Polyester Brush Coatings for Circularity: Grafting, Degradation, and Repeated Growth

Polymer brushes are widely used as versatile surface modifications. However, most of them are designed to be long-lasting by using nonbiodegradable materials. This generates additional plastic waste and hinders the reusability of substrates. To address this, we present a synthetic strategy for grafting degradable polymer brushes via organocatalytic surface-initiated ring-opening polymerization (SI-ROP) from stable PGMA-based macroinitiators. This yields polyester brush coatings (up to 50 nm in thickness) that hydrolyze with controlled patterns and can be regrown on the same substrate after degradation. We chose polyesters of different hydrolytic stability and degradation mechanism, i.e., poly-(lactic acid) (PLA), polycaprolactone (PCL), and polyhydroxybutyrate (PHB), which are grown from poly-(glycidyl methacrylate) (PGMA)-based macroinitiators for strong surface binding and initiating site reuse. Brush degradation is monitored via thickness changes in pH-varied buffer solutions and seawater with PHB brushes showing rapid degradation in all solutions. PLA and PCL brushes show higher stability in solutions of up to pH 8, while all coatings fully degrade after 14 days in seawater. These brushes offer surface modifications with well-defined degradation patterns that can be regrown after degradation, making them an interesting alternative to (meth)-acrylate-based, nondegradable polymers brushes.

Automated summary

Polymer brushes are widely used for versatile surface modifications but most of them are nonbiodegradable. In this study, the researchers presented a synthetic strategy for grafting degradable polymer brushes via organocatalytic surface-initiated ring-opening polymerization. The polymer brushes produced were able to hydrolyze with controlled patterns and be regrown on the same substrate after degradation. The research showed that the polyester brush coatings exhibited different levels of hydrolytic stability and degradation mechanism, making them a potential alternative to nondegradable polymer brushes.