Liquid epoxy resin composition useful for making polymers
A liquid epoxy resin composition is provided. In preferred embodiments, the liquid epoxy resin composition is free of bisphenol A, bisphenol F, and bisphenol S, including epoxides thereof, and is useful in preparing a polyether polymer having utility in coating compositions, including, e.g., coating compositions for use on food or beverage containers.
1. A liquid epoxy resin composition suitable for use in forming a polyether polymer that can be used to coat a food or beverage container; wherein the liquid epoxy resin composition is a liquid at 20° C. and atmospheric pressure and is substantially free of bisphenol A, bisphenol F, bisphenol S, epoxides of bisphenol A, epoxides of bisphenol F, and epoxides of bisphenol S;
wherein the liquid epoxy resin composition is prepared from reactants comprising one or more epihalohydrins and one or more ortho-substituted diphenol compounds comprising an organic ortho-substituted group;
wherein the liquid epoxy resin composition comprises diepoxide resins comprising a base structure unit derived from the one or more ortho-substituted diphenol compounds and an “n” number of additional structural units derived from the one or more ortho-substituted diphenol compounds;
wherein the liquid epoxy resin composition comprises more than 60 and less than about 75 weight percent of n=0 diepoxide resins derived from the one or more ortho-substituted diphenol compounds and at least 15 and less than about 25 weight percent of n=1 diepoxide resins derived from the one or more ortho-substituted diphenol compounds, based on the total weight of any unreacted ortho-substituted diphenol compounds that may be present and any compounds including at least one structural unit derived from the one or more ortho- substituted diphenol compounds; and
wherein the liquid epoxy resin composition has a hydrolysable chloride content of less than or equal to 0.05 weight percent.
2. The composition of claim 1 , wherein the liquid epoxy resin composition comprises more than 60 and less than about 70 weight percent of n=0 diepoxide resins derived from the one or more ortho-substituted diphenol compounds, based on the total weight of any unreacted ortho-substituted diphenol compounds that may be present and any compounds including at least one structural unit derived from the one or more ortho-substituted diphenol compounds.
3. The composition of claim 1 , wherein the composition comprises at least 15 and less than about 20 weight percent of n=1 diepoxide resin derived from the one or more ortho-substituted diphenol compounds, based on the total weight of any unreacted ortho-substituted diphenol compounds that may be present and any compounds including at least one structural unit derived from the one or more ortho-substituted diphenol compounds.
4. The composition of claim 1 , wherein the one or more epihalohydrins comprises epichlorohydrin.
5. The composition of claim 1 , wherein each aromatic ring of the one or more ortho-substituted diphenol compounds is substituted with a methyl group at an ortho position.
6. The composition of claim 1 , wherein each aromatic ring of the one or more ortho-substituted diphenol compounds is substituted with a methyl group at two ortho positions.
7. The composition of claim 1 , wherein the one or more ortho-substituted diphenol compounds comprises an ortho-substituted bisphenol.
8. The composition of claim 7 , wherein two aromatic rings of the ortho-substituted bisphenol are attached to one another by a —CH2— linkage.
9. The composition of claim 1 , wherein the one or more ortho-substituted diphenol compounds comprises tetramethyl bisphenol F.
10. The composition of claim 1 , wherein the n=0 and n=1 diepoxide resins derived from the one or more ortho-substituted diphenol compounds constitute at least 85 weight percent of the total weight of any unreacted ortho-substituted diphenol compounds that may be present and any compounds including at least one structural unit derived from one or more ortho-substituted diphenol compounds.
11. The composition of claim 1 , wherein: the one or more epihalohydrins comprises epichlorohydrin; the one or more ortho-substituted diphenol compounds comprises tetramethyl bisphenol F (TMBPF); the composition optionally further comprises TMBPF-containing monoepoxide resins; and the n=0 and n=1 tetramethyl bisphenol F containing diepoxide resins constitute at least 85 weight percent and the TMBPF-containing monoepoxide resins constitute less than 5 weight percent, of the total weight of any unreacted TMBPF that may be present and any compounds including at least one structural unit derived from TMBPF.
12. The composition of claim 11 , wherein the composition comprises more than 60 and less than about 75 weight percent of n=0 diepoxide compounds derived from tetramethyl bisphenol F, based on the total weight of any unreacted ortho-substituted diphenol compounds that may be present and any compounds including at least one structural unit derived from the one or more ortho-substituted diphenol compounds.
13. The composition of claim 11 , wherein the n=0 and n=1 TMBPF-containing diepoxide resins constitute at least 85 weight percent of the total weight of any unreacted ortho-substituted diphenol compound that may be present and any compounds including at least one structural unit derived from the one or more ortho-substituted diphenol compounds.
14. The composition of claim 1 , wherein the liquid epoxy resin composition has a hydrolysable chloride content of less than or equal to 0.02 weight percent.
