Controlling the synthesis of degradable vinyl polymers by xanthate-mediated polymerization
Controlling the synthesis of degradable vinyl polymers by xanthate-mediated polymerization
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DOI：
10.1039/c5py01156f
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发表时间：
2015-01-01
影响因子：
4.6
通讯作者：
Dove, Andrew P.
中科院分区：
文献类型：
--
作者：
Bell, Craig A.;Hedir, Guillaume G.;Dove, Andrew P.
本文报道了醋酸乙烯酯（VAc）与2-亚甲基-1，3-二氧杂环庚烷（MDO）的共聚合，以及在对甲氧基苯基黄原酸酯链转移剂（CTA）存在下MDO的均聚反应，并与其它已知黄原酸酯的均聚反应进行了比较。深入研究表明，黄原酸酯官能度的损失是Z-基团断裂导致形成二硫代碳酸酯基团的结果，如C-13 NMR光谱所证实的。使用具有取代的苯基Z-基团的黄原酸酯大大减少了通过Z-基团的断裂，因此在使用RAFT/MADIX技术的聚合期间显著增加了链端保留。通过原位氨解和碱催化的Michael加成反应，对聚多学科氧烷（poly（MDO））的链端进行了后聚合改性，得到了具有炔功能的聚多学科氧烷（poly（MDO））。
The copolymerization of vinyl acetate (VAc) and 2-methylene-1,3-dioxepane (MDO), as well as the homo-polymerization of MDO in the presence of a p-methoxyphenyl xanthate chain transfer agent (CTA) is reported and comparison of the homopolymerization of MDO with other known xanthates was also investigated. In depth investigation showed loss of the xanthate functionality was a result of Z-group fragmentation leading to the formation of carbonodithioate groups, as confirmed by C-13 NMR spectroscopy. The use of the xanthate with a substituted phenyl Z-group drastically reduces fragmentation through the Z-group and hence significantly increases chain-end retention during the polymerization using the RAFT/MADIX technique. Post-polymerization modification of the chain-end of poly(MDO) was achieved by in situ aminolysis and base-catalyzed Michael addition of propargyl methacrylate onto the terminal thiol to form alkyne functional poly(MDO).