Multi-modal vinyl ester resins

Abstract

Multi-modal vinyl ester resins having one or more of good fracture toughness, good processing viscosity, and low volatile organic compound emissions are provided. The multi-modal vinyl ester resins are the reaction product of a liquid or crystalline epoxy and an amorphous, solid epoxy, as determined at 25° C., with a vinyl carboxylic acid. The multi-modal vinyl ester resins may contain a reactive diluent, though generally, lower reactive diluent contents are required for such resins than for similar, commercially available vinyl ester resins.

1. Vinyl A vinyl ester resins having a defined multi-modal molecular weight distribution resin comprising a reaction product of a reaction mixture comprising at least one low molecular weight vinyl ester that is derived from only a vinyl carboxylic acid or a blend of vinyl carboxylic acids and an epoxy resin or a combination of epoxy resins that is liquid or crystalline at 25° C. and at least one high molecular weight vinyl ester that is derived from only a vinyl carboxylic acid or a blend of vinyl carboxylic acids and an epoxy resin or a combination of epoxy resins that is amorphous and solid at 25° C.; selected from the group consisting of an epoxy resin derived from bisphenol A, an epoxy resin derived from hexafluorobisphenol A, an epoxy resin derived from bisphenol E, an epoxy resin derived from bisphenol F, an epoxy resin derived from tetramethyl bisphenol E, an epoxy resin derived from tetramethyl bisphenol F, an epoxy resin derived from bisphenol M, an epoxy resin derived from bisphenol C, an epoxy resin derived from bisphenol P, an epoxy resin derived from bisphenol Z, an epoxy resin derived from methacrylates of ethoxylated bisphenols, an epoxy resin derived from acrylates of ethoxylated bisphenols, epoxy novolacs, acrylates of tris-hydroxyphenylmethane glycidyl ether, ethoxy phenol novolacs, an epoxy resin derived from ethoxylated tris-hydroxyphenylmethane and brominated versions of these epoxy resins, and from 0% up to 60% by weight of a reactive diluent, wherein said vinyl ester resin has a defined multi-modal molecular weight distribution. 
     
     
       2. Vinyl The vinyl ester resins resin as claimed in  claim 1 , wherein at least one low molecular weight said vinyl ester comprises 5-65% by weight, of the overall resin weight resin has a bi-modal molecular weight distribution. 
     
     
       3. Vinyl ester resins as claimed in  claim 1 , wherein at least one high molecular weight vinyl ester comprises 5-65% by weight, of the overall resin weight. 
     
     
       4. Vinyl The vinyl ester resins resin as claimed in claim  1  2, wherein the at least one low molecular weight vinyl ester comprises 5-65% by weight, of the overall resin weight, and at least one high molecular weight vinyl ester comprises 5-65% by weight, of the overall resin weight. 
     
     
       5. Vinyl ester resins as claimed in  claim 4 , wherein the reaction mixture comprises 1% to 60% by weight of a reactive diluent. 
     
     
       6. Vinyl The vinyl ester resins resin as claimed in claim  5  4, wherein the reaction mixture comprises 1% to 40% by weight of the reactive diluent and the reactive diluent is selected from the group consisting of fatty acid monomers, styrene, ortho-methylstyrene, para-methylstyrene, 2-hydroxymethacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, cyclohexyl methacrylate, and isobornyl methacrylate. 
     
     
       7. Vinyl The vinyl ester resins resin as claimed in  claim 6 , comprising up to 40 30% by weight of a reactive diluent. 
     
     
       8. Vinyl The vinyl ester resins resin as claimed in  claim 6 , comprising up to 30 20% by weight of a reactive diluent. 
     
     
       9. Vinyl ester resins as claimed in  claim 6 , comprising up to 20% by weight of a reactive diluent. 
     
     
       10. Vinyl The vinyl ester resins resin as claimed in claim  6  2, wherein the reaction mixture comprises 1% to 60% by weight of the reactive diluent and the reactive diluent comprises at least one fatty acid monomer. 
     
     
       11. Vinyl The vinyl ester resins resin as claimed in  claim 6 , wherein the reactive diluent comprises styrene. 
     
     
       12. Vinyl The vinyl ester resins resin as claimed in claim  1  2, wherein the low molecular weight vinyl esters ester and high molecular weight vinyl ester are independently selected from the group consisting of acrylic vinyl esters and alkyl-acrylic vinyl esters. 
     
     
       13. Vinyl The vinyl ester resins resin as claimed in claim  1  2, wherein the low molecular weight vinyl esters ester and high molecular weight vinyl ester are independently selected from bisphenol vinyl esters. 
     
