Chemo-Enzymatic Synthesis and Characterization of Renewable Thermoplastic and Thermoset Isocyanate-Free Poly(hydroxy)urethanes from Ferulic Acid Derivatives

Abstract

This study presents the syntheses and characterization of renewable nonisocyanate polyurethanes (NIPUs) from a new family of aromatic C5-cyclocarbonate precursors with different functionalities obtained from nontoxic ferulic acid derivatives by glycidylation and carbonation under high carbon dioxide pressure. Depending on the functionality, linear NIPU chains (thermoplastics) or cross-linked NIPU networks (thermosets) have been obtained. The thermoplastic NIPUs molar masses were determined using SEC and 1H NMR. The thermal and thermo-mechanical properties of the NIPUs were assessed by DSC, DMA (for thermosets), and TGA to determine the influence of the NIPU chemical structure on its properties. The range of T g obtained (17–72 °C) was efficiently correlated with the degree of freedom and the molar mass of the NIPU repeat unit.

Polymers Based on Cyclic Carbonates as Trait d'Union Between Polymer Chemistry and Sustainable CO2 Utilization

“…[155] 4v was obtained by Averous and co-workers from the reaction of the bisacyl halide of aD FA (Radiacid 0970) with two equivalents of GC. [147] and of sinapyl alcohol-derived 4t reported by Janvier et al [150] (TEBAC: triethylbenzylammoniumc hloride). Similarly, 4w was prepared by the esterification of commercially availableP ripol 1009 (hydrogenated dimerized linoleic acid) with GC, by using nonrenewable coupling reagents such as 1,3-dicyclohexylcarbodiimide (DCC, 2equiv) and employed for the synthesis PHUs in bulk and miniemulsion processes.…”

“…[147] To produce carbonates 4r and 4s,f erulic acid was hydrogenateda tt he conjugated double bond and esterified with ethanol.T wo equivalentso f the resulting compound werec oupled with potentially renewable polyalcohols such as 1,4-butanediol (4r), [148] isosorbide [149] (4s)and with renewable glycerol(see below) by transesterification reactionc atalyzed by Candida antarctica lipase B(CALB). MØnard et al used ap henolic buildingb lock derived from ferulic acid, av ersatile aromatic synthon that can be extracted from non-edible lignocellulosic biomass, for the preparation of isocyanate-free PHU thermosets.…”

“…[185] 6e has been recently used for the synthesis of thermoresponsive PHUs. [147] The high renewable content of this monomer is provided by the use of glyceroland ferulic acid as building blocks and by the coupling reagent-free enzymatic transesterification procedure for the ester bond formation. [187] As the latter aldehydes can be derived from bio-alcohols or from the fermentation of glucose, [188] 6d and 6e can be regarded as potentially renewable carbonates.…”

“…[147] In principle, this method could also be appliedt ot ransesterifications with GD or GC (Scheme 23 d). [83,105,120,133,134,147,157,167,175,184] For more challenging internal epoxides,e ven harsher reaction conditions, [106,181] the use of supercritical CO 2 ,a nd/orl ong reaction times (up to 4-7 d) have been reported. [210] The use of supported Mo, Ti,T a, or Wc atalysts in the presence of potentially renewable H 2 O 2 as oxidant (Scheme23f)i su nder investigation as ag reener method for the epoxidation of olefinicc ompounds such as fatty acids and vegetableo ils that are precursorsi nt he synthesis of bio-based carbonates.…”

Preparation of five‐membered bis(cyclic carbonate)s at atmospheric pressure for polyhydroxyurethane coatings

“…Compared to traditional PUs, these new PUs have hydroxyl groups, so they are called polyhydroxyurethanes (PHUs). [13][14][15][16][17][18][19][20][21] Fleischer et al 15 investigated catalytic carbon dioxide fixation by carbonation of glycerol, trimethylolpropane, and pentaerythritol glycidyl ether, followed by curing with citric acid amino amides in the presence of cellulose carbonate. [10][11][12] Among all the cyclic carbonates, fivemembered bis(cyclic carbonate)s have stable performance and are the most widely studied.…”