Acetoacetoxy and enamine compounds and coatings therefrom

1. An acetoacetylated resin which is the reaction product of:

a) a polyol having 4 or more hydroxyl groups and

b) at least one acetoacetate;

wherein a portion of the hydroxyl groups of the polyol are replaced by acetoacetate groups; and

wherein the remaining hydroxyl groups are replaced by a saturated monofunctional carboxylic acid ester, an unsaturated monofunctional carboxylic acid ester, or a mixture thereof selected from a vegetable or seed oil carboxylic acid ester,

wherein the polyol having 4 or more hydroxyl groups is sucrose.

2. An enamine resin which is the reaction product of:

a) an acetoacetylated resin of claim 1 , and

b) a C 1 -C 20 alkyl amine or a mixture of C 1 -C 20 alkyl amines.

3. An enamine resin of claim 2 , wherein substantially all hydroxyl groups of the polyol are replaced by acetoacetate groups.

4. An enamine resin of claim 2 , wherein only a portion of the hydroxyl groups of the polyol are replaced by acetoacetate groups.

5. An enamine resin of claim 4 , wherein the remaining hydroxyl groups are replaced by a saturated monofunctional carboxylic acid ester, unsaturated monofunctional carboxylic acid ester, or a mixture thereof.

6. A resin of claim 2 , wherein:

a) the polyol having 4 or more hydroxyl groups is selected from pentaerithritol, di-trimethylolpropane, di-pentaerithritol, tri-pentaerithritol, sucrose, glucose, mannose, fructose, galactose, raffinose, copolymers of styrene and allyl alcohol, polyglycidol and poly(dimethylpropionic acid).

7. A resin of claim 1 , wherein:

the saturated monofunctional carboxylic acid ester, unsaturated monofunctional carboxylic acid ester, or a mixture thereof is a fatty acid of soybean oil.

8. An enamine resin of claim 2 wherein substantially all of the acetoacetoxy groups are replaced by enamine groups.

9. An enamine resin of claim 2 wherein only a portion of the acetoacetoxy groups are replaced by enamine groups.

10. An enamine resin of claim 8 , wherein the C 1 -C 20 alkyl amine is butylamine, hexylamine, octylamine, decylamine, dodecylamine, octadecylamine, or a mixture thereof.

11. An enamine resin of claim 9 , wherein the C 1 -C 20 alkyl amine is butylamine, hexylamine, octylamine, decylamine, dodecylamine, octadecylamine, or a mixture thereof.

12. An enamine resin of claim 5 , wherein:

the polyol having 4 or more hydroxyl groups is selected from pentaerithritol, di-trimethylolpropane, di-pentaerithritol, tri-pentaerithritol, sucrose, glucose, mannose, fructose, galactose, raffinose, copolymers of styrene and allyl alcohol, polyglycidol and poly(dimethylpropionic acid); and

the saturated monofunctional carboxylic acid ester, unsaturated monofunctional carboxylic acid ester, or a mixture thereof is a vegetable or seed oil carboxylic acid ester; and

the C 1 -C 20 alkyl amine is butylamine, hexylamine, octylamine, decylamine, dodecylamine, octadecylamine, or a mixture thereof.

13. A resin of claim 12 , wherein:

a) the polyol having 4 or more hydroxyl groups is sucrose; and

b) the saturated monofunctional carboxylic acid ester, unsaturated monofunctional carboxylic acid ester, or a mixture thereof is a fatty acid of soybean oil.

14. A curable coating composition comprising:

a) a resin of claim 1 or 2 ,

b) at least one metallic drier compound, and

c) optionally, one or more solvents.

15. A curable coating composition comprising:

a) an acetoacetylated resin of claim 1 ;

b) enamine resin which is the reaction product of:

an acetoacetylated resin, and

a C 1 -C 20 alkyl amine or a mixture of C 1 -C 20 alkyl amines,

wherein the acetoacetylated resin forming the enamine is the reaction product of:

a polyol having 4 or more hydroxyl groups; and

at least one acetoacetate;

and wherein only a portion of the acetoacetoxy groups are replaced by enamine groups;

c) an poly-functional amine compound having two or more primary amine groups;

d) at least one metallic drier; and

e) optionally one or more solvents.

16. A curable coating composition of claim 15 , wherein:

in the acetoacetylated resin a)

the polyol having 4 or more hydroxyl groups is selected from pentaerithritol, di-trimethylolpropane, di-pentaerithritol, tri-pentaerithritol, sucrose, glucose, mannose, fructose, galactose, raffinose, copolymers of styrene and allyl alcohol, polyglycidol and poly(dimethylpropionic acid); and

the saturated monofunctional carboxylic acid ester, unsaturated monofunctional carboxylic acid ester, or a mixture thereof is a vegetable or seed oil carboxylic acid ester; and

in the enamine resin b)

the polyol having 4 or more hydroxyl groups is selected from pentaerithritol, di-trimethylolpropane, di-pentaerithritol, tri-pentaerithritol, sucrose, glucose, mannose, fructose, galactose, raffinose, copolymers of styrene and allyl alcohol, polyglycidol and poly(dimethylpropionic acid); and

the saturated monofunctional carboxylic acid ester, unsaturated monofunctional carboxylic acid ester, or a mixture thereof is a vegetable or seed oil carboxylic acid ester; and

the C 1 -C 20 alkyl amine is butylamine, hexylamine, octylamine, decylamine, dodecylamine, octadecylamine, or a mixture thereof.

17. A curable coating composition of claim 16 , wherein:

in the acetoacetylated resin a) the polyol having 4 or more hydroxyl groups is sucrose; and the saturated monofunctional carboxylic acid ester, unsaturated monofunctional carboxylic acid ester, or a mixture thereof is a fatty acid of soybean oil; and

in the enamine resin b) the polyol having 4 or more hydroxyl groups is sucrose; and the saturated monofunctional carboxylic acid ester, unsaturated monofunctional carboxylic acid ester, or a mixture thereof is a fatty acid of soybean oil.

18. An article coated with a cured coating composition according to claim 14 .

19. An article coated with a cured coating composition according to claims 15 .

20. A resin of claim 5 , wherein:

the saturated monofunctional carboxylic acid ester, unsaturated monofunctional carboxylic acid ester, or a mixture thereof is a vegetable or seed oil carboxylic acid ester.