Bradley Olsen, Massachusetts Institute of Technology
Amino acid–derived poly(ester urea)s (PEUs) have emerged as promising materials due to their excellent thermomechanical properties and inherent biodegradability, attributed to the presence of both ester and urea linkages in the polymer backbone. These features make them attractive candidates for biomedical uses, and they could also be viable as engineering plastics. However, their synthesis typically relies on interfacial polymerization involving phosgene like toxic chemicals and amino acid–based diester salts with p-toluenesulfonic acid, which suffers from low atom economy. Moreover, this approach presents challenges in terms of safety, sustainability, and scalability for large-scale production. Developing an alternative synthetic route that is safer, scalable, and potentially derived from renewable resources is therefore highly desirable.
This work studies the synthesis and properties of PEUs and their corresponding diol monomers derived from amino alcohols (AA) containing 2-6 carbon atoms in alkyl chain. Both linear AAs and branched AAs derived from amino acid, L-Valine and L-phenylalanine were used for making new diol monomers. The potential production of all the AAs by microbial fermentation was investigated using retrosynthesis tools.The diol monomers were synthesized using AAs and urea without using any catalyst or solvent. The reaction was carried out at high temperature where urea undergoes homolytic degradation to produce ammonia and an isocyanate group that preferentially reacts in situ with the amine functional group of amino alcohols, yielding symmetric urea diol monomers. Urea-diols were then copolymerized with dimethyl adipate to produce PEUs by melt polycondensation. Cyclization of urea diols and transamidation were observed in the presence of transesterification catalyst, with the rate of these reactions depending upon the monomer structure. Urea-diols obtained from 6-aminohexanol and phenylalaninol were found to be more stable and suitable for polycondensation. Thermal, mechanical, crystallographic, and biodegradation properties were then characterized for a variety of these PEU materials to identify candidates that combine sustainable synthesis with favorable performance properties.