Chong Wang,Rong-Chao Xue,Ze-Zhong Lin,Xing-Ping Zhang,Pei-Yao Chen,Yu Chen,Hai-Chao Li
Flexible plasticized poly(vinyl chloride) (PPVC) is widely used in medical devices; however, achieving persistent antibiofouling functionality after significant mechanical deformation and long-term water exposure remains a critical challenge. In this work, we introduce amphiphilic heterografted multi-arm star copolymers, polyethylenimine (PEI) cores functionalized with polyethylene glycol (PEG) and poly(ε-caprolactone) (PCL) arms (denoted as PEI-g-PEG-PCLs), as multifunctional additives for modifying PPVC. Dynamic light scattering (DLS) and optical transmittance measurements confirmed the formation of PEI-g-PEG-PCL micelles within the PPVC matrix. The incorporation of PEI-g-PEG-PCLs improved not only the mechanical and thermal properties of PPVC but also its surface hydrophilicity. The resulting composites demonstrated exceptional resistance to biofouling, reducing protein adsorption by 96.2–97.3 % for bovine serum albumin and 98.0–99.8 % for lysozyme, and lowering bacterial adhesion rates to 11 % for Escherichia coli and 19 % for Staphylococcus aureus. Furthermore, platelet adhesion and hemolysis assays confirmed the biocompatibility of the PEI-g-PEG-PCL/PPVC composites. Notably, even after undergoing three cycles of 50 % strain, the optimal PEI-g-PEG-PCL/PPVC composite retained over 91 % of its initial anti-protein fouling performance. Long-term immersion in physiological conditions (28 days) further demonstrated its durability, with more than 92 % of the original antifouling efficacy maintained. The multi-arm star topology accompanied with the long PCL arm is proposed to resolve the “entanglement–migration paradox” commonly encountered in linear or less branched polymer additives. This study presents a molecular engineering strategy for developing durable antibiofouling polymers capable of withstanding both mechanical stress and prolonged aqueous exposure in medical applications.
Homoarm and heteroarm core cross-linked star (CCS) polymers based on poly(N,N-dimethylacrylamide) (PDMA) as the high-polarity arm and poly(2-methoxyethylacrylate) (PMEA) as the low-polarity arm were efficiently prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization in a dispersion polymerization system. PDMA and PMEA arm polymers exhibited similar conversion rates, such that their composition in the heteroarm CCS polymers was easily controlled by the feed ratio in the synthesis. The ability to control the arm composition allowed facile tuning of the polarity of the CCS polymers. Heteroarm CCS polymers self-assembled in water to form aggregates and their size was related to the composition and polarity of the CCS polymers. The composition and polarity of the CCS polymers significantly affected the emulsifying behaviour of the CCS polymers as emulsifiers. Oil-in-water (o/w) emulsions were favoured for CCS polymers with relatively high polarity and lowering the polarity of CCS polymers to a certain degree enhanced the stability of the emulsions. Multiple emulsions, both o/w and water-in-oil (w/o), were gradually produced when the polarity of CCS polymers was gradually lowered and the oil fraction in the emulsion samples was gradually increased, and at the same time the emulsions also became increasingly less stable.
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