Aliphatic polyester coating compositions containing tetramethyl cyclobutanediol

Abstract

Disclosed are aliphatic polyester resins containing 2,2,4,4-tetramethyl-1,3-cyclobutanediol and solvent borne, thermosetting coating compositions prepared therefrom. The aliphatic polyesters exhibit good hardness and flexibility when formulated into thermosetting coatings compositions.

1 . A curable, aliphatic polyester, comprising:
 i. diacid residues, comprising about 50 to 100 mole percent of a cycloaliphatic dicarboxylic acid;   ii. diol residues, comprising about 50 to 100 mole percent, based on the total moles of diol residues, of the residues of 2,2,4,4-tetramethyl-1,3-cyclobutanediol; and   iii. about 2 to about 40 mole percent of the residues of at least one polyol, based on the total moles of diol and polyol residues;   wherein said curable, aliphatic polyester contains 90 or greater mole percent aliphatic diacid residues based on the total moles of diacid residues, and wherein said curable, aliphatic polyester has a number average molecular weight of about 300 to about 10,000 daltons, a hydroxyl number of about 20 to about 450 mg KOH/g of polyester, and an acid number of 0 to about 80 mg KOH/g of polyester.   
     
     
         2 . The curable, aliphatic polyester according to  claim 1  wherein said diacid residue comprises about 50 to about 100 mole percent of the residues of at least one cycloaliphatic dicarboxylic acid chosen from 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, hexahydrophthalic anhydride, and about 50 to about 0 mole percent of the residues at least one-acyclic aliphatic dicarboxylic acid chosen from adipic acid, dodecanedioic acid, sebacic acid, azelaic acid, succinic acid, and glutaric acid; and said diol residues comprise about 50 to 0 mole percent of the residues of at least one diol chosen from neopentyl glycol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, nonaethylene glycol, decaethylene glycol, 1,3-propanediol, 2,4-dimethyl-2-ethyl-hexane-1,3-diol, 2,2-dimethyl-1,2-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, thiodiethanol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4-trimethyl 1,3-pentanediol, p-xylenediol, hydroxypivalyl hydroxypivalate, 1,10-decanediol, and hydrogenated bisphenol A. 
     
     
         3 . The curable, aliphatic polyester according to  claim 2  wherein said diacid residues comprise about 50 to about 100 mole percent of the residues of 1,4-cyclohexanedicarboxylic acid, hexahydrophthalic anhydride, or a mixture thereof, and about 0 to about 50 mole percent of the residues of adipic acid; and said diol residues comprise about 50 to 0 mole percent of the residues of neopentyl glycol. 
     
     
         4 . The curable, aliphatic polyester according to  claim 3  wherein said diacid residues comprise about 100 mole percent of the residues of hexahydrophthalic anhydride; and said diol residues comprise, about 50 to 100 mole percent of the residues of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and about 50 to 0 mole percent of the residues of neopentyl glycol. 
     
     
         5 . The curable, aliphatic polyester according to  claim 1  which comprises about 3 to about 30 mole percent of the residues of at least one polyol selected from trimethylolpropane, pentaerythritol, trimethylolethane, erythritol, threitol, dipentaerythritol, sorbitol, and glycerine. 
     
     
         6 . The curable, aliphatic polyester according to  claim 1  which has a Tg of about −35 to about 35° C. 
     
     
         7 . The curable, aliphatic polyester
 according to  claim 1  which has a hydroxyl number of about 30 to about 250 mg KOH/g of polyester, an acid number of about 2 to about 15 mg KOH/g of polyester, a number average molecular weight of about 700 to about 7000 daltons, and a Tg of about −35 to about 35° C.   
     
     
         8 . A thermosetting coating composition, comprising:
 (A). about 50 to about 90 weight percent, based on the total weight of (A) and (B) of at least one curable, aliphatic polyester, comprising
 i. diacid residues, comprising about 50 to 100 mole percent of a cycloaliphatic dicarboxylic acid; 
 ii. diol residues, comprising about 50 to 100 mole percent, based on the total moles of diol residues, of the residues of 2,2,4,4-tetramethyl-1,3-cyclobutanediol; and 
 iii. about 2 to about 40 mole percent of the residues of at least one polyol, based on the total moles of diol and polyol residues; 
 wherein said curable, aliphatic polyester contains 90 or greater mole percent aliphatic diacid residues based on the total moles of diacid residues, and wherein said curable, aliphatic polyester has a number average molecular weight of about 300 to about 10,000 daltons, a hydroxyl number of about 20 to about 450 mg KOH/g of polyester, and an acid number of 0 to about 80 mg KOH/g of polyester; 
   (B). about 10 to about 50 weight percent, based on the total weight of (A) and (B) of a crosslinker comprising at least one compound reactive with a carboxylic acid or a hydroxyl group;   (C). about 10 to about 60 weight percent, based on the total weight of (A), (B), and (C) of at least one nonaqueous solvent.   
     
