Degradation of a Wholly Aromatic Main-Chain Thermotropic Liquid-Crystalline Polymer Mediated by Superbases

Abstract

Plastic circular economy needs to be established to solve environmental issues related to plastic waste. Superengineering plastics such as liquid-crystalline (LC) polymers exhibit excellent thermal and mechanical properties, resulting in poor degradability in natural environment. Herein, we report the degradation of a wholly aromatic thermotropic LC polyester, poly(4-hydroxybenzoic acid-co-6-hydroxy-2-naphthoic acid) (Vectra) mediated by superbases. Methanolysis and hydrolysis of Vectra yield its monomeric compounds, 4-hydroxybenzoic acid, 6hydroxy-2-naphthoic acid, and their methyl esters. Among several transesterification catalysts explored, 1,5,7-triazabicylco[4.4.0]dec-5-ene (TBD) is the most suitable for the methanolysis of Vectra. The complete degradation of Vectra is achieved under reflux. The degradation proceeds heterogeneously via a surface erosion mechanism, preferentially starting from less chain-packed regions. Model reactions using aryl arylates reveal that monomeric compound−superbase complexes could mediate the cleavage of the ester bonds in both homogeneous and heterogeneous systems. The ester bonds of Vectra have inherent poor reactivity and are protected by oriented robust structures of the polymer. Nevertheless, the superbases enable the degradation of Vectra via the cleavage of the ester bonds by methanol. These outcomes open the way for recycling high-performance plastics as well as demonstrate the feasibility of recovering precious aromatic compounds from plastic waste as aromatic feedstock.