claim 1, wherein said polycaprolactone polyol is a triol having an average molecular weight of about 900 and an average hydroxyl number of about 187 and said anhydride is succinic anhydride.

22. A water insoluble adduct as claimed in claim 1, wherein said polycaprolactone polyol is a triol having an average molecular weight of about 300 and an average hydroxyl number of about 560 and said anhydride is succinic anhydride.

23. A water insoluble adduct as claimed in claim 1, wherein said polycaprolactone polyol is a mixture of a triol having an average molecular weight of about 540 and an average hydroxyl number of about 310 with a triol having an average molecular weight of about 300 and an average hydroxyl number of about 560 and said anhydride is phthalic anhydride.

24. A water insoluble adduct as claimed in claim 1, wherein said polycaprolactone polyol is a mixture of a triol having an average molecular weight of about 540 and an average hydroxyl number of about 310 with a triol having an average molecular weight of about 300 and an average hydroxyl number of about 560 and said anhydride is succinic anhydride.

25. A water insoluble adduct as claimed in claim 1, wherein said polycaprolactone polyol is an octaol having an average molecular weight of 3,160 and an average hydroxyl number of 395 and said anhydride is phthalic anhydride.

26. A water soluble composition comprising the adduct reaction product of a polycaprolactone polyol and an intramolecular anhydride of a polycarboxylic acid, wherein said polycaprolactone polyol has at least two hydroxyl groups in the molecule, a hydroxyl number of from 15 to 600 and an average molecular weight of from 290 to about 6,000, and wherein said anhydride has at least one intramolecular carboxylic anhydride group and an inorganic or organic base in an amount sufficient to neutralize the free carboxyl groups of said adduct.

27. A water soluble composition as claimed in claim 26 wherein said polycaprolactone in said adduct has from 2 to 6 hydroxyl groups and said base is an organic amine.

28. A water soluble composition as claimed in claim 26 wherein said polycaprolactone in said adduct has from 2 to 4 hydroxyl groups and said base is an organic amine.

29. A water soluble composition as claimed in claim 26 wherein said polycaprolactone in said adduct has a molecular weight of from 290 to 3,000 and said base is an organic amine.

30. A water soluble composition as claimed in claim 26 wherein said polycaprolactone in said adduct is a diol having an average molecular weight of from about 290 to about 500 and said base is an organic amine.

31. A water soluble composition as claimed in claim 26 wherein said polycaprolactone in said adduct is a triol having an average molecular weight of from about 300 to about 1,000 and said base is an organic amine.

32. A water soluble composition as claimed in claim 26 wherein said polycaprolactone in said adduct is a mixture of polycaprolactone polyols and said base is an organic amine.

33. A water soluble composition as claimed in claim 26, wherein said anhydride in said adduct is phthalic anhydride and said base is an organic amine.

34. A water soluble composition as claimed in claim 26, wherein said anhydride in said adduct is hexahydrophthalic anhydride and said base is an organic amine.

35. A water soluble composition as claimed in claim 26, wherein said anhydride in said adduct is maleic anhydride and said base is an organic amine.

36. A water soluble composition as claimed in claim 26, wherein said anhydride in said adduct is trimellitic anhydride and said base is an organic amine.

37. A water soluble composition as claimed in claim 26, wherein said anhydride in said adduct is succinic anhydride and said base is an organic amine.

38. A water soluble compositions as claimed in claim 26, wherein said anhydride in said adduct is isatoic anhydride and said base is an organic amine.

39. A water soluble composition as claimed in claim 26, wherein in said adduct from 0.1 to 1 anhydride equivalent per hydroxyl equivalent is initially charged and reacted, and said base is an organic base.

40. A water soluble composition as claimed in claim 26, wherein in said adduct from 0.1 to 0.4 anhydride equivalent per hydroxyl equivalent is initially charged and reacted, and said base is an organic base.

41. A water soluble composition as claimed in claim 26, wherein said polycaprolactone in said adduct is a triol having an average hydroxyl number of 310, said anhydride is phthalic anhydride, and said base is N,N-dimethyl diethanolamine.

42. A water soluble composition as claimed in claim 26, wherein said polycaprolactone in said adduct is a triol having an average molecular weight of 540 and an average hydroxyl number of 310, said anhydride is hexahydrophthalic anhydride, and said base is N,N-dimethyl diethanolamine.

43. A water soluble composition as claimed in claim 26, wherein said polycaprolactone in said adduct is a triol having an average molecular weight of 540 and an average hydroxyl number of 310, said anhydride is maleic anhydride, and said base is N,N-dimethyl diethanolamine.

44. A water soluble composition as claimed in claim 26, wherein said polycaprolactone in said adduct is a triol having an average molecular weight of about 300 and an average hydroxyl number of about 560, said anhydride is maleic anhydride, and said base is N,N-dimethyl ethanolamine.

45. A water soluble composition as claimed in claim 26, wherein said polycaprolactone in said adduct is a diol having an average molecular weight of about 530 and an average hydroxyl number of about 212, said anhydride is succinic anhydride, and said base is N,N-dimethyl ethanolamine.

46. A water soluble composition as claimed in claim 26, wherein said polycaprolactone in said adduct is a triol having an average molecular weight of about 900 and an average hydroxyl number of about 187, said anhydride is succinic anhydride, and said base is N,N-dimethyl ethanolamine.

47. A water soluble composition as claimed in claim 26, wherein said polycaprolactone in said adduct is a triol having an average molecular weight of about 300 and an average hydroxyl number of about 560, said anhydride is succinic anhydride, and said base is N,N-dimethyl ethanolamine.

