Process to produce blended (meth)acrylate/vinyl ester resin cross-linkers

Patent metadata

Field	Value
Publication number	US-11208420-B2
Application number	US-201716462741-A
Country	US
Kind code	B2
Filing date	Nov 16, 2017
Priority date	Nov 22, 2016
Publication date	Dec 28, 2021
Grant date	Dec 28, 2021

Abstract

This invention outlines a method for synthesizing a blended resin system in a one pot reaction that may utilize, for example, bio-based anhydrosugars such as isosorbide as a principle component to produce isosorbide dimethacrylate and other monomeric materials for thermosetting applications. This invention establishes a one-pot procedure for reacting a hydroxy group containing compound with methacrylic anhydride in the first step and using the by-product methacrylic acid to react with glycidyl ethers to form additional methacrylate compounds in the second step. This methodology can be formulated to produce a wide array of resin systems that have controlled ratios of hydroxy group containing compound/crosslinker/reactive diluent. Additionally, the novel resin systems may be partially to fully biobased, promoting global sustainability and reducing costs, and when free radically polymerized have properties that meet or exceed their petroleum derived counterparts.

First claim

What is claimed is:

1. A method for producing a curable resin in a one-pot, two step reaction, said method comprising:
i) reacting isosorbide with a (meth)acrylic anhydride to produce a reaction product containing a (meth)acrylic ester and (meth)acrylic acid, wherein a molar ratio of the isosorbide to the (meth)acrylic anhydride is from about 1:1.5 to about 1:2.5;
ii) reacting said reaction product from step i) with at least one organic compound containing at least one epoxy group to form a reaction product; and
iii) optionally blending the reaction product from step ii) with up to about 75 wt % of a reactive diluent, based on a total weight of the reaction product from step ii), to produce the curable resin.

2. The method of claim 1 , wherein the organic compound containing at least one epoxy group comprises a glycidyl ether.

3. The method of claim 1 , wherein the organic compound containing at least one epoxy group comprises at least one compound selected from the group consisting of epoxidized oils, epoxidized cardanol, and epoxidized ricinoleic acid compounds.

4. The method of claim 1 , wherein the step ii) is carried out at a temperature of 25° C. to about 100° C.

5. The method of claim 1 , wherein the reactive diluent is blended with the reaction product of step ii) and the reactive diluent is selected from the group consisting of: styrene, 2-hydroxymethacrylate, methyl methacrylate, methyl acrylate, furfuryl methacrylate, methacrylated lauric acid, and methacrylated fatty acids.

6. A method of making a cured resin, comprising carrying out the method of claim 1 , and further comprising a step of curing the curable resin by free-radical curing to provide the cured resin.

7. The method of claim 6 , further comprising a step of curing the curable resin by one of sequential epoxy polymerization, epoxy homopolymerization, epoxy-amine polymerization, and epoxy-anhydride polymerization to provide an interpenetrating polymer network.

8. The method of claim 1 , wherein prior to step i) the and the methacrylic anhydride are melted and step i) is carried out in the presence of a basic catalyst.

9. The method of claim 1 , wherein the reaction of step i) is carried out until said (meth)acrylic anhydride is consumed.

10. The method of claim 2 , A method for producing a curable resin in a one-pot, two step reaction, said method comprising:
i) reacting an organic compound having at least one hydroxy group with a (meth)acrylic anhydride to produce a reaction product containing a (meth)acrylic ester and (meth)acrylic acid;
ii) reacting said reaction product from step i) with at least one organic compound containing at least one epoxy group is a glycidyl ether is-selected from the group consisting of diglycidyl ether of bisphenol A, oligomers of diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of bisguiaicol F, glycidyl acrylate, glycidyl methacrylate, phenyl glycidyl ether, acrylated glycidyl ethers of bisphenol, methacrylated glycidyl ethers of bisphenol, hydrogenated and brominated versions of the above, and mixtures of any of these chemicals, to form a reaction product; and
iii) optionally blending the reaction product from step ii) with up to about 75 wt % of a reactive diluent, based on a total weight of the reaction product from step ii), to produce the curable resin.

11. The method of claim 10 , wherein the glycidyl ether comprises diglycidyl ether of bisphenol A or oligomers of diglycidyl ether of bisphenol A.

