New bio-based monomers: Tuneable polyester properties using branched diols from biomass

TY - JOUR

T1 - New bio-based monomers:

T2 - Tuneable polyester properties using branched diols from biomass

AU - Farmer, Thomas James

AU - Comerford, James William

AU - Mascal, Mark

AU - Schmid, Maximilian

AU - Perocheau Arnaud, Sacha

AU - Wu, Linglin

AU - Wong Chang, Maria-Angelica

AU - Chang, Fei

AU - Li, Zheng

N1 - © The Royal Society of Chemistry 2017. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details.

PY - 2017/9

Y1 - 2017/9

N2 - A family of monomers including 2,5-hexandiol, 2,7-octandiol, 2,5-furandicarboxylic acid (FDCA) , terephthalic acid (TA), and branched-chain adipic and pimelic acid derivatives all find a common derivation in the biomass-derived platform molecule 5-(chloromethyl)furfural (CMF). The diol monomers, previously little known to polymer chemistry, have been combined with FDCA and TA derivatives to produce a range of novel polyesters. It is shown that the use of secondary diols leads to polymers with higher glass transition temperatures (Tg) than those prepared from their primary diol equivalents. Two methods of polymerisation were investigated, the first employing activation of the aromatic diacids via the corresponding diacid chlorides and the second using a transesterification procedure. Longer chain diols were found to be more reactive than the shorter chain alternatives, generally giving rise to higher molecular weight polymers, an effect shown to be most dramatic when using the transesterification route. Finally, novel diesters with high degrees of branching in their hydrocarbon chains are introduced as potential monomers for low surface energy materials applications.

AB - A family of monomers including 2,5-hexandiol, 2,7-octandiol, 2,5-furandicarboxylic acid (FDCA) , terephthalic acid (TA), and branched-chain adipic and pimelic acid derivatives all find a common derivation in the biomass-derived platform molecule 5-(chloromethyl)furfural (CMF). The diol monomers, previously little known to polymer chemistry, have been combined with FDCA and TA derivatives to produce a range of novel polyesters. It is shown that the use of secondary diols leads to polymers with higher glass transition temperatures (Tg) than those prepared from their primary diol equivalents. Two methods of polymerisation were investigated, the first employing activation of the aromatic diacids via the corresponding diacid chlorides and the second using a transesterification procedure. Longer chain diols were found to be more reactive than the shorter chain alternatives, generally giving rise to higher molecular weight polymers, an effect shown to be most dramatic when using the transesterification route. Finally, novel diesters with high degrees of branching in their hydrocarbon chains are introduced as potential monomers for low surface energy materials applications.

KW - bio-based monomers

KW - bio-based polymer

KW - Platform molecules

KW - tranesterification

KW - polymerisation

U2 - 10.1039/c7fd00057J

DO - 10.1039/c7fd00057J

M3 - Article

SN - 1359-6640

SP - 61

EP - 77

JO - FARADAY DISCUSSIONS

JF - FARADAY DISCUSSIONS

IS - 202

M1 - FD-ART-02-2017-000057.R1

ER -