氧化还原引发的可逆加成-断裂链转移（RAFT）乳液聚合诱导的酮酯功能单体自组装
Redox-Initiated RAFT Emulsion Polymerization-Induced Self-Assembly of -Ketoester Functional Monomers.
作者信息
Wu Yanfei, Han Min, Shen Xianrong, Song Qingping, Liu Dongdong, Zhang Wei
机构信息
School of Chemical and Environmental Engineering, Anhui Polytechnic University, Wuhu 241000, China.
State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, Jiangsu Engineering Laboratory of Novel Functional Polymeric Materials, Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China.
出版信息
Polymers (Basel). 2025 Mar 24;17(7):870. doi: 10.3390/polym17070870.
Amphiphilic block copolymers are essential for developing advanced polymer nanomaterials with applications in bioimaging, drug delivery, and nanoreactors. In this study, we successfully synthesized functional block copolymer assemblies at high concentrations through redox-initiated reversible addition-fragmentation chain transfer (RAFT) emulsion polymerization of 2-(acetoacetoxy)ethyl methacrylate (AEMA), a -ketoester functional monomer. Utilizing a redox initiation system at 50 °C, we produced poly(poly(ethylene glycol) methyl ether methacrylate)--PAEMA (PPEGMA-PAEMA). Kinetic studies demonstrated rapid monomer conversion exceeding 95% within 30 min, with distinct polymerization phases driven by micelle formation and monomer depletion. Transmission Electron Microscopy (TEM) and Dynamic Light Scattering (DLS) revealed the formation of diverse morphologies, including worm-like, vesicular structures, and spherical micelles, depending on the macro-CTA molecular weight and monomer concentration. Additionally, post-polymerization modification with aggregation-induced emission (AIE) luminogens, such as 1-(4-aminophenyl)-1,2,2-tristyrene (TPE-NH), resulted in AIE-active polymer assemblies exhibiting strong fluorescence in aqueous dispersions. These AIE-active polymer assemblies also exhibited good biocompatibility. These findings demonstrate the efficacy of redox-initiated RAFT emulsion polymerization in fabricating functional, scalable block copolymer assemblies with potential applications in the field of life sciences.
两亲性嵌段共聚物对于开发在生物成像、药物递送和纳米反应器等领域有应用的先进聚合物纳米材料至关重要。在本研究中，我们通过氧化还原引发的可逆加成-断裂链转移（RAFT）乳液聚合2-(乙酰乙酰氧基)乙基甲基丙烯酸酯（AEMA），一种α-酮酯功能单体，成功地在高浓度下合成了功能性嵌段共聚物聚集体。利用50℃的氧化还原引发体系，我们制备了聚（聚（乙二醇）甲基醚甲基丙烯酸酯）-聚甲基丙烯酸乙酰乙酰氧基乙酯（PPEGMA-PAEMA）。动力学研究表明，在30分钟内单体转化率迅速超过95%，由胶束形成和单体消耗驱动的聚合阶段明显。透射电子显微镜（TEM）和动态光散射（DLS）显示，根据大分子链转移剂（macro-CTA）分子量和单体浓度的不同，形成了多种形态，包括蠕虫状、囊泡结构和球形胶束。此外，用聚集诱导发光（AIE）发光体，如1-(4-氨基苯基)-1,2,2-三苯乙烯（TPE-NH）进行聚合后修饰，得到了在水分散体中表现出强荧光的AIE活性聚合物聚集体。这些AIE活性聚合物聚集体也表现出良好的生物相容性。这些发现证明了氧化还原引发的RAFT乳液聚合在制备具有潜在生命科学应用的功能性、可扩展嵌段共聚物聚集体方面的有效性。
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