12. The method of claim 10 , wherein the glycidyl ether comprises a mixture of diglycidyl ether of bisphenol A and phenyl glycidyl ether in a molar ratio of 0.1 to 99.

13. The method of claim 10 , wherein the step ii) has a molar ratio of (meth)acrylic acid to said glycidyl ether of from about 0.1 to about 1.2.

14. The method of claim 10 , wherein the step ii) has a molar ratio of (meth)acrylic acid to said glycidyl ether of from about 0.9 to about 1.1.

15. The method of claim 10 , wherein the step ii) is carried out at a temperature of 25° C. to about 100° C.

16. The method of claim 10 , wherein the reactive diluent is blended with the reaction product of step ii) and the reactive diluent is selected from the group consisting of: styrene, 2-hydroxymethacrylate, methyl methacrylate, methyl acrylate, furfuryl methacrylate, methacrylated lauric acid, and methacrylated fatty acids.

17. The method of claim 10 , wherein the organic compound having at least one hydroxy group is selected from a sugar and an alcohol.

18. A method of making a cured resin, comprising carrying out the method of claim 10 , and further comprising a step of curing the curable resin by free-radical curing to provide the cured resin.

19. The method of claim 18 , further comprising a step of curing the curable resin by one of sequential epoxy polymerization, epoxy homopolymerization, epoxy-amine polymerization, and epoxy-anhydride polymerization to provide an interpenetrating polymer network.

20. The method of claim 1 , A method for producing a curable resin in a one-pot, two step reaction, said method comprising:
i) reacting an organic compound having at least one hydroxy group with a (meth)acrylic anhydride to produce a reaction product containing a (meth)acrylic ester and (meth)acrylic acid, wherein in the step i) a molar ratio of the at least one hydroxy group of the organic compound to the (meth)acrylic anhydride is from about 0.75 to about 1.25 and step i) is carried out in the presence of a basic catalyst;
ii) reacting said reaction product from step i) with at least one organic compound containing at least one epoxy group to form a reaction product; and
iii) optionally blending the reaction product from step ii) with up to about 75 wt % of a reactive diluent, based on a total weight of the reaction product from step ii), to produce the curable resin.

21. The method of claim 20 , wherein the step ii) is carried out at a temperature of 25° C. to about 100° C.

22. The method of claim 20 , wherein the reactive diluent is blended with the reaction product of step ii) and the reactive diluent is selected from the group consisting of: styrene, 2-hydroxymethacrylate, methyl methacrylate, methyl acrylate, furfuryl methacrylate, methacrylated lauric acid, and methacrylated fatty acids.

23. The method of claim 20 , wherein the organic compound containing at least one epoxy group comprises a glycidyl ether selected from the group consisting of diglycidyl ether of bisphenol A, oligomers of diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of bisguiaicol F, glycidyl acrylate, glycidyl methacrylate, phenyl glycidyl ether, acrylated glycidyl ethers of bisphenol, methacrylated glycidyl ethers of bisphenol, hydrogenated and brominated versions of the above, and mixtures of any of these chemicals.

24. The method of claim 20 , wherein the organic compound having at least one hydroxy group is selected from a sugar and an alcohol.

25. The method of claim 20 , wherein the organic compound containing at least one epoxy group comprises at least one compound selected from the group consisting of epoxidized oils, epoxidized cardanol, and epoxidized ricinoleic acid compounds.

26. A method of making a cured resin, comprising carrying out the method of claim 20 , and further comprising a step of curing the curable resin by free-radical curing to provide the cured resin.

Assignees

• Univ Drexel
• The Government Of The Us Secretary Of The Army
• Us Army

Inventors

• Sadler Joshua Matthew
• La Scala John Joseph
• Palmese Giuseppe R

Classifications

• C07D493/04 Primary

  Ortho-condensed systems · CPC title

• C08G59/42

  Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof · CPC title

• C08L63/00

  Compositions of epoxy resins; Compositions of derivatives of epoxy resins · CPC title

• C08L33/10

  Homopolymers or copolymers of methacrylic acid esters · CPC title

• C08G59/4238

  heterocyclic · CPC title