Isosorbide-based polymethacrylates

• US 9,988,393 B2
• Filed: 02/09/2016
• Issued: 06/05/2018
• Est. Priority Date: 02/09/2015
• Status: Active Grant

• Current Assignee: Regents of The University of Minnesota (University of Minnesota)
• Original Assignee: Regents of The University of Minnesota (University of Minnesota)
• Inventors: Hillmyer, Marc A., Reineke, Theresa, Gallagher, James
• Primary Examiner(s): Choi, Ling
• Assistant Examiner(s): Wang, Chun-Cheng
• Application Number:
  US15/019,777
• Publication Number:
  US 20160229863A1
• Time in Patent Office: 847 Days
• Field of Search: 526270
• 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 220/1804 C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
• CPC Class Codes: C08F 220/283 and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
• CPC Class Codes: C08F 2438/03 Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
• CPC Class Codes: C08F 293/00 Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule on to polymers modified by introduction of unsaturated end groups C08F290/02

Abstract

A monomer comprises the structure

wherein R¹ comprises H or a substituted hydrocarbyl or unsubstituted hydrocarbyl, and wherein R² comprises H, a halide, or a substituted or unsubstituted (C₁-C₄) hydrocarbyl. A method comprises (a) reacting a dianhydrohexitol precursor having the structure

with an acyl-group containing compound having the structure

wherein R¹ comprises H or a substituted hydrocarbyl or unsubstituted hydrocarbyl, and X comprises a halide, a hydroxyl group, or an acyl group to form an acylated dianhydrohexitol ester intermediate having the structure

and (b) reacting the acylated dianhydrohexitol ester intermediate with an acrylic-based compound having the structure

wherein R² comprises H, a halide, or a substituted or unsubstituted (C₁-C₄) hydrocarbyl, and Y comprises a halide, a hydroxyl group, or an acyl group, to form a dianhydrohexitol-based monomer having the structure

Claims

1. A monomer comprising the structure

2. The monomer of claim 1, wherein R¹ comprises H or a methyl group (CH₃).

3. The monomer of claim 1, wherein R² comprises H or a methyl group (CH₃).

4. The monomer of claim 1, wherein the monomer is an acetylated methacrylic isosorbide having the structure

5. A polymer or a copolymer comprising, as a repeating unit, the structure

6. The polymer or copolymer of claim 5, wherein R¹ comprises H or a methyl group (CH₃).

7. The polymer or copolymer of claim 5, wherein R² comprises H or a methyl group (CH₃).

8. A method comprising:

(a) reacting a dianhydrohexitol precursor having the structure

9. The method of claim 8, wherein R¹ comprises H or a methyl group (CH₃).

10. The method of claim 8, wherein R² comprises H or a methyl group (CH₃).

11. The method of claim 8, wherein the dianhydrohexitol-based monomer comprises an acetylated methacrylic isosorbide having the structure

12. A method comprising:

(a) reacting a dianhydrohexitol precursor having the structure

13. The method of claim 12, wherein R¹ comprises H or a methyl group (CH₃).

14. The method of claim 12, wherein R² comprises H or a methyl group (CH₃).

15. The method of claim 12, wherein the dianhydrohexitol-based monomer comprises an acetylated methacrylic isosorbide having the structure

16. The method as in either one of claims 8 or 12, further comprising (c) polymerizing the dianhydrohexitol-based monomer to form a polymer or copolymer comprising, as a repeating unit, the structure

17. The method of claim 16, wherein polymerizing the dianhydrohexitol-based monomer comprises one of:

linear chain growth polymerization of the dianhydrohexitol-based monomer;

free-radical polymerization of the dianhydrohexitol-based monomer;

or

controlled block polymerization.

18. The method of claim 16, wherein polymerizing the dianhydrohexitol-based monomer comprises reversible addition-fragmentation chain transfer with a chain-transfer agent to form a chain-transfer polymer.