     
       14. Vinyl The vinyl ester resins resin as claimed in claim  1  2, wherein the vinyl ester resin has a viscosity from about 30 cP to about 2000 cP at 25° C. and a glass transition temperature from about 60° C. to about 200° C. 
     
     
       15. Vinyl The vinyl ester resins resin as claimed in claim  1  2, wherein the vinyl ester resin has a viscosity from about 30 cP to about 500 cP at 25° C. and a glass transition temperature from about 60° C. to about 200° C. 
     
     
       16. Vinyl ester resins as claimed in  claim 1 , wherein the vinyl ester resins have a glass transition temperature from about 60° C. to about 200° C. 
     
     
       17. Vinyl ester resins as claimed in  claim 14 , wherein the vinyl ester resins have a glass transition temperature from about 60° C. to about 200° C. 
     
     
       18. A method for the preparation of a vinyl ester resin having a defined multi-modal molecular weight distributions, said method comprising the step of: reacting at least one low molecular weight vinyl ester that is derived from only a vinyl carboxylic acid or a blend of vinyl carboxylic acids and an epoxy resin or a combination of epoxy resins that is liquid or crystalline at 25 C. and, at least one high molecular weight vinyl ester that is derived from only a vinyl carboxylic acid or a blend of vinyl carboxylic acids and an epoxy resin or a combination of epoxy resins that is amorphous and solid at 25° C. selected from the group consisting of an epoxy resin derived from bisphenol A, an epoxy resin derived from hexafluorobisphenol A, an epoxy resin derived from bisphenol E, an epoxy resin derived from bisphenol F, an epoxy resin derived from tetramethyl bisphenol E, an epoxy resin derived from tetramethyl bisphenol F, an epoxy resin derived from bisphenol M, an epoxy resin derived from bisphenol C, an epoxy resin derived from bisphenol P, an epoxy resin derived from bisphenol Z, an epoxy resin derived from methacrylates of ethoxylated bisphenols, an epoxy resin derived from acrylates of ethoxylated bisphenols, epoxy novolacs, acrylates of tris-hydroxyphenylmethane glycidyl ether, ethoxy phenol novolacs, an epoxy resin derived from ethoxylated tris-hydroxyphenylmethane and brominated versions of these epoxy resins and from 0% up to 60% by weight of a reactive diluent, at a temperature and for a time sufficient to form said blend of vinyl ester monomers resin having a defined multi-modal molecular weight distribution. 
     
     
       19. A method as claimed in  claim 18 , wherein the at least one low molecular weight vinyl ester comprises from about 5 to about 65% by weight, of the overall resin weight, and at least one high molecular weight vinyl ester comprises from about 5 to about 65% by weight of the overall resin weight resin has a bi-modal molecular weight distribution. 
     
     
       20. A method as claimed in  claim 19 , wherein said reacting step further comprises reacting up to about 60% by weight of a reactive diluent with said at least one low molecular weight vinyl ester comprises from about 5% to about 65% by weight, of the overall resin weight, and said at least one high molecular weight vinyl ester comprises from about 5% to about 65% by weight of the overall resin weight. 
     
     
       21. A method as claimed in  claim 20 , wherein in said reacting step comprises reacting up from about 1% to about 40% by weight of a reacting reactive diluent is reacted with said at least one low molecular weight vinyl ester and said at least one high molecular weight vinyl ester. 
     
     
       22. A method as claimed in claim  20  21, wherein said reacting step comprises reacting up to about 30% by weight of a reacting the reactive diluent is reacted with said at least one low molecular weight vinyl ester and said at least one high molecular weight vinyl ester. 
     
     
       23. A method as claimed in claim  20  21, wherein said reacting step comprises reacting up to about 20% by weight of a reacting the reactive diluent is reacted with said at least one low molecular weight vinyl ester and said at least one high molecular weight vinyl ester. 
     
     
       24. A method as claimed in claim  20  21, wherein the reactive diluent comprises at least one fatty acid monomer. 
     
     
       25. A method as claimed in claim  20  21, wherein the reactive diluent comprises styrene. 
     
     
       26. A method as claimed in claim  20  21, wherein the reactive diluent comprises a reactive diluent selected from the group consisting of styrene, methyl methacrylate, fatty acid monomers, cyclohexyl methacrylate, 2-hydroxyethylmethacrylate, para-methyl styrene, ortho-methyl styrene, isobomyl methacrylate, and mixtures thereof. 
     