48. A water soluble composition as claimed in claim 26, wherein said polycaprolactone in said adduct is a mixture of a triol having an average molecular weight of about 540 and an average hydroxyl number of about 310 with a triol having an average molecular weight of about 300 and an average hydroxyl number of about 560, said anhydride is phthalic anhydride, and said base is N,N-dimethyl ethanolamine.

49. A water soluble composition as claimed in claim 26, wherein said polycaprolactone in said adduct is a mixture of a triol having an average molecular weight of about 540 and an average hydroxyl number of about 310 with a triol having an average molecular weight of about 300 and an average hydroxyl number of about 560, said anhydride is succinic anhydride and said base is N,N-dimethyl ethanolamine.

50. A water soluble composition as claimed in claim 26, wherein said polycaprolactone in said adduct is an octaol having an average molecular weight of about 3,160 and an average hydroxyl number of about 395, said anhydride is phthalic anhydride, and said base is N,N-dimethyl diethanolamine.

51. A coating composition comprising a water soluble composition as claimed in claim 26 and additionally containing from 25 to 200 weight percent of a crosslinking agent based on the weight of water soluble adduct present.

52. A coating composition comprising a water soluble composition as claimed in claim 27 and additionally containing from 25 to 200 weight percent of a crosslinking agent based on the weight of water soluble adduct present.

53. A coating composition comprising a water soluble composition as claimed in claim 28 and additionally containing from 25 to 200 weight percent of a crosslinking agent based on the weight of water soluble adduct present.

54. A coating composition comprising a water soluble composition as claimed in claim 29 and additionally containing from 25 to 200 weight percent of a crosslinking agent based on the weight of water soluble adduct present.

55. A coating composition comprising a water soluble composition as claimed in claim 30 and additionally containing from 25 to 200 weight percent of a crosslinking agent based on the weight of water soluble adduct present.

56. A coating composition comprising a water soluble composition as claimed in claim 31 and additionally containing from 25 to 200 weight percent of a crosslinking agent based on the weight of water soluble adduct present.

57. A coating composition comprising a water soluble composition as claimed in claim 32 and additionally containing from 25 to 200 weight percent of a crosslinking agent based on the weight of water soluble adduct present.

58. A coating composition comprising a water soluble composition as claimed in claim 33 and additionally containing from 25 to 200 weight percent of a crosslinking agent based on the weight of water soluble adduct present.

59. A coating composition comprising a water soluble composition as claimed in claim 34 and additionally containing from 25 to 200 weight percent of a crosslinking agent based on the weight of water soluble adduct present.

60. A coating composition comprising a water soluble composition as claimed in claim 35 and additionally containing from 25 to 200 weight percent of a crosslinking agent based on the weight of water soluble adduct present.

61. A coating composition comprising a water soluble composition as claimed in claim 36 and additionally containing from 25 to 200 weight percent of a crosslinking agent based on the weight of water soluble adduct present.

62. A coating composition comprising a water soluble composition as claimed in claim 37 and additionally containing from 25 to 200 weight percent of a crosslinking agent based on the weight of water soluble adduct present.

63. A coating composition comprising a water soluble composition as claimed in claim 38 and additionally containing from 25 to 200 weight percent of a crosslinking agent based on the weight of water soluble adduct present.

64. A coating composition comprising a water soluble composition as claimed in claim 39 and additionally containing from 25 to 200 weight percent of a crosslinking agent based on the weight of water soluble adduct present.

65. A coating composition comprising a water soluble composition as claimed in claim 40 and additionally containing from 25 to 200 weight percent of a crosslinking agent based on the weight of water soluble adduct present.

66. A coating composition comprising a water soluble composition as claimed in claim 41 and additionally containing from 25 to 200 weight percent of hexamethoxymethylmelamine based on the weight of water soluble adduct present.

67. A coating composition comprising a water soluble compositions as claimed in claim 42 and additionally containing from 25 to 200 weight percent of hexamethoxymethylmelamine based on the weight of water soluble adduct present.

68. A coating composition comprising a water soluble composition as claimed in claim 43 and additionally containing from 25 to 200 weight percent of hexamethoxymethylmelamine based on the weight of water soluble adduct present.

69. A coating composition comprising a water soluble composition as claimed in claim 44 and additionally containing from 25 to 200 weight percent of hexamethoxymethylmelamine based on the weight of water soluble adduct present.

70. A coating composition comprising a water soluble composition as claimed in claim 45 and additionally containing from 25 to 200 weight percent of hexamethoxymethylmelamine based on the weight of water soluble adduct present.

71. A coating composition comprising a water soluble composition as claimed in claim 46 and additionally containing from 25 to 200 weight percent of hexamethoxymethylmelamine based on the weight of water soluble adduct present.

72. A coating composition comprising a water soluble composition as claimed in claim 47 and additionally containing from 25 to 200 weight percent of hexamethoxymethylmelamine based on the weight of water soluble adduct present.

73. A coating composition comprising a water soluble composition as claimed in claim 48 and additionally containing from 25 to 200 weight percent of hexamethoxymethylmelamine based on the weight of water soluble adduct present.

74. A coating composition comprising a water soluble composition as claimed in claim 49 and additionally containing from 25 to 200 weight percent of hexamethoxymethylmelamine based on the weight of water soluble adduct present.

75. A coating composition comprising a water soluble composition as claimed in claim 50 and additionally containing from 25 to 200 weight percent of hexamethoxymethylmelamine based on the weight of water soluble adduct present.