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

Abstract

A tandem Diels–Alder addition and lactonisation between bio-derivable itaconic anhydride and furfuryl alcohol can be used to prepare novel monomers for ROMP.

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

“…26 Anhydrous CH 2 Cl 2 was obtained from a solvent purification system by passage through a dry alumina column. All other reagents were purchased from Sigma Aldrich and used without purification.…”

“…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). This observation was also reported independently and simultaneously by Hoye et al who were investigating the Diels-Alder addition of itaconic anhydride 6 to a range of furans.…”

“…As a fully bio-derived molecule made in a virtually waste-free process (except for a small amount of solvent used for washing or recrystallisation), acid 7 is a very promising candidate for green and sustainable polymer chemistry. We previously reported 26 that the methyl ester 8a of acid 7 could be polymerised to homopolymer 9a by Ring Opening Metathesis Polymerisation (ROMP) 31 on treatment with second generation Grubbs catalyst 10. 32 This was the first report of ROMP of a substrate with the hindered substitution pattern around the oxa-norbornene bridgehead present in monomer 8a.…”

Rapid Ring‐Opening Metathesis Polymerization of Monomers Obtained from Biomass‐Derived Furfuryl Amines and Maleic Anhydride

“…All of the polymers also have the ability to undergo post-polymerization modification by treatment with thiols and end-group modification. Amines 10 a-c then underwent tandem Diels-Alder and lactamization reactions to give acids 12 a-c when treated with maleic anhydride 7.I nc ontrast to our previously reporteds ynthesis of acid 8, [11] it wasn ecessary to use as olvent (toluene) for this reaction owing to the viscous nature of amines 10 a-c.I ne ach case, the Diels-Alder product (12 a-c) precipitated from the reaction mixture and could be further purified by recrystallization from acetone. [17] Results and Discussion Three secondary furfuryla mines (10 a-c)w ere prepared by the reductivea mination of aldehydes 11 a-c with furfurylamine 3 (Scheme2).…”

“…[11,13,19] Once this was established, it was evident that the cause of the increased polydispersity was that the rate of propagation K p was rapid relative to the rate of initiation K i for these monomers when using Grubbs second-generation catalyst. Thisw as initially thought to be ac onsequence of unwanted back-biting or intermolecular metathesis side reactions, and therefore the influence of reaction time on the degree of polymerization wasi nvestigated.…”