Epoxy resins of controlled conversion and a process for their preparation

• US 4,722,981 A
• Filed: 01/29/1987
• Issued: 02/02/1988
• Est. Priority Date: 02/14/1986
• Status: Expired due to Term

• Current Assignee: The Dow Chemical Company (Dow, Inc.)
• Original Assignee: The Dow Chemical Company (Dow, Inc.)
• Inventors: Elliott, Brian W., Koenig, Raymond A.
• Primary Examiner(s): NOT, DEFINED
• Application Number:
  US07/010,057
• Time in Patent Office: 369 Days
• Field of Search: 528/89, 528/87, 528/104, 528/99, 525/481, 525/507
• US Class Current: 525/481
• CPC Class Codes: C08G 59/1405 with inorganic compounds
• CPC Class Codes: C08G 59/1433 with organic low-molecular-weight compounds
• CPC Class Codes: C08G 59/621 Phenols

Abstract

Epoxy resins containing both terminal hydroxyl groups and epoxy or epoxy-derived groups are prepared by advancing a polyepoxide with a polyol and terminating the reaction at a point such that the epoxy resin reaction product contains both epoxy and terminal hydroxyl groups. The controlled conversion resins have improved cure rates. The epoxy groups can be further reacted to form epoxy-derived groups to improve the cure rate even further. The epoxy resins exhibit lower melt and solution viscosities than those exhibited by conventional epoxy resins having the same epoxy equivalent weight, as well as curing quickly when used. The resins are usefully employed at high solids levels in can coating formulations and other epoxy formulations wherein the resin is applied from an organic liquid solution or aqueous dispersion.

Claims

1. An epoxy resin comprising the reaction product of a polyepoxide and a polyol wherein the reaction product contains both epoxy groups and terminal phenolic hydroxyl groups in an amount of at least about 0.25 weight percent of each of the epoxy groups and the terminal phenolic hydroxyl groups, said weight percent being based on the total weight of the epoxy resin reaction product, and which reaction product exhibits an essentially constant viscosity over time.

2. The epoxy resin as claimed in claim 1, wherein the resin contains from about 0.5 to less than about 20 weight percent epoxy groups and from about 0.25 to less than about 10 weight percent terminal hydroxyl groups.

3. The epoxy resin as claimed in claim 1, wherein the reaction product has a number average molecular weight of less than about 10,000.

4. A process for preparing an epoxy resin which method comprises reacting a polyepoxide with a polyhydric phenol in the presence of a catalyst for the reaction of an epoxy group with a hydroxyl group and terminating the reaction at a point when the reaction product contains at least about 0.25 weight percent of each of the epoxy groups and the terminal hydroxyl groups, said weight percent being based on the total weight of the epoxy resin reaction product

5. The process as claimed in claim 4, wherein the reaction is terminated by the addition of a solvent to the reaction mixture at desired conversion.

6. The process as claimed in claim 4, wherein the reaction is terminated by the addition of a material which effectively inhibits further reaction of the epoxy and hydroxyl groups, the material being added in an amount sufficient to effectively inhibit the

7. The process as claimed in claim 4, wherein the reaction is terminated when from about 10 to about 95 percent of the deficient component or if the polyepoxide and polyhydric phenol components are employed in equivalent amounts, from about 10 to about 95 percent of both components have reacted.

8. The process as claimed in claim 6, wherein the inhibitor is a strong acid or an anhydride or ester of a strong acid.

9. The process as claimed in claim 6, wherein the inhibitor is added in an amount of at least about 1 equivalent per equivalent of catalyst employed

10. A product of the process of claim 4.

11. A product of the process of claim 5.

12. A product of the process of claim 6.

13. A product of the process of claim 7.

14. A product of the process of claim 8.

15. A product of the process of claim 9.

16. An epoxy resin comprising the reaction product of a polyepoxide and a polyol wherein the reaction product contains

(a) terminal phenolic hydroxyl groups in an amount of at least about 0.15 equivalents per kilogram resin (eq/kg),

(b) groups derived from epoxy groups, and optionally

(c) epoxy groups

the total amount of groups (b), and, if present (c) in the resin being at least about 0.05 equivalents, per kilogram of resin.

17. An epoxy resin as claimed in claim 16, wherein the total amount of groups (b) and, if present (c) groups in the resin is from about 0.058 to about 2 equivalents per kilogram of resin.

18. An epoxy resin as claimed in claim 17, wherein the resin contains substantially no epoxy groups.

19. An epoxy resin as claimed in claim 16, wherein the resin contains from 1 to 3 terminal phenolic hydroxyl group equivalents per kilogram of resin.

20. A process for preparing an epoxy resin which method comprises reacting a polyepoxide with a polyol in the presence of a catalyst for the reaction of an epoxy group with a hydroxyl group and terminating the reaction at a point when the reaction product contains at least about 0.05 equivalents epoxy groups per kilogram of resin and about 0.15 equivalents terminal phenolic hydroxyl groups per kilogram of resin, then reacting at least a portion of the epoxy groups to form epoxy-derived groups.

21. A process as claimed in claim 20, wherein the epoxy groups are reacted with water.

22. A process as claimed in claim 21, wherein the epoxy groups are reacted with water and acid.

23. A process as claimed in claim 22, wherein the epoxy groups are reacted with water and phosphoric acid.

24. A process as claimed in claim 20, wherein the reaction of the polyepoxde and polyol is terminated and the epoxy groups are reacted with phosphoric acid in a single process step.