Backbone-Degradable Polymers via Radical Copolymerizations of Pentafluorophenyl Methacrylate with Cyclic Ketene Acetal: Pendant Modification and Efficient Degradation by Alternating-Rich Sequence
Backbone-Degradable Polymers via Radical Copolymerizations of Pentafluorophenyl Methacrylate with Cyclic Ketene Acetal: Pendant Modification and Efficient Degradation by Alternating-Rich Sequence
复制标题
通过甲基丙烯酸五氟苯酯与环状乙烯酮缩醛的自由基共聚得到主链可降解聚合物：通过交替富序列进行悬垂改性和有效降解
DOI：
10.1021/acsmacrolett.1c00513
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发表时间：
2021
影响因子：
7.015
通讯作者：
Ouchi Makoto
中科院分区：
文献类型：
--
作者：
Lai Haiwang;Ouchi Makoto
本工作通过甲基丙烯酸五氟苯基酯（PFMA）与5，6-苯并-2-亚甲基-1，3-二氧杂环庚烷（BMDO）的自由基共聚反应，通过开环增长得到酯键主链，合成了主链可降解的聚合物。缺电子甲基丙烯酸酯与富电子环状单体的组合允许高交叉共聚，并且通过与甲基丙烯酸甲酯（MMA）和BMDO的共聚的比较来阐明电子效应。共聚物中的PFMA单元随着侧链的官能化而发生定量的醇解或氨解转化为甲基丙烯酸酯或甲基丙烯酰胺单元沿着。通过进料过量比例的BMDO实现交替富集序列，其通过RAFT共聚获得的共聚物的MALDI-TOF-MS得到支持。含MMA单元的甲醇转化共聚物在碱性条件下发生降解，由于富序列交替，其降解效率上级优于MMA与BMDO自由基共聚得到的共聚物。
This work deals with syntheses of backbone-degradable polymers via the radical copolymerization of pentafluorophenyl methacrylate (PFMA) with 5,6-benzo-2-methylene-1,3-dioxepane (BMDO), which undergoes ring-opening propagation to afford an ester-bonded backbone. The combination of the electron-deficient methacrylate with the electron-rich cyclic monomer allowed high crossover copolymerization, and the electronic effect was clarified by the comparison with the copolymerization of methyl methacrylate (MMA) and BMDO. The PFMA units of the resultant copolymer underwent quantitative alcoholysis or aminolysis transformation into methacrylate or methacrylamide units along with the pendant functionalization. The alternating-rich sequence was achieved by feeding an excess ratio of BMDO, which was supported by MALDI-TOF-MS of the copolymer obtained by the RAFT copolymerization. The methanolysis-transformed copolymer carrying MMA units was decomposed under basic condition, and the degradation efficiency was superior to that of the copolymer obtained via radical copolymerization of MMA with BMDO because of the alternating-rich sequence.