Solvent-free mechanochemical polycondensation to generate tyrosine-based polyphosphoramidates
Year: 2026
Type: article
Abstract: Polyphosphoramidates are polymers featuring phosphorus-nitrogen bonds within their side or main chain, which impart unique characteristics such as acid-lability and flame retardancy. However, polyphosphoramidates generally require clever design of (P-N)-containing monomers which can then be linked together through conventional polymerisation strategies. Recently, an amino acid-derived polyphosphoramidate was reported, providing an avenue to a bio-renewable feedstock for polyphosphoramidates. Herein we report the synthesis and characterisation of tyrosine-based polyphosphoramidates (DPn> 30; Mw>10,000 Da) via solvent-free mechanochemically-assisted polycondensation. This polymer synthesis takes advantage of the bifunctional amino and phenolic moieties of tyrosine to form a random copolymer of N-P-N, N-P-O, and O-P-O bonding motifs between tyrosine methyl ester and phenyldichlorophosphate. While polycondensation routes to polyphosphoramidates have been reported previously, this work also represents the first example of a mechanochemical synthesis of a polyphosphoramidate. The use of solid phase synthesis enables the formation of high molecular weight linear species unobtainable under traditional solution phase methods. The obtained polymer exhibits a Tg of ca. 81 ℃, resists degradation up to 250 ℃, and has a char yield of 45.0% remaining at 700 ℃ in N2. These results demonstrate a solvent-free mechanochemical route to partially bio-based polyphosphoramidates.
Source: European Polymer Journal
Authors: Anastasia E. Gater, Mitchell A. Nascimento, Malachy M. Gilbert, Erin M. Leitao
Language: English
Subfield: Polymers and Plastics
Field: Materials Science
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,330
Award: G5186120412
OpenAlex ID: W7119469964