15. The composition of claim 1 , wherein the liquid epoxy resin composition optionally further contains water, in an amount of less than 1 weight percent.
16. The composition of claim 1 , wherein the liquid epoxy resin composition optionally further contains unreacted epichlorohydrin, in an amount of less than 50 ppm.
17. The composition of claim 1 , wherein the liquid epoxy resin composition optionally further contains unreacted ortho-substituted diphenol compounds, in an amount of less than 1,000 ppm.
18. The composition of claim 1 , wherein the liquid epoxy resin composition optionally further contains mono-epoxide resins of the one or more ortho-substituted diphenol compounds, in an amount of less than 5 weight percent.
19. The composition of claim 1 , wherein the liquid epoxy resin composition optionally further contains n≥2 diepoxide resins derived from the one or more ortho-substituted diphenol compounds, in an amount of less than 10 weight percent based on the total weight of any unreacted ortho-substituted diphenol compounds that may be present and any compounds including at least one structural unit derived from the one or more ortho-substituted diphenol compounds.
20. The composition of claim 1 , wherein the liquid epoxy resin composition is storage stable for at least 1 month at about 20° C. at atmospheric pressure.
21. The composition of claim 1 , wherein the liquid epoxy resin composition is storage stable for at least 6 months at about 20° C. at atmospheric pressure.
22. The composition of claim 1 , wherein the liquid epoxy resin composition has a viscosity at 52° C. of 2,000 to 4,000 cps.
23. The composition of claim 1 , wherein the liquid epoxy resin composition optionally further contains:
water, in an amount of less than 0.05 weight percent;
unreacted epichlorohydrin, in an amount of less than 10 ppm;
unreacted ortho-substituted diphenol compounds, in an amount of less than 1,000 ppm;
mono-epoxide resins of the one or more ortho-substituted diphenol compounds, in an amount of less than 3 weight percent; and n≥2 diepoxide resins derived from the one or more ortho-substituted diphenol compounds, in an amount of less than 5 weight percent based on the total weight of any unreacted ortho-substituted diphenol compounds that may be present and any compounds including at least one structural unit derived from the one or more ortho-substituted diphenol compounds;
wherein unless specified, the indicated concentration is based on the total weight of the liquid epoxy resin composition.
24. The composition of claim 1 , wherein the final weight per epoxy equivalent of the liquid epoxy resin composition is within from about 10% to about 20% of the theoretical weight per epoxide equivalent for the n=0 diepoxide resin derived from the one or more ortho-substituted diphenol compounds.
25. The composition of claim 1 , wherein TMBPF is the sole ortho-substituted diphenol compound reacted with the one or more epihalohydrins; and the weight per epoxide equivalent of the liquid epoxy resin composition is from about 200 to about 220 grams/epoxy equivalent.
26. The composition of claim 1 , wherein the liquid epoxy resin composition comprises at least 90% by weight of diepoxide resin derived from the one or more ortho-substituted diphenol compounds, based on the total weight of the liquid epoxy resin composition.
27. The composition of claim 1 , wherein the liquid epoxy resin composition when tested under ambient conditions using the Pour Test described herein, begins flowing out of the beaker within 180 minutes or less.
28. The composition of claim 1 , wherein the liquid epoxy resin composition when tested under ambient conditions using the Pour Test described herein, begins flowing out of the beaker within 15 minutes or less.
29. A method for forming the liquid epoxy resin composition of claim 1 comprising reacting epichlorohydrin with the one or more ortho-substituted diphenol compounds in a molar ratio of from about 7:1 to about 1:1.
30. A method for forming the liquid epoxy resin composition of claim 1 comprising reacting epichlorohydrin with the one or more ortho-substituted diphenol compounds in a molar ratio of from about 5:1 to about 3:1.
31. An aromatic polyether polymer derived from the liquid epoxy resin composition of claim 1 , wherein the polyether polymer is substantially free of bisphenol A, bisphenol F, and bisphenol S, epoxides of bisphenol A, epoxides of bisphenol F, and epoxides of bisphenol S thereof.
32. The aromatic polyether polymer of claim 31 , wherein the polyether polymer is a reaction product of ingredients including the liquid epoxy resin composition of claim 1 and a diphenol, wherein the polyether polymer has a number average molecular weight of at least 2,000 and a Tg of at least 60° C.
33. The aromatic polyether polymer of claim 31 , wherein the polyether polymer is a reaction product of ingredients including the liquid epoxy resin composition of claim 1 and a diphenol, wherein the polyether polymer has a number average molecular weight of at least 4,000 and a Tg of at least 70° C.
34. The aromatic polyether polymer of claim 31 , wherein at least 50 weight percent of the polyether polymer constitutes structural units derived from the liquid epoxy resin composition.