Unperturbed dimensions of atactic poly(dibenzyl itaconate)s

Ring opening metathesis polymerisation of a new bio-derived monomer from itaconic anhydride and furfuryl alcohol

“…As benzylic and other aromatic itaconate esters are known to produce polymers with higher T g than their alkyl equivalents, 17 we attempted to synthesise a bio-derived analogue of these by preparing itaconate esters with furfuryl alcohol 1. However, when 1 was reacted with itaconic anhydride 2 (Scheme 1), at room temperature in acetonitrile solution for 24 hours, a crystalline solid formed that proved to be a novel oxa-norbornene structure 5 (61%), generated via a 100% atom economical tandem ring-opening and Diels-Alder addition, rather than the expected mono-esters 3a or 3b.…”

Ring-Opening Metathesis Polymerization of Tertiary Amide Monomers Derived from a Biobased Oxanorbornene

“…There are generally two distinct approaches for the preparation of biobased plastics: either the development of sustainable routes to monomers chemically equivalent to those derived from petrochemical sources (bioreplacement), or the synthesis of novel structures from biomass as new sustainable monomer species (bioadvantage) . We had previously been interested in the development of aromatic itaconate esters, with the intention of producing biobased furan analogues of poly­(benzyl)­itaconates, through radical polymerization. − It was expected that these would possess higher glass transition temperatures ( T g ) than their poly­(dialkyl)­itaconate equivalents . However, the reaction between itaconic anhydride 1 and furfuryl alcohol 2 gave not ester 3 , but the unusual oxanorbornene-lactone 4 as a single product (Scheme ).…”

“…5−8 It was expected that these would possess higher glass transition temperatures (T g ) than their poly(dialkyl)itaconate equivalents. 9 However, the reaction between itaconic anhydride 1 and furfuryl alcohol 2 gave not ester 3, but the unusual oxanorbornene-lactone 4 as a single product (Scheme 1). 10 This outcome was reported independently and simultaneously by Pehere et al 11 The formation of acid 4 occurs via a tandem Diels−Alder cycloaddition followed by lactone formation.…”

Wholly biomass derivable sustainable polymers by ring-opening metathesis polymerisation of monomers obtained from furfuryl alcohol and itaconic anhydride

“…This restricts the uses of these polymers and excludes them from applications in engineering materials or packaging as substitutes for the ubiquitous and versatile polyacrylates and similar materials for which they might at first appear to be useful biobased replacements. Poly(benzyl)itaconates, by contrast, are reported to be glassy solids at room temperature, 21 however, these are less readily produced in a sustainable way due to the difficulty in sourcing simple benzene derivatives from biomass. 22 Therefore, we initiated a project aimed at producing a bio-based analogue of benzyl itaconates by esterification of itaconic acid 1 or the derived cyclic anhydride 6, which may be produced directly by reactive distillation of citric acid, 23 (which is itself a product of fermentation 24 However, as we recently reported, 26 reaction of anhydride 6 with alcohol 5 led not to an itaconate ester, but rather gave oxa-norbornene derivative 7 as the only product (Scheme 1).…”