Vegetable‐based building‐blocks for the synthesis of thermoplastic renewable polyurethanes and polyesters

Abstract

Fatty acid derivatives, viz, methyl oleate and methyl 10‐undecenoate were systematically explored to obtain a set of monomers with defined functionality. More specifically, AB‐type self‐condensable monomers containing hydroxyl‐acyl azide functionality and diols with pre‐formed ester linkage were synthesized. A series of polyurethanes was prepared using two methods: (i) AB‐type self‐polycondensation reaction of hydroxyl‐acyl azide moiety, and (ii) polymerization of diols with isophorone diisocyanate and methylene diphenyl diisocyanate. The diols were also reacted with a bio‐sourced diester using organocatalyst to obtain a set of polyesters. The obtained polyurethanes and polyesters were thoroughly analyzed with fourier‐transformed infrared, nuclear magnetic resonance, size exclusion chromatography, differential scanning calorimetry and thermogravimetric analysis experiments. The polymers displayed amorphous to semi‐crystalline behaviors with regard to the structure of the monomers. Both, polyurethanes and polyesters displayed a good thermal stability with no significant weight loss below 200°C.

Ultrasound-assisted self-metathesis reactions of monounsaturated fatty acids

“…However, the chemical process is also of potential interest. It does not rely on an oxidative process, but is instead based on redistribution of the olefinic bonds of unsaturated fatty acids via a self-metathesis reaction (Behr et al, 2014;Chikkali and Mecking, 2012;Jenkins et al, 2015;Levin et al, 2015;Meier, 2000;Montero de Espinosa and Meier, 2012;More et al, 2013;Ngo and Foglia, 2009;Nicolaou et al, 2005;Ohlmann et al, 2012;Ozturk et al, 2015;Le Ravalec et al, 2010;Tomasek and Schatz, 2013;Vilela et al, 2012;Vyshnavi et al, 2013;Wels et al, 2013;Winkler and Meier, 2014). For example, Foglia has shown that 1,18-octadec-9-enedioic acid (2) can be obtained with a yield of 71% from oleic acid (1) if it is stirred mechanically at 45…”

Effect of danling chain content on properties of 10-undecenoic acid-based polyurethane

“…There are a lot of researches about polyurethane containing the dangling chain have been reported [2][3][4][5] . Xu et al [6] fabricated segmented PUs with six-carbon dangling chain, they found that the presence of the six-carbon short dangling chain in each repeating unit of the soft segments does not limit the overall bulk properties.…”

Monomers and polymers from plant oils via click chemistry reactions

“…On the other hand, thiol-ene addition of T3 to methyl 10-undecenoate has also been investigated as an initial step in the preparation of fatty acid-derived isocyanates (M13) via Curtius rearrangement. 36 Moreover, it is worth nothing at this point the isocyanatefree approach to polyurethanes based on hydroxy-acyl azide monomer M4, in which hydroxyl group was also introduced via hydrothiolation with T1. 30 Finally, Gandini and coworkers also investigated the functionalization of methyl 10-undecenoate with 2-furfuryl thiol (T7) to prepare Diels-Alder reactive monomers (vide infra).…”

“…36 Moreover, it is worth nothing at this point the isocyanatefree approach to polyurethanes based on hydroxy-acyl azide monomer M4, in which hydroxyl group was also introduced via hydrothiolation with T1. 30 Finally, Gandini and coworkers also investigated the functionalization of methyl 10-undecenoate with 2-furfuryl thiol (T7) to prepare Diels-Alder reactive monomers (vide infra). 44,45 Hydrothiolation has also been applied to the functionalization of oleic acid with several commercial thiols including T5 hydrochloride, T6, and T1 giving a variety of difunctional monomers (M10, M12, and M5).…”

“…However, Auvergne and coworkers demonstrated that using the appropriate irradiation, T1 addition to oleic acid can be performed under mild conditions requiring neither solvent nor photoinitiator in 1 h. 46 The prepared oleic acid-derived polycondensation monomers were used to obtain polyanhydrides, polyamides, as well as isocyanate-free polyurethanes that usually behave as amorphous materials because of the presence of dangling chains. 30,31,34,35 On the other hand, Lapinte and coworkers recently used this strategy to prepare an oleic acid-based initiator for 2-methyl-2-oxazoline cationic ring-opening polymerization. 47 Thus, methyl oleate was coupled with T1 under UV irradiation to introduce hydroxyl groups, which were further transformed in p-toluenesulfonyl, trifluoromethanesulfonyl, or chloroacetyl esters.…”