The aza-Michael reaction: towards semi-crystalline polymers from renewable itaconic acid and diamines

Abstract

This paper reports, for the first time, semi-crystalline polymers based on bis-pyrrolidone dicarboxylic acids (BPDA) obtained from the aza-Michael reaction between renewable itaconic acid and various diamines.

High‐Molecular‐Weight Polyampholytes Synthesized via Daylight‐Induced, Initiator‐Free Radical Polymerization of Renewable Itaconic Acid

“…It is a renewable unsaturated dicarboxylic acid, rated by the U.S. Department of Energy as one of the twelve most important biomass‐derived compounds that can be transformed into a wide range of valuable chemicals or materials . IA is a key substrate for production of aliphatic, unsaturated and saturated polyesters, degradable polyamides as well as condensation polymers bearing pyrrolidine ring in the main chain . The acid is also a well‐known low reactive vinyl monomer, and its free radical polymerization typically requires long reaction times and high amounts of an initiator .…”

Cascade aza-Michael Addition-Cyclizations; Toward Renewable and Multifunctional Carboxylic Acids for Melt-Polycondensation

“…This instability makes the use of these monomers via melt-polycondensation reactions challenging as the final products are heavily colored and either have low molecular weights or are cross-linked (Noordzij et al, 2018). Instead, when reacting these monomers with itaconic acid, thermally stable dicarboxylic acid monomers are obtained that can readily be used in melt-polycondensation reactions (Noordzij et al, 2019). In addition, the presence of the pyrrolidone ring adds to the rigidity of the newly obtained monomers, leading to a change in physicochemical properties.…”

“…The reaction between itaconates and aliphatic diamines ( c , e.g., with 1,2-ethylene diamine or 1,12-dodecanediamine) leads to symmetrical bis-(pyrrolidone-methylcarboxylate) (BPDA) monomers. These BPDA monomers can be polymerized with various diols ( f , e.g., with 1,3-propanediol or 1,12-dodecanediol) into amorphous polyesters with a T g ranging from 62 to −22°C (Qi et al, 2016; Noordzij et al, 2019). BPDA monomers obtained from rigid diamines ( c , e.g., with p -phenylenediamine or trans -cyclohexanediamine) can be polymerized into semi-crystalline polyesters with various diols ( f , e.g., with 1,8-octanediol), with a T g between 65 and 33°C, and a melting temperature ( T m ) between 214 and 149°C (Noordzij et al, 2019).…”

“…These BPDA monomers can be polymerized with various diols ( f , e.g., with 1,3-propanediol or 1,12-dodecanediol) into amorphous polyesters with a T g ranging from 62 to −22°C (Qi et al, 2016; Noordzij et al, 2019). BPDA monomers obtained from rigid diamines ( c , e.g., with p -phenylenediamine or trans -cyclohexanediamine) can be polymerized into semi-crystalline polyesters with various diols ( f , e.g., with 1,8-octanediol), with a T g between 65 and 33°C, and a melting temperature ( T m ) between 214 and 149°C (Noordzij et al, 2019). Furthermore, the reaction between itaconates and aliphatic or aromatic diamines ( c , e.g., with 1,6-hexanediamine or p -phenylenediamine) followed by subsequent polymerization with various aliphatic or aromatic diamines ( g , e.g., with 1,6-hexanediamine or p -phenylenediamine), leads to the formation of high T g , amorphous polyamides.…”

Improving the Hydrolysis Rate of the Renewable Poly(hexamethylene sebacate) Through Copolymerization of a Bis(pyrrolidone)-Based Dicarboxylic Acid

“…In particular, the aza-Michael addition between the α,β-unsaturation of itaconic acid with an alkyl-amine can be used to generate renewable pyrrolidone-based dicarboxylic acid (BPDA) monomers. In turn, these BPDA monomers have successfully been used for the synthesis of polyesters [18,19], polyamides [20,21,22,23], and poly(ester-amide)s [24,25,26]. Though the presence of the cyclic pyrrolidone moieties are generally used to enhance the glass transition temperature [18], they also enhance the polymer’s affinity to water, resulting in an increased moisture uptake.…”