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

Abstract

Ring-opening metathesis polymerisation (ROMP) of oxanorbornene esters by Grubbs second generation catalyst is used to prepare a range of wholly biomass-derivable homo and copolymers.

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

“…[11,13,16] Differential scanning calorimetry (DSC) in the range À60 to 250 8Cu sing "pinhole" sample pans indicated that the homoand copolymers of 13 a, 13 b and 13 c all had glass transitions (T g )i nt he range 160-168 8C. These values are comparable to those we have previously reported for polymers obtained from esters and amides of acid 8.…”

“…For both monomers, the rate of polymerization could be determined ( Figure 4) and the observed first-order rate constants K pobs for the polymerizations of 13 a and 13 b, respectively,w ere 4 10 À3 s À1 and 5 10 À3 s À1 ,w hich are approximately 200 times greater than the previously determined K p fort he methyl ester of acid 8 (2.2 10 À5 s À1 ). [13] This large increase in the rate of propagation is entirely consistentw ith the absence of substituents in the endo-positionso fm onomers 13.…”

“…Fully assigned 1 Ha nd 13 Cs pectra of oxanorbornenes 12 and 13 are given in the Supporting Information. Ethanol and methanol were kept over activated molecular sieves for am inimum of 24 hb efore use.…”

“…[11] The same result was obtained independently and simultaneously by the group of Hoye. [13] However,t he polymerization of these monomers was very slow,w ith at ypical reaction taking 72 ht or each completion.T his limited the variety of polymer architectures that could be produced as "dead"c hain ends become as ignificant problem over extended polymeri-Well-controlled and extremelyr apid ring-opening metathesis polymerization of unusualo xanorbornene lactam esters by Grubbs third-generation catalysti su sed to preparearange of bio-based homo-a nd copolymers. [13] However,t he polymerization of these monomers was very slow,w ith at ypical reaction taking 72 ht or each completion.T his limited the variety of polymer architectures that could be produced as "dead"c hain ends become as ignificant problem over extended polymeri-Well-controlled and extremelyr apid ring-opening metathesis polymerization of unusualo xanorbornene lactam esters by Grubbs third-generation catalysti su sed to preparearange of bio-based homo-a nd copolymers.…”

“…[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.…”