Work-hardening Photopolymer from Renewable Photoactive 3,3’-(2,5-Furandiyl)bisacrylic Acid

TY - JOUR

T1 - Work-hardening Photopolymer from Renewable Photoactive 3,3’-(2,5-Furandiyl)bisacrylic Acid

AU - Lie, Yann

AU - Pellis, Alessandro

AU - Funes-Ardoiz, Ignacio

AU - Sampedro, Diego

AU - Macquarrie, Duncan J.

AU - Farmer, Thomas J.

N1 - © 2020 The Authors.

PY - 2020/8/24

Y1 - 2020/8/24

N2 - The design of a photopolymer around a renewable furan-derived chromophore is presented herein. An optimised semi-continuous oxidation method using MnO2 affords 2,5-diformylfuran from 5-(hydroxymethyl)furfural in gram quantities, allowing the subsequent synthesis of 3,3’-(2,5-furandiyl)bisacrylic acid in good yield and excellent stereoselectivity. The photoactivity of the diester of this monomer is confirmed by reaction under UV irradiation, and the proposed [2+2] cycloaddition mechanism supported further by TD-DFT calculations. Oligoesters of the photoreactive furan diacid with various aliphatic diols are prepared via chemo- and enzyme-catalysed polycondensation. The latter enzyme-catalysed (Candida antarctica lipase B) method results in the highest Mn (3.6 kDa), suggesting milder conditions employed with this protocol minimised unwanted side reactions, including untimely [2+2] cycloadditions, whilst preserving the monomer's photoactivity and stereoisomerism. The photoreactive polyester is solvent cast into a film where subsequent initiator-free UV curing leads to an impressive increase in the material stiffness, with work-hardening characteristics observed during tensile strength testing.

AB - The design of a photopolymer around a renewable furan-derived chromophore is presented herein. An optimised semi-continuous oxidation method using MnO2 affords 2,5-diformylfuran from 5-(hydroxymethyl)furfural in gram quantities, allowing the subsequent synthesis of 3,3’-(2,5-furandiyl)bisacrylic acid in good yield and excellent stereoselectivity. The photoactivity of the diester of this monomer is confirmed by reaction under UV irradiation, and the proposed [2+2] cycloaddition mechanism supported further by TD-DFT calculations. Oligoesters of the photoreactive furan diacid with various aliphatic diols are prepared via chemo- and enzyme-catalysed polycondensation. The latter enzyme-catalysed (Candida antarctica lipase B) method results in the highest Mn (3.6 kDa), suggesting milder conditions employed with this protocol minimised unwanted side reactions, including untimely [2+2] cycloadditions, whilst preserving the monomer's photoactivity and stereoisomerism. The photoreactive polyester is solvent cast into a film where subsequent initiator-free UV curing leads to an impressive increase in the material stiffness, with work-hardening characteristics observed during tensile strength testing.

KW - density functional theory

KW - enzyme catalysis

KW - furandiyl diacrylic esters

KW - photochemistry

KW - renewable polyester

UR - http://www.scopus.com/inward/record.url?scp=85088803438&partnerID=8YFLogxK

U2 - 10.1002/cssc.202000842

DO - 10.1002/cssc.202000842

M3 - Article

AN - SCOPUS:85088803438

SN - 1864-5631

VL - 13

SP - 4140

EP - 4150

JO - ChemSusChem

JF - ChemSusChem

ER -