High‐Performance BioNylons from Itaconic and Amino Acids with Pepsin Degradability

Abstract

dianhydro-d-mannitol (isomannide), and 1,4,3,6-dianhydro-l-iditol (isoidide). [5][6][7][8] However, low T g values of biobased polyamides restrict their application. [3][4][5][6][7][8] On the other hand, considerable progress has been made in the syntheses of enantiomeric d-and l-poly(hexamethylene di-Omethyltartaramide)s {P6DMT(d-/l-)} a pair of stereoregular polyamides is reported. [9][10][11] The (+)-3-carene based chiral polyamides such as poly-3R-caranamide and poly-3S-caranamide have high T g (70-100 °C). [2] Besides, terpenes-based chiral polyamide, which were derived from (R)-(+)-, (S)-(-)limonene, and (-)-β-pinene showed the T g value in the range of 40-42 °C. [2,12,13] Enhancement of interchain interaction based on chirality should be effective on increasing the softening temperature of the polymers. The polyamides have a synergistic effect on chiral interaction and hydrogen bonding between the different moieties. [11,14,15] Recently, we have reported the preparation of polyamides with heterocyclic amide ring such as pyrrolidone to increase the T g , owing to the rigidity and interchain hydrogen bonding. [16][17][18] The pyrrolidone ring was derived from itaconic acid (IA), which is a notable bio-renewable resource that can be mass-produced from Aspergillus terreus via fermentation using glucose. [17][18][19] IA reacted with amine compounds through its corresponding salt monomer to form heterocyclic pyrrolidone by aza-Michael addition of amines to IA's double bond successive ring-closing condensation with a carboxylic acid upon heating. [20,21] N-substituted amide linkage restricts water absorption, which can contribute to reducing the thermal and mechanical properties of the resulting polymer. [22] The pyrrolidone ring-based polyamides showed corrosive behavior in soil and photo-induced solubilization under UV light, which induce hydrolytic ring-opening. [21,23,24] In particular, symmetrical bis(pyrrolidone)-based dicarboxylic acids prepared from itaconic acid are polymerized and yield amorphous and degradable polymers with low T g values that are susceptible to enzymatic depolymerization. [25,26] However, conventional nonchiral polyamides such as nylon 6, nylon 66, and nylon 11 are not degradable whereas polyamides (nylon 4 and its copolymer nylon-4,4 and -5,4), which were derived from γ-aminobutyric acid (GABA) are biodegradable. [27][28][29] The polyamides from symmetrical monomers were studied, but monomers having head-tail asymmetry such as amino acids should be effective on The use of renewable feedstock for polymers has led to poor thermomechanical properties with high production costs. Herein, the production of novel chiral dicarboxylic acids derived from renewable itaconic and amino acids (d-or l-leucine) is reported. In this study, rigid chiral heterocyclic dicarboxylic acid monomers are obtained with high purity from itaconic acid-derived dimethyl itaconate as a starting material. Chirally interactive polyamides are prepared via melt polycondensation of hexamethylenediamine with heterocycl...

Bio-based monomers for amide-containing sustainable polymers

“…81 Recently, the same group reported novel diacids ( M62 and M63 ) with one pyrrolidone ring using dimethyl itaconate and l -leucine methyl ester. 82 Chirally interactive high molecular weight polyamides ( M n = 62 kDa) were prepared from polycondensation with hexamethylenediamine and showed susceptibility to pepsin-degradation. To deactivate the double bond from cross-linking while introducing anti-flammability to polyamides, a phosphonated telechelic diacid ( M64 ) was made from the addition reaction of itaconic acid and DOPO.…”