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Synthesis of thermoresponsive block and graft copolymers via the combination of living cationic polymerization and RAFT polymerization using a vinyl ether-type RAFT agent
Polymer ( IF 4.1 ) Pub Date : 2014-03-01 , DOI: 10.1016/j.polymer.2014.02.053
Akmal Hadi Ma'Radzi , Shinji Sugihara , Soichiro Miura , Naoto Konegawa , Yasushi Maeda

A novel vinyl ether-type RAFT agent, benzyl 2-(vinyloxy)ethyl carbonotrithioate (BVCT) was synthesized for various block copolymers via the combination of living cationic polymerization of vinyl ethers and reversible addition−fragmentation chain transfer (RAFT) polymerization. The novel BVCT–trifluoroacetic acid adduct play an important role to produce well-defined block copolymers, which is both as a cationogen under EtAlCl2 initiation system in the presence of ethyl acetate for living cationic polymerization and a RAFT agent for blocks by RAFT polymerization. The resulting polymer, poly(vinyl ether)s, by living cationic polymerization had a high number average α-end functionality (≥0.9) as determined by both 1H NMR and MALDI-TOF-MS spectrometry. In addition, this poly(vinyl ether)s worked well as a macromolecular chain transfer agent for RAFT polymerization. The RAFT polymerization of radically polymerizable monomers was conducted in toluene using 2,2′-azobis(isobutyronitrile) at 70 °C. For example, a double thermoresponsive block copolymer (MOVE61-b-NIPAM150) consisting of 2-methoxyethyl vinyl ether (MOVE) and N-isopropylacrylamide (NIPAM) was prepared via the combination of living cationic polymerization and RAFT polymerization. The block copolymer reversibly formed and deformed micellar assemblies above the phase separation temperature (Tps) of poly(NIPAM) block in water. This BVCT is not only functioned as an initiator, but also acted as a monomer. When BVCT was copolymerized with MOVE by living cationic polymerization, followed by graft copolymerization with NIPAM via RAFT polymerization, well-defined graft copolymers (MOVEn-co-BVCTm)-g-NIPAMx (n = 62–73, m = 1–9, x = 19–214) were successfully obtained. However, no micelle formed in water above Tps of poly(NIPAM) graft chain unlike the case of block copolymers.



中文翻译:

使用乙烯基醚型RAFT试剂通过活性阳离子聚合和RAFT聚合的合成热敏性嵌段和接枝共聚物

通过乙烯基醚的活性阳离子聚合与可逆加成-断裂链转移(RAFT)聚合相结合,合成了一种新型的乙烯基醚型RAFT剂2-三乙烯基苄基(CV)的碳三硫代酸酯(BVCT)。新型的BVCT-三氟乙酸加合物在生产定义明确的嵌段共聚物中起着重要作用,该嵌段共聚物既在EtAlCl 2引发体系下,在乙酸乙酯存在下作为阳离子阳离子用于活性阳离子聚合,又作为RAFT试剂用于RAFT聚合用于嵌段。将得到的聚合物,聚(乙烯基醚)类,通过活性阳离子聚合具有如通过确定高的数均α-端功能(≥0.9)11 H NMR和MALDI-TOF-MS光谱。另外,该聚乙烯醚作为用于RAFT聚合的大分子链转移剂很好地起作用。自由基可聚合单体的RAFT聚合是在70°C下使用2,2'-偶氮二(异丁腈)在甲苯中进行的。例如,通过活性阳离子聚合和RAFT聚合的组合,制备了由2-甲氧基乙基乙烯基醚(MOVE)和N-异丙基丙烯酰胺(NIPAM)组成的双热响应性嵌段共聚物(MOVE 61 - b- NIPAM 150)。高于相分离温度(T ps)的嵌段共聚物可逆地形成和变形的胶束组件。(NIPAM)嵌段在水中)。该BVCT不仅起引发剂的作用,而且还起单体的作用。当BVCT通过活性阳离子聚合与MOVE共聚,然后通过RAFT聚合与NIPAM接枝共聚时,定义明确的接枝共聚物(MOVE n - co -BVCT m-g -NIPAM xn  = 62-73,m  = 1 –9,x  = 19–214)已成功获得。然而,与嵌段共聚物的情况不同,在聚(NIPAM)接枝链的T ps以上的水中没有形成胶束。

更新日期:2014-03-01
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