休眠单体策略在高分子序列可控中的研究进展

宋雨阳; 宣孙婷; 黄智豪; 张正彪

休眠单体策略在高分子序列可控中的研究进展

苏州大学材料与化学化工学部, 苏州, 215123

基金项目: 国家自然科学基金（21925107，22171204）；国家级大学生创新创业训练计划（202010285052）

详细信息

作者简介:
宋雨阳（2000—），女，四川人，硕士，主要从事序列可控高分子的合成研究。E-mail：yysong2000@163.com

通讯作者:
黄智豪，E-mail: zhhuang@suda.edu.cn

张正彪，E-mail: zhangzhengbiao@suda.edu.cn

中图分类号: O63
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- 被引次数: 0
出版历程
- 网络出版日期: 2022-04-06

Recent Advances of Sequence Regulation via Latent Monomer Strategy

College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, China

摘要

摘要: 序列是指高分子链中的单体单元通过共价键连接的次序。自然界中生物大分子，如蛋白质和DNA等，他们的精确序列结构决定了其复杂且精密的功能。受此启发，序列可控高分子的合成及其结构性能研究日益成为高分子学科的热点，受到越来越多研究者的关注。本文将聚焦于近年来在序列调控中重要成果，突出介绍本课题组提出的休眠单体策略在序列可控高分子合成中的研究进展。最后，基于这些研究进展对休眠单体策略进行了总结和展望。
- 高分子序列调控 /
- 活性/可控自由基聚合 /
- 休眠单体策略 /
- Diels-Alder反应 /
- 马来酰亚胺
Abstract: The precisely-defined sequence structure of biomacromolecule, e.g., protein and DNA, enable the sophisticated and unique functions. Inspired by this, polymer scientists have made enormous efforts to achieve the precise sequence regulation in synthetic polymers. Up to date, a variety of approaches toward efficient sequence-regulation based on step-growth and chain-growth polymerization have been developed. This review summarizes the recent progress on the sequence regulation approaches, and highlights the latent monomer strategy for sequence regulation. The latent monomer strategy for sequence regulation developed by our group relies on the thermal-responsive furan/maleimide Diels-Alder reaction. By programmatically manipulation of the polymerization temperature, varieties of sequence-controlled structures are readily produced. Moreover, this approach also bridges from sequence-controlled polymers to graft copolymers with functions and architectures. Finally, a critical outlook on the latent monomer strategy and future research directions are also provided.
- Sequence regulation /
- Living/controlled radical polymerization /
- Latent monomer strategy /
- Diels-Alder reaction /
- Maleimide

HTML全文

图 1 A）呋喃保护马来酰亚胺休眠单体的低温“休眠”和高温“激活”原理示意图^[14]；B）休眠单体策略合成序列可控高分子示意图；C）休眠单体及功能化休眠单体示例

Figure 1. A) Schematic illustration of the mechanism of the deactivation and activation of furan-protected maleimide as the latent monomer ^[14]; B) Synthesis of diverse sequence-controlled polymers via the latent monomer strategy; C) Chemical structures of the latent monomer examples

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图 2 A）呋喃保护的马来酰亚胺休眠单体和苯乙烯单体共聚合成序列可控高分子示意图，B）序列控制FMI与苯乙烯的ATRP聚合的动力学曲线图，C）聚合物链MI的累积组成（F_cum）和瞬时组成（F_inst）与归一化链长之间的关系，D) 链增长和马来酰亚胺单体插入示意图^[14]

Figure 2. A) Schematic illustration of the synthesis of sequence-controlled polymer based on furan-protected maleimide as a latent monomer, B) Kinetic plots of sequence-controlled ATRP polymerization of FMI and St, C) cumulative (F_cum) and instantaneous (F_inst) content of MI in polymer chains as a function of normalized chain length, D) SEC traces ^[14]

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图 3 A）MMA/PMI二嵌段梯度共聚物的合成，B）序列控制多种MMA/PMI梯度共聚物的合成示意图^[15]

Figure 3. A) Synthesis of MMA/PMI di-block gradient copolymers, B) Schematic illustration of sequenced-controlled synthesis of multiple MMA/PMI gradient copolymers ^[15]

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图 4 A）endo-和exo-两种立构不同的休眠单体的高温“激活”原理及序列控制四元RAFT共聚示意图，B）endo-和exo-两种立体构型的逆D-A反应行为动力学，C）序列控制endo-FMI、exo-FHMI与苯乙烯的RAFT三元共聚^[16]

Figure 4. A) Schematic illustration of the actived mechanisms at high temperature for endo- and exo- latent monomers and the sequence-controlled RAFT quaternary polymerization, B) Kinetics of retro D-A reactions of endo- and exo- latent monomers, C) Sequence-controlled RAFT ternary polymerization of endo-FMI, exo-FHMI, and St ^[16]

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图 5 A）二噻吩基呋喃保护的马来酰亚胺D-A加合物可逆D-A反应的光热双重控制原理示意图；B）光热双重控制下的BMA、FMOH和DTFMMI-c的RAFT三元共聚，C）动力学曲线图，D）聚合物链中MOH和MMI的瞬时组成（F_inst）和累积组成（F_cum）与归一化链长之间的关系^[18]

Figure 5. A) Schematic illustration of the photo-thermal dual-regulated mechanism of the reversible D-A reaction of dithienylfuran-protected maleimide D-A adduct; B) Photo-thermal dual-regulated RAFT ternary polymerization of BMA, FHOH, and DTFMMI-c, C) kinetic plots, D) cumulative (F_cum) and instantaneous (F_inst) contents of the MOH and MMI in polymer chains as a function of normalized chain length ^[18]

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图 6 A）功能化休眠单体的低温“休眠”和高温“激活”原理示意图，B）温控下休眠单体与苯乙烯RAFT共聚生成多种序列的聚合物^[19]

Figure 6. A) Schematic illustration of the mechanism of the deactivation and activation of functionalized latent monomers, B) Synthesis of multiple sequence-controlled polymers by manipulating the temperature via RAFT polymerization by using the functionalized latent monomers and St ^[19]

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图 7 A）序列可控聚合物的后修饰示意图，B）后修饰前后核磁氢谱对比，C）后修饰前后红外谱对比^[20]

Figure 7. A) Schematic illustration of the post-modified polymers with controlled sequence, B) The ¹H NMR spectra of post-modified polymers, C) The FT-IR spectra of post-modified polymers ^[20]

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图 8 A）拓扑结构的可控生长示意图，B）大分子休眠单体与苯乙烯通过温度调控RAFT聚合实现拓扑结构实时调控^[21]

Figure 8. A) Schematic illustration of the controllably growing topology, B) Controlled topology growth in real time by manipulating the temperature via RAFT polymerization by using the macro-latent monomer and St ^[21]

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图 9 休眠单体策略下的RAFT聚合与ROP聚合连用合成不同拓扑结构的接枝聚合物^[22]

Figure 9. Schematic illustration of synthesis of sequence-controlled graft polymers via RAFT polymerization over the latent monomer strategy as well as ROP polymerization ^[22]

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图 10 A）序列控制NIPAM与MFAN的RAFT共聚，B）不同序列聚合物的热响应行为^[23]

Figure 10. A) Sequence-controlled RAFT polymerization of NIPAM and MFAN, B) Thermo-responsive behavior of polymers with different sequences ^[23]

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