Wu Jiarui, Zhang Li, Chen Ying, Tan Jianbo
Department of Polymeric Materials and Engineering, School of Materials and Energy, Guangdong University of Technology, Guangzhou 510006, China.
Guangdong Provincial Key Laboratory of Functional Soft Condensed Matter, Guangzhou 510006, China.
ACS Macro Lett. 2022 Jul 19;11(7):910-918. doi: 10.1021/acsmacrolett.2c00314. Epub 2022 Jul 6.
Herein, an ω,ω-heterodifunctional macromolecular reversible addition-fragmentation chain transfer (macro-RAFT) agent containing two different RAFT end groups was synthesized and employed to mediate aqueous photoinitiated RAFT dispersion polymerization of a methacrylic monomer. Because of the different RAFT controllability of two RAFT end groups toward methacrylic monomers, the RAFT end group with good controllability dominated the polymerization while the other RAFT end group with poor controllability was unreacted, leading to the formation of linear block copolymers. Because of the unique structure of the linear block copolymers, a diverse set of block copolymer nanoparticles with rich RAFT groups at the interface of the hydrophilic corona/the hydrophobic core were successfully prepared. Finally, μ-A(BC)C miktoarm star block copolymer nanoparticles were prepared by RAFT seeded emulsion polymerization of an acrylic monomer, which enables the further morphological control over polymer nanoparticles. We believe that the utilization of an ω,ω-heterodifunctional macro-RAFT agent in heterogeneous RAFT polymerization will offer considerable opportunities for the rational synthesis of well-defined molecular architectures and polymer nanoparticles.
在此，合成了一种含有两个不同RAFT端基的ω,ω-异双官能大分子可逆加成-断裂链转移（macro-RAFT）试剂，并将其用于介导甲基丙烯酸单体的水性光引发RAFT分散聚合。由于两个RAFT端基对甲基丙烯酸单体的RAFT可控性不同，具有良好可控性的RAFT端基主导聚合反应，而另一个可控性较差的RAFT端基未反应，从而形成线性嵌段共聚物。由于线性嵌段共聚物的独特结构，成功制备了一系列在亲水性冠层/疏水性核界面处具有丰富RAFT基团的嵌段共聚物纳米粒子。最后，通过丙烯酸单体的RAFT种子乳液聚合制备了μ-A(BC)C米克托臂星形嵌段共聚物纳米粒子，这使得能够对聚合物纳米粒子进行进一步的形态控制。我们相信，在非均相RAFT聚合中使用ω,ω-异双官能macro-RAFT试剂将为合理合成明确的分子结构和聚合物纳米粒子提供大量机会。
