Perfluorocyclobutyl‐containing Amphiphilic Block Copolymers Synthesized by RAFT Polymerization
Perfluorocyclobutyl‐containing Amphiphilic Block Copolymers Synthesized by RAFT Polymerization
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DOI：
10.1002/cjoc.200990379
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发表时间：
2009-11
影响因子：
5.4
通讯作者：
Yong-Jun Chen;Sen Zhang;Chun Feng;Yaqin Zhang;Qingnuan Li;Wenxin Li;Xiaoyu Huang
中科院分区：
文献类型：
--
作者：
Yong-Jun Chen;Sen Zhang;Chun Feng;Yaqin Zhang;Qingnuan Li;Wenxin Li;Xiaoyu Huang
通过可逆加成断裂链转移（RAFT）聚合制备了含有疏水性全氟环丁基（PFCB）聚丙烯酸酯和亲水性聚乙二醇（PEG）链段的两亲性嵌段共聚物。含PFCB的丙烯酸酯单体，对-(2-(对甲苯氧基)全氟环丁氧基)-丙烯酸苯酯，首先由市售化合物以良好的产率合成，并且这种丙烯酸酯单体可以通过自由基聚合或RAFT聚合进行均聚。动力学研究表明，2,2'-偶氮二异丁腈（AIBN）引发和二硫代苯甲酸枯基酯（CDB）介导的RAFT聚合处于活跃状态，数均分子量（Mn）随着单体转化率线性增加，而多分散指数保持小于1.10这一事实表明。采用4-氰基戊酸二硫代苯甲酸酯端基封端的PEG单甲醚作为大链转移剂(mPEG-CTA)，通过RAFT聚合制备具有窄分子量分布(Mw/Mn≤1.21)的嵌段聚合物。疏水链段的长度可以通过PFCB基丙烯酸酯单体的进料比和聚合时间的延长来调节。通过荧光探针技术研究了嵌段共聚物在水介质中的胶束化行为。
Amphiphilic block copolymers containing hydrophobic perfluorocyclobutyl-based (PFCB) polyacrylate and hydrophilic poly(ethylene glycol) (PEG) segments were prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization. The PFCB-containing acrylate monomer, p-(2-(p-tolyloxy)perfluorocyclobutoxy)-phenyl acrylate, was first synthesized from commercially available compounds in good yields, and this kind of acrylate monomer can be homopolymerized by free radical polymerization or RAFT polymerization. Kinetic study showed the 2,2′-azobis(isobutyronitrile) (AIBN) initiated and cumyl dithiobenzoate (CDB) mediated RAFT polymerization was in a living fashion, as suggested by the fact that the number-average molecular weights (Mn) increased linearly with the conversions of the monomer, while the polydispersity indices kept less than 1.10. The block polymers with narrow molecular weight distributions (Mw/Mn≦1.21) were prepared through RAFT polymerization using PEG monomethyl ether capped with 4-cyanopentanoic acid dithiobenzoate end group as the macro chain transfer agent (mPEG-CTA). The length of the hydrophobic segment can be tuned by the feed ratio of the PFCB-based acrylate monomer and the extending of the polymerization time. The micellization behavior of the block copolymers in aqueous media was investigated by the fluorescence probe technique.