Low viscosity adducts of a polycaprolactone polyol and a polyepoxide

• US 4,725,653 A
• Filed: 11/13/1985
• Issued: 02/16/1988
• Est. Priority Date: 10/27/1983
• Status: Expired due to Fees

• Current Assignee: Union Carbide Corporation (Dow, Inc.)
• Original Assignee: Union Carbide Corporation (Dow, Inc.)
• Inventors: Koleske, Joseph V.
• Primary Examiner(s): Nielsen, Earl
• Application Number:
  US06/797,471
• Time in Patent Office: 825 Days
• Field of Search: 525/510, 525/511, 525/514, 525/482, 525/507, 528/110, 528/103, 528/361, 528/90, 522/170
• US Class Current: 525/510
• CPC Class Codes: C08G 59/62 Alcohols or phenols
• CPC Class Codes: C08L 2666/18 Polyesters or polycarbonates according to C08L67/00 - C08L69/00; Derivatives thereof
• CPC Class Codes: C09D 163/00 Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins

Abstract

This invention is directed to adducts of a polycaprolactone polyol and a polyepoxide comprising the reaction product of at least one polycaprolactone polyol and a polyepoxide containing two or more epoxy groups per molecule in a molar ratio of polycaprolactone polyol to polyepoxide of from about 2:1 to about 3:1, said adducts having an oxirane content of less than about 0.10 percent and a viscosity of less than about 3700 centistokes at 54.5° C. The adducts are useful in the formulation of high solids coating compositions, polyurethane elastomers, inks, sealants, adhesives and the like.

Claims

1. Curable coating composition comprising:

(1) a polyepoxide containing two or more epoxy groups per molecule, or an amino-formaldehyde resin;

(2) an adduct of a polycaprolactone polyol and a polyepoxide comprising the reaction product of at least one polycaprolactone polyol and a polyglycidyl epoxide containing two or more epoxy groups per molecule, said polycaprolactone polyol being employed in an amount at least sufficient to effect substantially complete reaction of the epoxy groups of the polyglycidyl epoxide; and

(3) a catalyst or a photoinitiator.

2. The curable coating composition as defined in claim 1 further including a substituted cycloaliphatic epoxide.

3. A cured film coating prepared from the curable coating composition of claim 1.

5. The curable coating composition as defined in claim 3 further including a substituted cycloaliphatic epoxide.

6. The curable coating composition as defined in claim 5 wherein the cycloaliphatic epoxide has the formula:

##STR26## wherein R₁ through R₁₈, which can be the same or different, are hydrogen or alkyl radicals generally containing one to nine carbon atoms inclusive; and

R is a valence bond or a divalent hydrocarbon radical generally containing one to twenty carbon atoms inclusive.

7. The curable coating composition as defined in claim 5 wherein the cycloaliphatic epoxide has the formula:

##STR27## wherein R¹ through R¹⁸, which can be the same or different are hydrogen or alkyl radicals generally containing one to nine carbon atoms inclusive.

8. The curable coating composition as defined in claim 5 wherein the cycloaliphatic epoxide has the formula:

##STR28## wherein the R prime and double prime groups are the same or different and are monovalent substitutes or monovalent hydrocarbon radicals.

9. The curable coating composition as defined in claim 5 wherein the cycloaliphatic epoxide is 3.4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate.

10. The curable coating composition as defined in claim 5 wherein the cycloaliphatic epoxide is bis(3,4-epoxycyclohexylmethyl)adipate.

11. The curable coating composition as defined in claim 5 wherein the cycloaliphatic epoxide is vinylcyclohexene diepoxide.

4. Curable coating composition comprising:

(1) a polyepoxide containing two or more epoxy groups per molecule, or an amino-formaldehyde resin;

(2) an adduct of a polycaprolactone polyol and a polyepoxide comprising the reaction product of at least one polycaprolactone polyol and a polyepoxide containing two or more epoxy groups per molecule in a molar ratio of polycaprolactone polyol to polyepoxide of from about 2;

1 to about 3;

1, said adduct having an oxirane content of less than about 0.10 percent and a viscosity of less than about 3700 centistokes at 54.5°

C.; and

(3) a catalyst or a photoinitiator.

12. The curable coating composition as defined in claim 4 wherein the polyepoxide containing two or more epoxy groups per molecule is a polyglycidyl epoxide.

13. The curable coating composition as defined in claim 12 wherein the polyglycidyl epoxide is a diglycidyl ether of Bisphenol A.

14. The curable coating composition as defined in claim 4 wherein the polyepoxide containing two or more epoxy groups per molecule is a mixture of a cycloaliphatic epoxide and a polyglycidyl epoxide.

15. The curable coating composition as defined in claim 4 wherein component (1) is a polyepoxide containing two or more epoxy groups per molecule.

16. The curable coating composition as defined in claim 4 wherein component (1) is an amino-formaldehyde resin.

17. The curable coating composition as defined in claim 16 wherein the amino-formaldehyde resin is a melamine formaldehyde resin, a urea formaldehyde resin or a benzoguanamine formaldehyde resin.

