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

• US 9,856,343 B2
• Filed: 03/30/2017
• Issued: 01/02/2018
• Est. Priority Date: 08/10/2011
• Status: Active Grant

• Current Assignee: Drexel University
• Original Assignee: Drexel University, The United States Of America As Represented By The Secretary Of The Army
• Inventors: Palmese, Giuseppe R., La Scala, John Joseph, Sadler, Joshua Matthew, Lam, Anh-Phuong Thy
• Primary Examiner(s): Choi, Ling
• Assistant Examiner(s): WANG, CHUN CHENG
• Application Number:
  US15/474,101
• Publication Number:
  US 20170298165A1
• Time in Patent Office: 278 Days
• Field of Search: 526268
• 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 polymerizable monomer selected from the group consisting of:

2. A polymerizable monomer as claimed in claim 1, wherein the monomer is:

3. A polymerizable monomer as claimed in claim 1, wherein the monomer is:

4. A polymerizable monomer as claimed in claim 1, wherein the monomer is:

5. A polymerizable monomer as claimed in claim 1, wherein the monomer is:

6. A polymerizable monomer as claimed in claim 1, wherein the monomer is:

7. A copolymer formed by curing a curable composition comprising at least one monomer selected from the group consisting of the polymerizable monomers of claim 1 using a free-radical initiator.

8. The copolymer of claim 7, wherein the curable composition comprises at least one vinyl ester resin monomer and/or at least one unsaturated polyester monomer.

9. The copolymer of claim 8, wherein the curable composition further comprises at least one reactive diluent.

10. The copolymer of claim 8, wherein the curable composition comprises 1-99% by weight of at least one monomer selected from the group consisting of the polymerizable monomers of claim 1, 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.

11. The copolymer of claim 8, wherein the curable composition comprises 5-95% by weight of at least one monomer selected from the group consisting of the polymerizable monomers of claim 1, 10-55% by weight of vinyl ester resin monomer and/or unsaturated polyester monomer and 0-50% by weight of at least one reactive diluent.

12. The copolymer of claim 9, wherein the composition comprises 15-90% by weight of at least one monomer selected from the group consisting of the polymerizable monomers of claim 1, 10-55% by weight of vinyl ester resin monomer and/or unsaturated polyester monomer and 5-45% by weight of at least one reactive diluent.

13. The copolymer of claim 8, comprising a vinyl ester resin monomer selected from the group consisting of (meth)acrylated glycidyl ethers of bisphenols, (meth)acrylated ethoxylated bisphenols and novolac vinyl esters.

14. The copolymer of claim 8, comprising a vinyl ester monomer 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.

15. The copolymer of claim 14, wherein the curable composition further comprises a reactive diluent selected from the group consisting of:

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

16. The copolymer of claim 15, wherein the monomer of claim 1 is selected from a monomer of the formula 5 and a monomer of the formula 5a.

17. The copolymer of claim 15, wherein the monomer of claim 1 is selected from a monomer of the formula 7 and a monomer of the formula 8.

18. The copolymer of claim 8, wherein the curable composition comprises an unsaturated polyester monomer 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.

19. The copolymer of claim 18, wherein the curable composition further comprises a reactive diluent selected from the group consisting of:

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

20. The copolymer of claim 19, wherein the monomer of claim 1 is selected from a monomer of the formula 5 and a monomer of the formula 5a.

21. The copolymer of claim 19, wherein the monomer of claim 1 is selected from a monomer of the formula 7 and a monomer of the formula 8.