Dual‐Functional Hyperbranched Additives for Antibacterial and Antifouling Soft PVC : A Molecular Design Strategy via ATRP

ABSTRACT

Soft polyvinyl chloride (PVC) is the dominant polymeric material for medical devices, yet its inherent susceptibility to bacterial colonization and biofilm formation during clinical use remains a critical safety risk. This work reports a novel multifunctional antifouling additive with a hyperbranched poly(ethyleneimine) ‐ poly(ε‐caprolactone) (PEI‐PCL) core. Poly(ethylene glycol) methyl ether methacrylate (PEGMA) and/or 2‐(dimethylamino)ethyl methacrylate (DMAEMA) were grafted onto the core via atom transfer radical polymerization (ATRP), followed by quaternization yielding two cationic variants (PEI‐PCLQ, PEI‐PCLQE). Thermal and structural characterizations confirm PEGMA incorporation preserves the core's semi‐crystallinity, imparting robust anti‐adhesion to PVC composites, while quaternary ammonium functionalization induces an amorphous transition, delivering > 90% bactericidal efficiency for PVC. Notably, the dual‐functional PEI‐PCLQE exhibits remarkable synergy: it enables fine tuning of additive‐PVC compatibility while integrating anti‐adhesion and bactericidal functions. The optimized composite delivers comprehensive antifouling performance (suppressed bacterial adhesion, inhibited biofilm formation, attenuated platelet activation) and excellent hemocompatibility (hemolysis rate < 2%). This study establishes a feasible design strategy for multifunctional polymeric additives, supporting the development of high‐performance biocompatible medical PVC with tailorable surface properties and dual‐mode antifouling functions.