Synthesis of Biobased Diethyl Terephthalate via Diels-Alder Addition of Ethylene to 2,5-Furandicarboxylic Acid Diethyl Ester: An Alternative Route to 100% Biobased Poly(ethylene terephthalate)

TY - JOUR

T1 - Synthesis of Biobased Diethyl Terephthalate via Diels-Alder Addition of Ethylene to 2,5-Furandicarboxylic Acid Diethyl Ester: An Alternative Route to 100% Biobased Poly(ethylene terephthalate)

AU - Ogunjobi, Joseph K.

AU - Farmer, Thomas J.

AU - McElroy, C. Robert

AU - Breeden, Simon W.

AU - MacQuarrie, Duncan J.

AU - Thornthwaite, David

AU - Clark, James H.

N1 - © 2019 American Chemical Society. 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 - 2019/5/6

Y1 - 2019/5/6

N2 - Poly(ethylene terephthalate) (PET) is a ubiquitous thermoplastic currently produced from nonrenewable fossil resources; as such, sustainable biobased routes to the key terephthalate monomer are being widely pursued. Herein is demonstrated a greener solventless route to biobased diethyl terephthalate via a one-pot heterogeneous Lewis acid catalyzed Diels-Alder addition and dehydration of 2,5-furandicarboxylic acid diethyl ester with ethylene, giving yields of terephthalate up to 59% for the key Diels-Alder addition step. A metrics-based comparison against alternative published biobased routes (available from sugars, cellulose and hemicellulose) shows that the clean synthetic pathway developed herein gives a practical atom economy, overall yield and selectivity, making it a viable alternative to routes currently under development.

AB - Poly(ethylene terephthalate) (PET) is a ubiquitous thermoplastic currently produced from nonrenewable fossil resources; as such, sustainable biobased routes to the key terephthalate monomer are being widely pursued. Herein is demonstrated a greener solventless route to biobased diethyl terephthalate via a one-pot heterogeneous Lewis acid catalyzed Diels-Alder addition and dehydration of 2,5-furandicarboxylic acid diethyl ester with ethylene, giving yields of terephthalate up to 59% for the key Diels-Alder addition step. A metrics-based comparison against alternative published biobased routes (available from sugars, cellulose and hemicellulose) shows that the clean synthetic pathway developed herein gives a practical atom economy, overall yield and selectivity, making it a viable alternative to routes currently under development.

KW - Biobased PET

KW - Biobased terephthalate

KW - Dielsa-Alder addition

KW - Furan diester

KW - Green metrics

KW - Heterogeneous catalysis

KW - Solventless

UR - http://www.scopus.com/inward/record.url?scp=85065079327&partnerID=8YFLogxK

U2 - 10.1021/acssuschemeng.8b06196

DO - 10.1021/acssuschemeng.8b06196

M3 - Article

AN - SCOPUS:85065079327

SN - 2168-0485

VL - 7

SP - 8183

EP - 8194

JO - ACS Sustainable Chemistry and Engineering

JF - ACS Sustainable Chemistry and Engineering

IS - 9

ER -