18. The curable coating composition as defined in claim 4 wherein the polycaprolactone polyol is a polycaprolactone triol.

19. The curable coating composition as defined in claim 4 wherein the polycaprolactone polyol is a polycaprolactone diol.

20. The curable coating composition as defined in claim 4 wherein the polycaprolactone polyol is a mixture of a polcaprolactone triol and a polycaprolactone diol.

21. Cured film coating prepared from the curable coating composition of claim 4.

22. Curable coating composition comprising:

(1) a polyepoxide containing two or more epoxy groups per molecule, or an amino-formaldehyde resin;

(2) an adduct of a polycaprolactone polyol and a polyepoxide comprising the reaction product of one polycaprolactone polyol and a polyepoxide containing two or more epoxy groups per molecule in a molar ratio of polycaprolactone polyol to polyepoxide of from about 2;

1 to about 3;

1, said adduct having an oxirane content of less than about 0.50 percent and a viscosity of less than about 20,000 centistokes at 54.5°

C.; and

(3) a catalyst or a photoinitiator.

23. The curable coating composition as defined in claim 22 further including a substituted cycloaliphatic epoxide.

24. The cured film prepared from the curable coating composition of claim 22.

25. Curable coating composition comprising:

(1) a polyepoxide containing two or more epoxy groups per molecule, or an amino-formaldehyde;

(2) a low viscosity adduct of a polycaprolactone polyol and a polyepoxide; and

(3) a catalyst or a photoinitiator, said adduct being prepared by the process comprises reacting at least one polycaprolactone polyol and a polyepoxide containing two or more epoxy groups per molecule in the presence of a sulfonic acid catalyst or derivative thereof at a temperature of from about 80°

to about 225°

C., said polycaprolactone polyol, polyepoxide and sulfonic acid catalyst or derivative thereof being employed in an amount at least sufficient to effect substantially complete reaction of the epoxy groups of the polyepoxide to give an oxirane content of less than about 0.10 percent and in a sufficiently short period of time or less than about 6 hours whereby to minimize the formation of high viscosity product.

26. The curable coating composition as defined in claim 25 further including a substituted cycloaliphatic epoxide.

27. Cured film coating prepared from the curable coating composition of claim 25.

28. Curable coating composition comprising:

(1) a polyepoxide containing two or more epoxy groups per molecule, or an amino-formaldehyde resin;

(2) an adduct of a polycaprolactone polyol and a polyepoxide; and

(3) a catalyst or a photointiator, said adduct being prepared by the process for preparing a low viscosity adduct of a polycaprolactone polyol and a polyepoxide which process comprises reacting at least one polycaprolactone polyol and a polyglycidyl epoxide containing two or more epoxy groups per molecule in the presence of a sulfonic acid catalyst or derivative thereof at a temperature of from about 80°

C., said polycaprolactone polyol, polyglycidyl epoxide and sulfonic acid catalyst or derivative thereof being employed in an amount at least sufficient to effect substantially complete reaction of the epoxy groups of the polyglycidyl epoxide in a sufficiently short period of time whereby to minimize the formation of a high viscosity product.

29. The curable coating composition as defined in claim 28 further including a substituted cycloaliphatic epoxide.

30. Cured film coating prepared from the curable coating composition of claim 28.

31. Curable coating composition comprising:

(1) a polyepoxide containing two or more epoxy groups per molecule, or an amino-formaldehyde resin;

(2) an adduct of a polycaprolactone polyol and a polyepoxide; and

(3) a catalyst or a photoinitiator, said adduct being prepared by the process for preparing a low viscosity adduct of a polycaprolactone polyol and a polyepoxide which process comprises reacting one polycaprolactone polyol and a polyepoxide containing two or more epoxy groups per molecule in the presence of a sulfonic acid catalyst or derivative thereof at a temperature of from about 80°

C. to about 225°

C., said polycaprolactone polyol, polyepoxide and sulfonic acid catalyst or derivative thereof being employed in an amount at least sufficient to effect substantially complete reaction of the epoxy groups of the polyepoxide in a sufficiently short period of time whereby to minimize the formation of a high viscosity product.

32. The curable coating composition as defined in claim 31 further including a substituted cycloaliphatic epoxide.

33. Cured film coating prepared from the curable coating composition of claim 31.

34. Curable coating composition comprising:

(1) a polyisocyanate;

(2) an adduct of a polycaprolactone polyol and a polyepoxide comprising the reaction product of at least one polycaprolactone polyol and a polyepoxide containing two or more epoxy groups per molecule in a molar ratio of polycaprolactone polyol to polyepoxide of from about 2;

1 to about 3;

1, said adduct having an oxirane content of less than about 0.10 percent and a viscosity of less about about 3700 centisokes at 54.5°

C.; and

(3) a catalyst or a photoinitiator.