Renewable bio-based (meth)acrylated monomers as vinyl ester cross-linkers

• US 10,053,529 B2
• Filed: 11/28/2017
• Issued: 08/21/2018
• Est. Priority Date: 08/10/2011
• Status: Active Grant

• Current Assignee: Drexel University, United States Of America As Represented By The Secretary Of The Army (Government of the United States of America)
• Original Assignee: Drexel University, United States Of America As Represented By The Secretary Of The Army (Government of the United States of America)
• Inventors: Palmese, Giuseppe R., La Scala, John Joseph, Sadler, Joshua Matthew, Lam, Anh-Phuong Thy
• Primary Examiner(s): Choi, Ling Siu
• Assistant Examiner(s): Grinsted, Ronald
• Application Number:
  US15/824,629
• Publication Number:
  US 20180142052A1
• Time in Patent Office: 266 Days
• Field of Search: 525186
• CPC Class Codes: C07D 493/04 Ortho-condensed systems
• CPC Class Codes: C08F 120/28 containing no aromatic rings in the alcohol moiety
• CPC Class Codes: C08F 122/20 Esters containing oxygen in addition to the carboxy oxygen
• CPC Class Codes: C08F 124/00 Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen cyclic esters of polyfunctional acids C08F118/00; cyclic anhydrides of unsaturated acids C08F120/00, C08F122/00
• CPC Class Codes: C08F 212/08 Styrene
• CPC Class Codes: C08F 220/1809 C9-(meth)acrylate
• CPC Class Codes: C08F 220/1812 C12-(meth)acrylate, e.g. lauryl (meth)acrylate
• CPC Class Codes: C08F 220/281 and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
• CPC Class Codes: C08F 220/282 and containing two or more oxygen atoms
• CPC Class Codes: C08F 220/32 containing epoxy radicals
• CPC Class Codes: C08F 220/325 containing glycidyl radical, e.g. glycidyl (meth)acrylate
• CPC Class Codes: C08F 222/102 of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
• CPC Class Codes: C08F 224/00 Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen cyclic esters of polyfunctional acids C08F218/00; cyclic anhydrides of unsaturated acids C08F220/00, C08F222/00

Abstract

Anhydrosugar-based monomers prepared from isosorbide, isomannide, and isoidide and resin systems containing these anhydrosugar-based monomers that are partially to fully bio-based, which may produce materials having properties that meet or exceed the properties of similar petroleum derived vinyl ester resins.

Claims

1. A method of making a polymer comprising the step of curing a composition comprising at least one polymerizable monomer selected from the group consisting of:

2. The method of claim 1, wherein the curing is carried out by free-radical curing.

3. The method of claim 1, wherein the composition further comprises from 1 to 99% by weight of at least one reactive diluent selected from the group consisting of:

styrene, 2-hydroxymethacrylate, methyl methacrylate, methyl acrylate, furfuryl methacrylate, methacrylated lauric acid, and methacrylated fatty acids.

4. The method of claim 1, wherein the composition further comprises from 1 to 99% by weight of at least one cross-linking agent.

5. The method of claim 4, wherein the crosslinker is selected from the group consisting of:

unsaturated polyester, vinyl ester and the structures in claim 1.

6. A polymer obtained by the process of claim 1.

17. The method of making a polymer as claimed in claim 1, wherein the at least one polymerizable monomer is selected from the group consisting of:

18. The method of making a polymer as claimed in claim 1, wherein the at least one polymerizable monomer is selected from the group consisting of:

20. The method of making a polymer as claimed in claim 1, wherein the at least one anhydrosugar-based polymerizable monomer is selected from the group consisting of:

7. A method of making a polymer comprising the step of curing a composition comprising at least one vinyl ester resin monomer or unsaturated polyester monomer and at least one anhydrosugar-based polymerizable monomer selected from the group consisting of:

8. The method of claim 7, wherein the composition comprises 1-99% by weight of anhydrosugar-based monomers, 1-70% by weight of vinyl ester resin monomer and/or unsaturated polyester monomer and 0-60% by weight of at least one reactive diluent.

9. The method of claim 7 wherein the composition comprises 5-95% by weight by weight of anhydrosugar-based monomers, 5-65% by weight of vinyl ester resin monomer and/or unsaturated polyester monomer and 0-50% by weight of at least one reactive diluent.

10. The method of claim 7, wherein the composition comprises 15-90% by weight of anhydrosugar-based monomers, 10-55% by weight of vinyl ester resin monomer and/or unsaturated polyester monomer and 0-45% by weight of at least one reactive diluent.

11. The method of claim 8, wherein 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.

12. The method of claim 11, wherein the vinyl ester monomer is selected from the group consisting of (meth)acrylated glycidyl ethers of bisphenols, (meth)acrylated ethoxylated bisphenols and novolac vinyl esters.

13. The method of claim 12, wherein the bisphenols are selected from the group consisting of:

bisphenol A, hexafluorobisphenol A, bisphenol E, bisphenol F, tetramethyl bisphenol E, tetramethyl bisphenol F, bisphenol M, bisphenol C, bisphenol P and bisphenol Z.

14. The method of claim 13, wherein the unsaturated polyester monomer is made from one or more of the following components:

phthalic acid, terephthalic acid, m-phthalic acid, suberic acid, adipic acid, succinic acid, maleic acid, fumaric acid, butylene glycol, propylene glycol, and ethylene glycol.

15. The method of claim 12, wherein said composition comprises 50-95% by weight of said at least one monomer and 5-50% by weight of said reactive diluent.

16. A polymer obtained by the method of claim 8.

19. The method of making a polymer as claimed in claim 8, wherein the at least one anhydrosugar-based polymerizable monomer is selected from the group consisting of: