Facile synthesis of advanced gradient polymers with sequence control using furan-protected maleimide as a comonomer
Facile synthesis of advanced gradient polymers with sequence control using furan-protected maleimide as a comonomer
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使用呋喃保护的马来酰亚胺作为共聚单体，通过序列控制轻松合成先进的梯度聚合物
DOI：
10.1039/c7py02125a
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发表时间：
2018-04-07
影响因子：
4.6
通讯作者：
Zhu, Xiulin
中科院分区：
文献类型：
--
作者：
Gu, Xue;Zhang, Liuqiao;Zhu, Xiulin
梯度聚合物由于其未知的结构/性能关系和潜在的应用而成为有趣的结构。本文以甲基丙烯酸甲酯和呋喃保护的丙基马来酰亚胺（FPMI）为共聚单体，通过可逆加成-断裂链转移（RAFT）聚合制备了高级梯度共聚物。在100 °C下RAFT聚合期间，丙基马来酰亚胺（PMI）由FPMI经由逆Diels-桤木（rDA）反应原位生成，以由于固有竞聚率而以梯度方式进行共聚。在40 °C下，未触发PMI释放的rDA反应。许多前所未有的梯度聚合物，包括同步，分级，二嵌段，对称，和三嵌段梯度共聚物，成功地制备。最后，序列依赖的热性能进行了探索。这一工作极大地丰富了梯度聚合物库，并推进了序列控制聚合的研究。
Gradient polymers are intriguing structures due to their unknown structure/property relationships and potential applications. Herein, advanced gradient copolymers were prepared from comonomers methyl methacrylate and furan-protected propyl maleimide (FPMI) via a reversible addition–fragmentation chain-transfer (RAFT) polymerization. During RAFT polymerization at 100 °C, propyl maleimide (PMI) was generated in situ from FPMI via a retro-Diels–Alder (rDA) reaction to undergo copolymerization in a gradient manner due to intrinsic reactivity ratios. At 40 °C, the rDA reaction for PMI release was not triggered. Many unprecedented gradient polymers, including simultaneous, hierarchical, di-block, symmetrical, and tri-block gradient copolymers, were successfully fabricated. Finally, the sequence-dependent thermal properties were explored. This work greatly enriches the library of gradient polymers and advances research into sequence-controlled polymerization.