     
         9 . The coating composition according to  claim 8  wherein said curable, aliphatic polyester comprises diacid residues comprising about 50 to about 100 mole percent of the residues of at least one cycloaliphatic dicarboxylic acid is chosen from 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and hexahydrophthalic anhydride, and about 50 to about 0 mole percent of the residues at least one acylic aliphatic dicarboxylic acid chosen from adipic acid, dodecanedioic acid, sebacic acid, azelaic acid, succinic acid, and glutaric acid; and diol residues comprising about 50 to 0 mole percent of the residues of at least one diol chosen from neopentyl glycol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, nonaethylene glycol, decaethylene glycol, 1,3-propanediol, 2,4-dimethyl-2-ethyl-hexane-1,3-diol, 2,2-dimethyl-1,2-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, thiodiethanol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4-trimethyl 1,3-pentanediol, p-xylenediol, hydroxypivalyl hydroxypivalate, 1,10-decanediol, and hydrogenated bisphenol A. 
     
     
         10 . The coating composition according to  claim 9  wherein said diacid residues comprise about 50 to about 100 mole percent of the residues of 1,4-cyclohexanedicarboxylic acid, hexahydrophthalic anhydride, or a mixture thereof, and about 50 to about 0 mole percent of the residues of adipic acid; and said diol residues comprise about 50 to 0 mole percent of the residues of neopentyl glycol. 
     
     
         11 . The coating composition according to  claim 8  wherein said curable, aliphatic polyester has a Tg of about −35 to about 35° C. 
     
     
         12 . The coating composition according to  claim 8  wherein said curable, aliphatic polyester comprises about 3 to about 30 mole percent of the residues of at least one polyol selected from trimethylolpropane, pentaerythritol, trimethylolethane, erythritol, threitol, dipentaerythritol, sorbitol, and glycerine. 
     
     
         13 . The coating composition according to  claim 8  wherein said curable, aliphatic polyester has a hydroxyl number of about 30 to about 250 mg potassium hydroxide per gram of polyester, an acid number of about 2 to about 15 mg potassium hydroxide per gram of polyester, and a number average molecular weight of about 700 to about 7000 daltons, and a Tg of about −35 to about 35° C. 
     
     
         14 . The coating composition according to  claim 8  wherein said crosslinker comprises at least one compound chosen from melamines, isocyanates, and isocyanurates. 
     
     
         15 . The coating composition according to  claim 14  wherein said crosslinker comprises at least one melamine compound chosen from hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, tetramethoxymethylurea, and mixed butoxy/methoxy substituted melamines. 
     
     
         16 . The coating composition according to  claim 14  wherein said crosslinker comprises isocyanurates of 1,6-hexamethylene diisocyanate, the biuret of 1,6-hexamethylene diisocyanate, the trimer of 1,6-hexamethylene diisocyanate, or combinations thereof. 
     
     
         17 . The coating composition according to  claim 8  wherein said nonaqueous solvent comprises benzene, xylene, mineral spirits, naptha, toluene, acetone, methyl ethyl ketone, methyl n-amyl ketone, methyl isoamyl ketone, n-butyl acetate, isobutyl acetate, t-butyl acetate, n-propyl acetate, isopropyl acetate, ethyl acetate, methyl acetate, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, ethylene glycol monobutyl ether, propylene glycol n-butyl ether, propylene glycol methyl ether, propylene glycol monopropyl ether, dipropylene glycol methyl ether, diethylene glycol monobutyl ether, trimethylpentanediol mono-isobutyrate, ethylene glycol mono-octyl ether, diacetone alcohol, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, or combinations thereof. 
     
     
         18 . A shaped object coated with the coating composition of  claim 8 .