Polyurethane coating formulations based on polyepoxide-caprolactone polyols and polyisocyanates

• US 3,989,676 A
• Filed: 05/05/1975
• Issued: 11/02/1976
• Est. Priority Date: 11/14/1973
• Status: Expired due to Term

• Current Assignee: Union Carbide Corporation (Dow, Inc.)
• Original Assignee: Union Carbide Corporation (Dow, Inc.)
• Inventors: Gerkin, Richard Michael, Comstock, Lowell Ray
• Primary Examiner(s): Welsh, M. J.
• Application Number:
  US05/574,377
• Time in Patent Office: 547 Days
• Field of Search: 260/77.5 AN
• US Class Current: 528/81
• CPC Class Codes: C08G 18/4244 containing oxygen in the form of ether groups
• CPC Class Codes: C08G 18/4277 Caprolactone and/or substituted caprolactone
• 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

Compositions useful for the formation of high performance coatings are provided as the reaction products of a caprolactone polyol having an average hydroxyl functionality of at least three and a polyepoxide. The products formed by reaction of a caprolactone triol and a cycloaliphatic diepoxide are used with particular advantage as the active hydrogen-containing component of polyurethane formulations to be applied as coatings on external surfaces of aircraft.

Claims

1. A two-package urethane coating formulation which comprises (1) an organic polyisocyanate, and (2) a polyol composition prepared by the reaction of (a) and (b) where (a) is a caprolactone polyol having an average of at least three hydroxyl groups per molecule and (b) is a polyepoxide having at least two vicinal epoxy groups per molecule, the amount of reactant (a) employed in forming said polyol composition being at least sufficient to effect substantially complete reaction of the epoxy groups of (b).

2. A two-package urethane coating formulation which comprises (1) an organic polyisocyanate, and (2) a polyol composition formed by reaction at a temperature from about 100°

to about 190°

C. of (a) and (b) where;

a. is a caprolactone polyol having an average of from three to six hydroxyl groups per molecule; and

b. is a cycloaliphatic diepoxide having the formula, ##SPC11##

where R represents hydrogen or an alkyl group having from one to four carbon atoms, R°

represents a valence bond or a bivalent hydrocarbon radical having from 1 to 9 carbon atoms, and a has a value of zero or one;

the mole ratio of (a) to (b) employed in forming said polyol composition being from about 1.8;

1 to about 2.5;

1.

3. A two-package urethane coating formulation which comprises (1) an organic polyisocyanate, and (2) a polyol composition prepared by the reaction of (a) and (b) where:

(a) is a caprolactone triol having an average hydroxyl number from about 185 to about 560 prepared by the reaction of trimethylolpropane and epsilon-caprolactone, and (b) is 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexane)carboxylate, the said reaction of (a) and (b) being effected at a temperature between about 100° and

about 190°

C. in the presence of a tin carboxylate as catalyst, employing about two moles of (a) per mole of (b).

4. A polyurethane coating composition comprising the reaction product of (1) an organic polyisocyanate and (2) a polyol composition prepared by the reaction of (a) and (b) where (a) is a caprolactone polyol having an average of at least three hydroxyl groups per molecule and (b) is a polyepoxide having at least two vicinal epoxy groups per molecule, the amount of reactant (a) employed in forming said polyol composition being at least sufficient to effect substantially complete reaction of the epoxy groups of (b).

5. A polyurethane coating composition comprising the reaction product of (1) an organic polyisocyanate and (2) a polyol composition formed by reaction at a temperature from about 100°

to about 190°

C. of (a) and (b) where;

a. is a caprolactone polyol having an average of from three to six hydroxyl groups per molecule; and

b. is a cycloaliphatic diepoxide having the formula, ##SPC12##

where R represents hydrogen or an alkyl group having from one to four carbon atoms, R°

represents a valence bond or a bivalent hydrocarbon radical having from 1 to 9 carbon atoms, and a has a value of zero or one;

the mole ratio of (a) to (b) employed in forming said polyol composition being from about 1.8;

1 to about 2.5;

1.

6. A polyurethane coating composition comprising the reaction product of (1) an organic polyisocyanate and (2) the polyol composition prepared by the reaction of (a) and (b) where (a) is a caprolactone triol having an average hydroxyl number from about 185 to about 560 prepared by the reaction of trimethylolpropane and epsilon-caprolactone, and (b) is 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexane) carboxylate, the said reaction of (a) and (b) being effected at a temperature between about 100°

and about 190°

C. in the presence of a tin carboxylate as catalyst, employing about two moles of (a) per mole of (b).

7. A polyurethane coating composition comprising the reaction product of:

1. a biuret-containing aliphatic polyisocyanate; and

2. a polyol composition prepared by the reaction of (a) and (b) where (a) is a caprolactone triol having an average hydroxyl number from about 185 to about 560 prepared by the reaction of trimethylolpropane and epsilon-caprolactone and (b) is 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexane) carboxylate, the said reaction of (a) and (b) being effected at a temperature between about 100° and

about 190°

C. in the presence of a tin carboxylate as catalyst, employing about two moles of (a) per mole of (b);

the amount of said reactants (1) and (2) employed in forming said coating composition being sufficient to provide an --NCO to --OH equivalent ratio of from about 1;

1 to about 1.4;

1.