     
       27. A method of making a cured polymer composition, said method comprising the step of:
 curing a curable vinyl ester resin composition having a viscosity from about 30 cP to about 2000 cP at 25° C., said vinyl ester resin composition having a multi-modal molecular weight distribution and comprising a reaction product of a reaction mixture comprising at least one low molecular weight vinyl ester that is derived from an epoxy resin or a combination of epoxy resins that is liquid or crystalline at 25° C., at least one high molecular weight vinyl ester that is derived from an epoxy resin or a combination of epoxy resins that is amorphous and solid at 25° C., and from 0% up to 60% by weight of a reactive diluent.   
     
     
       28. A method as claimed in claim 27, wherein said curable vinyl ester resin composition further comprises styrene. 
     
     
       29. A method as claimed in claim 27, wherein said vinyl ester resin has a bi-modal molecular weight distribution. 
     
     
       30. A method as claimed in claim 27, wherein the reaction mixture comprises 1% to 40% by weight of the reactive diluent and the reactive diluent is selected from the group consisting of fatty acid monomers, styrene, ortho-methylstyrene, para-methylstyrene, 2-hydroxymethacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, cyclohexyl methacrylate, and isobornyl methacrylate. 
     
     
       31. A method as claimed in claim 27, wherein the reaction mixture comprises up to 30% by weight of a reactive diluent. 
     
     
       32. A method as claimed in claim 27, wherein the reaction mixture comprises up to 20% by weight of a reactive diluent. 
     
     
       33. A method as claimed in claim 27, wherein said cured polymer composition has a fracture toughness of at least 191 J/m 2 . 
     
     
       34. A method as claimed in claim 33 wherein said cured polymer composition has a fracture toughness of from 191 J/m 2  to 500 J/m 2 . 
     
     
       35. A method as claimed in claim 27, wherein said cured polymer composition is a composite. 
     
     
       36. A method as claimed in claim 27, wherein said vinyl ester resin has a glass transition temperature from about 60° C. to about 200° C. 
     
     
       37. A method as claimed in claim 27, wherein said curable vinyl ester resin composition has a viscosity from about 156 cP to about 670 cP at 25° C. 
     
     
       38. A method of making a cured polymer composition, said method comprising the step of:
 curing a curable vinyl ester resin composition having a multi-modal molecular weight distribution, said vinyl ester resin composition being derived from only a vinyl carboxylic acid or a blend of vinyl carboxylic acids and an epoxy resin or a combination of epoxy resins that is liquid or crystalline at 25° C. and at least one high molecular weight vinyl ester that is derived from only a vinyl carboxylic acid or a blend of vinyl carboxylic acids and an epoxy resin or a combination of epoxy resins that is amorphous and solid at 25° C. selected from the group consisting of an epoxy resin derived from bisphenol A, an epoxy resin derived from hexafluorobisphenol A, an epoxy resin derived from bisphenol E, an epoxy resin derived from bisphenol F, an epoxy resin derived from tetramethyl bisphenol E, an epoxy resin derived from tetramethyl bisphenol F, an epoxy resin derived from bisphenol M, an epoxy resin derived from bisphenol C, an epoxy resin derived from bisphenol P, an epoxy resin derived from bisphenol Z, an epoxy resin derived from methacrylates of ethoxylated bisphenols, an epoxy resin derived from acrylates of ethoxylated bisphenols, epoxy novolacs, acrylates of tris-hydroxyphenylmethane glycidyl ether, ethoxy phenol novolacs, an epoxy resin derived from ethoxylated tris-hydroxyphenylmethane and brominated versions of these epoxy resins.   
     
     
       39. A method as claimed in claim 38, wherein said vinyl ester resin has a bi-modal molecular weight distribution. 
     
     
       40. A method as claimed in claim 38, wherein said vinyl ester resin composition further comprises styrene. 
     
     
       41. A method as claimed in claim 38, wherein said cured polymer composition is a composite. 
     
     
       42. A method as claimed in claim 38, wherein the reaction mixture comprises 1% to 40% by weight of the reactive diluent and the reactive diluent is selected from the group consisting of fatty acid monomers, styrene, ortho-methylstyrene, para-methylstyrene, 2-hydroxymethacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, cyclohexyl methacrylate, and isobornyl methacrylate. 
     
     
       43. A method as claimed in claim 38, wherein the reaction mixture comprises up to 30% by weight of a reactive diluent. 
     
     
       44. A method as claimed in claim 38, wherein the reaction mixture comprises up to 20% by weight of a reactive diluent.