Phenolic curing agents for epoxy resins

• US 4,767,832 A
• Filed: 05/29/1987
• Issued: 08/30/1988
• Est. Priority Date: 05/29/1987
• Status: Expired due to Term

• Current Assignee: Resolution Performance Products LLC (Bakelite UK TopCo Ltd.)
• Original Assignee: Shell Oil Company (Shell Plc)
• Inventors: Marx, Edward J.
• Primary Examiner(s): NOT, DEFINED
• Application Number:
  US07/055,653
• Time in Patent Office: 459 Days
• Field of Search: 525/523, 525/529, 525/524, 528/94, 528/104
• US Class Current: 525/523
• CPC Class Codes: C08G 59/182 using pre-adducts of epoxy compounds with curing agents
• CPC Class Codes: C08G 59/621 Phenols

Abstract

A phenolic curing agent for epoxy resin powder coatings is prepared by combining (a) a linear phenolic hydroxyl-terminated resin having a weight per phenolic within the range of about 650 to about 8,000, preferably about 850 to about 950, (b) a dihydric phenol present in an amount such that the weight per hydroxyl of the mixture of (a) and (b) is within the range of about 240 to about 280, and (c) at least about 2 weight percent, based on the weight of the composition, of an imidazole cure accelerator. The described imidazole-accelerated curing agent is less susceptible to melting point depression and to sintering with storage than conventional imidazole-containing phenolic curing agents. The dihydric phenol-terminated epoxy resin is preferably prepared by reacting a dihydric phenol with a linear diepoxy resin in the presence of a phosphonium halide catalyst so as to produce a phenolic hydroxyl-terminated resin having a weight per hydroxyl within the range of about 650 to about 8,000.

Claims

1. A composition comprising:

(a) a linear phenolic hydroxyl-terminated resin having a phenolic equivalent weight within the range of about 650°

to about 8,000;

(b) a dihydric phenol present in the composition in an amount such that the weight per phenolic of a mixture of (a) and (b) is within the range of about 240 to about 280; and

(c) an imidazole compound present in an amount of at least about 2 weight percent, based on the weight of the composition.

2. The composition of claim 1 in which the dihydric phenol is bisphenol-A.

3. The composition of claim 1 in which the linear phenolic hydroxyl-terminated resin is a product of advancing a linear diepoxy resin having a weight per epoxide within the range of about 170 to about 210 with a dihydric phenol to an advanced epoxy resin having a weight per epoxide within the range of about 500 to about 3500, and reacting said advanced epoxy resin with a molar excess of a dihydric phenol under conditions effective to produce a linear phenolic hydroxyl-terminated resin having a phenolic equivalent weight within the range of about 650 to about 8,000.

4. The composition of claim 1 in which the linear phenolic hydroxyl-terminated resin is a reaction product of bisphenol-A and a linear diglycidyl ether of bisphenol-A.

5. The composition of claim 1 in which the imidazole compound is selected from 1-methylimidazole, 2-methyl imidazole, 2,4-ethylmethylimidazole, 2-isopropylimidazole, 1-decylimidazole and 2-phenylimidazole.

6. The composition of claim 1 in which the imidazole compound is present in an amount of from about 3 to about 12 weight percent.

7. The composition of claim 6 in which the imidazole compound is 2-methylimidazole.

8. The composition of claim 1 which has a melting point greater than about 75°

C.

14. A powder coating composition comprising the composition of claim 1.

9. A process for preparing a curing agent for an epoxy resin, said process comprising:

(a) contacting a linear diepoxy resin having a weight per epoxide within the range of about 170 to about 210 with a dihydric phenol in the presence of a catalytic amount of an epoxy advancement catalyst under conditions effective to produce a diepoxy resin having an average weight per epoxide within the range of about 500 to about 8000;

(b) contacting the reaction product of step (a) with a molar excess of the dihydric phenol in the presence of the advancement catalyst to produce a linear phenolic hydroxyl-terminated resin having a weight per hydroxyl within the range of about 240 to about 280; and

(c) adding to the product of step (b) at least about 2 weight percent of an imidazole compound.

10. The process of claim 9 in which the linear diepoxy resin is a diglycidyl ether of bisphenol-A.

11. The process of claim 9 in which the dihydric phenol is bisphenol-A.

12. The process of claim 9 in which the imidazole compound is 2-methyl imidazole.

13. The process of claim 9 in which the diepoxy resin product of step (a) has a weight per epoxide within the range of about 850 to about 950.

15. A powder coating composition comprising the curing agent product of the process of claim 9.