Linear Semicrystalline Polyesters from Fatty Acids by Complete Feedstock Molecule Utilization

Abstract

Complete and linear incorporation of fatty acids into polyesters is achieved by isomerizing carbonylation to give polymerization‐quality diesters and their polycondensation with the corresponding diols obtained by reduction. The strictly linear and long‐chain hydrocarbon nature of these polyesters results in a high degree of crystallinity and melting behavior akin to common thermoplastics.

Polymer precursors from catalytic reactions of natural oils

“…177 In order to make the C 12 diester, we attempted the methoxycarbonylation of methyl 2-undecenoic acid, which requires the double bond to move eight bonds into the least thermodynamically favoured position before being trapped there by methoxycarbonylation. Previously the maximum distance for isomerisation that we had observed in this Chemistry was 8 bonds (for methyl oleate [64][65][66][67]140,141 or methyl erucate 66,67,141 ) or 7 bonds where the double bond was conjugated to an ester (second carbonylation of 1-octyne to give dimethyl 1,10-decanedioate). 99 Gratifyingly the reaction worked well and produced dimethyl 1,12-dodecanedioate with high selectivity.…”

“…The oils were obtained from a local supermarket and were chosen for their different proportions of oleic, linoleic and linolenic acid esters (Table 2.1). Using a method very similar to that described previously 67,141 for the methoxycarbonylation of methyl oleate, a one-pot synthesis of Dino from natural oils has been successfully achieved, affording the desired product as an analytically pure snowy white powder, with NMR spectra as reported earlier. 67,141 This one-pot process represents a significant enhancement in production of Dino since it starts from standard quality natural oils with no extra purification and avoids the multiple reaction and purification steps usually required for high purity methyl oleate as a feedstock.…”

“…64,65 The monomers yield long-chain polyesters with properties very similar to polyethylene and might represent a potential replacement for it. [66][67][68] Finally, polyesters from natural oils can be obtained from biologically-based reactions. 69,70 However, these processes are out of the scope of the present introduction.…”

“…The phenomenon of isomerisation of the C=C bond has been recently used for the alkoxycarbonylation of unsaturated fatty esters where the C=C bond is deep buried in the carbon chain. 64,65,67,141 In these studies, the authors showed that the one-pot methanolysis/isomerisation/methoxycabonylation of triglycerides originating from natural oils was possible, yielding to long chain diesters with high selectivity to the linear species. One exception to the linear selectivity has been reported, however this is valid only in a specific case, while the C=C bond is trapped between two unreactive functions towards the methoxycarbonylation, 142 and for the methoxycarbonylation of styrene and vinyl acetate (see 1.4.3.3).…”

“…Mecking and co-workers have shown that these precursors can be copolymerised to aliphatic polyesters with properties very similar to those of polyethylene. 66,67,141 It was subsequently shown that unpurified olive, rapeseed and sunflower oils, could provide much cheaper alternatives to purified methyl oleate for achieving the synthesis of the Dino. 65 Walther and co-workers employed a variety of sunflower oil with a high oleic acid content.…”