Rubber-like and Antifouling Poly(trimethylene carbonate-ethylphosphonate) Copolymers with Tunable Hydrolysis

Controlling the degradation and cell interaction of polymer materials is vital for numerous applications. Transitioning from enzymatic to nonenzymatic hydrolysis offers precise control over degradation processes. In this study, we synthesized high molar mass poly(trimethylene carbonate) (PTMC)-polyphosphonate copolymers to achieve distinctive antifouling and controlled degradation properties. 2-Ethyl-2-oxo-1,3,2-dioxaphospholane (EtPPn) is copolymerized with trimethylene carbonate (TMC) to random P(TMC-<i>co</i>-EtPPn) copolymers through ring-opening copolymerization, utilizing Sn(Oct)₂ as the catalyst. Copolymers with molar masses reaching up to <i>M</i>_n = 218 kg/mol and molar mass dispersities of <i>D̵</i> < 1.9 are obtained. To maintain hydrophobicity, 10 and 20 mol % of hydrophilic phosphonate units are incorporated into PTMC-copolymers. While copolymers with 10 mol % EtPPn display mechanical properties akin to the homopolymer PTMC, a deviation in elongation at break and yield strength results when 20 mol % EtPPN is incorporated. PTMC-PPE copolymers demonstrate antifouling behavior, i.e., cell repulsion for human mesenchymal stem cells (hMSCs) and inhibited enzymatic degradation by lipase in contrast to PTMC-homopolymers. Conversely, P(TMC-<i>co</i>-EtPPn) undergo abiotic hydrolytic degradation with hydrolysis rates increasing with increasing phosphonate contents. In conclusion, copolymerization with EtPPn enables the switch from enzymatic PTMC degradation to adjustable hydrolytic degradation, offering controlled stabilities of such copolymers in the desired applications.