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

Patent metadata

Field	Value
Publication number	US-9644059-B2
Application number	US-201615130165-A
Country	US
Kind code	B2
Filing date	Apr 15, 2016
Priority date	Aug 10, 2011
Publication date	May 9, 2017
Grant date	May 9, 2017

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.

First claim

What is claimed is:

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 method for producing a polymerizable monomer comprising the step of acylating one or more hydroxyl groups of an anhydrosugar using acrylic anhydride or methacrylic anhydride and a base catalyst in an aprotic solvent, wherein the anhydrosugar is selected from the group consisting of: isosorbide, isomannide, and isoidide.

5. The method of claim 4 , wherein the one or more hydroxyl groups of the anhydrosugar are acylated using methacrylic anhydride and the base catalyst in the aprotic solvent.

6. 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.

7. The copolymer of claim 6 , wherein the curable composition comprises at least one vinyl ester resin monomer and/or at least one unsaturated polyester monomer.

8. The copolymer of claim 7 , wherein the curable composition further comprises at least one reactive diluent.

9. The copolymer of claim 7 , 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.

10. The copolymer of claim 7 , 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.

11. The copolymer of claim 8 , 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.

12. The copolymer of claim 7 , 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.

13. The copolymer of claim 7 , 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.

14. The copolymer of claim 13 , wherein the curable composition further comprises a reactive diluent selected from the group consisting of: styrene, 2-hydroxymethacrylate, methyl methacrylate, methyl acrylate, furfuryl methacrylate, methacyrlated lauric acid and methacrylated fatty acids.

15. The copolymer of claim 14 , wherein the monomer of claim 1 is selected from a monomer of the formula 2 and a monomer of the formula 2a.

16. The copolymer of claim 7 , wherein the curable composition comprises an unsaturated polyester monomer made from one or more of the following components: phthalic acid, terephtalic acid, m-phthalic acid, suberic acid, adipic acid, succinic acid, maleic acid, fumaric acid, butylene glycol, propylene glycol, and ethylene glycol.

17. The copolymer of claim 16 , wherein the curable composition further comprises a reactive diluent selected from the group consisting of: styrene, 2-hydroxymethacrylate, methyl methacrylate, methyl acrylate, furfuryl methacrylate, methacyrlated lauric acid and methacrylated fatty acids.

18. The copolymer of claim 17 , wherein the monomer of claim 1 is selected from a monomer of the formula 2 and a monomer of the formula 2a.

Assignees

• Univ Drexel
• Us Army

Inventors

• Palmese Giuseppe R
• La Scala John Joseph
• Sadler Joshua Matthew
• Lam Anh-Phuong Thy

Classifications

• C08F220/282

  and containing two or more oxygen atoms · CPC title

• C08F122/20

  Esters containing oxygen in addition to the carboxy oxygen · CPC title

• C07D493/04

  Ortho-condensed systems · CPC title

• C08F124/00

  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 title

• C08F224/00

  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) · CPC title