Bio‐Based Aliphatic Polyurethanes Through ADMET Polymerization in Bulk and Green Solvent

Abstract

A new route to α,ω-diene urethane monomer is proposed by converting 10-undecenoic acid into the corresponding acyl azide, followed by urethanization with 10-undecenol. ADMET polymerizations of this α,ω-diene urethane monomer as well as other bio-based α,ω-dienes bearing various organic functions (ester, carbonate, ether, amide) were carried out in bulk and solution conditions. A screening of the most commonly used metathesis catalysts allows to evaluate their tolerance toward the urethane function as well as toward Polarclean, a "green" and nontoxic high boiling point solvent. The influence of the nature of the central organic function in these α,ω-diene monomers on the thermomechanical properties is investigated.

Novel thermoplastic polyhydroxyurethane elastomers as effective damping materials over broad temperature ranges

“…Renewable resources such as carbonated soybean oil, linseed oil [33][34][35][36], limonene [37], cellulose [38], isosorbide [39], cashew nut shell liquid [40], and glycerol [41] have been used to make crosslinked PHUs [33][34][35][36][37][38][39][40][41][42][43][44]. Other investigators have studied various routes to generate cyclic carbonate monomers for synthesizing single-phase and crosslinked PHUs [44][45][46][47][48][49] as well as the increased reactivity of eight-membered ring carbonates allowing room temperature synthesis without the aid of catalysts [12].…”

Integrating plant oils into thermally curable main-chain benzoxazine polymers via ADMET polymerization

“…Inspired by the molecular structure of biobased ,-diene monomers reported by Meier and others [34,35], a benzoxazine-containing diene monomer (BzD, Scheme 2) was designed based on 10-undecenoic acid, a castor oil derived platform chemical. [36] Thus, 10-undecenoyl chloride was first reacted with an excess of hydroquinone to give mainly 4-hydroxyphenyl-10-undecenoate, which was isolated by crystallization from heptanes.…”

“…The ADMET polymerization of the BzD monomer was initially investigated using the HG-2 catalyst because has demonstrated notorious tolerance and activity toward coordinative and non-coordinative heteroatom-containing dienes (Table 1) [35,[39][40][41]. ADMET reactions were run for 15h at 50ºC in absence of solvent and under vacuum to remove the released ethylene.…”

Dimerization of abietic acid for the design of renewable polymers by ADMET

“…In order to decrease the steric hindrance around the reactive functions and to get around the problem of the hydroxyl group from the lactone opening, abietic acid dimer (fraction 3) was esterified with undecenol to react via ADMET polymerization, which revealed to be an efficient polymerization method [38,39]. The so-formed bis unsaturated dimers were then copolymerized with undecenyl undecenoate by ADMET polymerization (Scheme 2).…”