高级检索

  • ISSN 1008-9357
  • CN 31-1633/O6

留言板

尊敬的读者、作者、审稿人, 关于本刊的投稿、审稿、编辑和出版的任何问题, 您可以本页添加留言。我们将尽快给您答复。谢谢您的支持!

姓名
邮箱
手机号码
标题
留言内容
验证码

休眠单体策略在高分子序列调控中的研究进展

宋雨阳 宣孙婷 黄智豪 张正彪

宋雨阳, 宣孙婷, 黄智豪, 张正彪. 休眠单体策略在高分子序列调控中的研究进展[J]. 功能高分子学报,2022,35(5):395-407 doi: 10.14133/j.cnki.1008-9357.20220307001
引用本文: 宋雨阳, 宣孙婷, 黄智豪, 张正彪. 休眠单体策略在高分子序列调控中的研究进展[J]. 功能高分子学报,2022,35(5):395-407 doi: 10.14133/j.cnki.1008-9357.20220307001
SONG Yuyang, XUAN Sunting, HUANG Zhihao, ZHANG Zhengbiao. Recent Advances of Polymer Sequence Regulation via Latent Monomer Strategy[J]. Journal of Functional Polymers, 2022, 35(5): 395-407. doi: 10.14133/j.cnki.1008-9357.20220307001
Citation: SONG Yuyang, XUAN Sunting, HUANG Zhihao, ZHANG Zhengbiao. Recent Advances of Polymer Sequence Regulation via Latent Monomer Strategy[J]. Journal of Functional Polymers, 2022, 35(5): 395-407. doi: 10.14133/j.cnki.1008-9357.20220307001

休眠单体策略在高分子序列调控中的研究进展

doi: 10.14133/j.cnki.1008-9357.20220307001
基金项目: 国家自然科学基金(21925107,22171204);苏州大学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,硕士,主要从事序列可控高分子合成研究。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

Recent Advances of Polymer Sequence Regulation via Latent Monomer Strategy

  • 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。自然界中的生物大分子,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关注。本文聚焦于近年来在序列调控中的重要成果,重点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。

     

  • 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;(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[14]

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

    图  2  (a)FMI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ATRP聚合的动力学曲线图;(c)聚合物链MI的累积组成(Fcum, MI)和瞬时组成(Finst, MI)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 (Fcum, MI) and instantaneous (Finst, MI) content of MI in polymer chains as a function of normalized chain length; (d) Illustration of chain growth and insertion of maleimide monomers [14]

    图  3  (a)MMA/MI二嵌段梯度共聚物的合成;(b)序列控制多种MMA/MI梯度共聚物的合成示意图[15]

    Figure  3.  (a) Synthesis of MMA/MI di-block gradient copolymers; (b) Schematic illustration of sequenced-controlled synthesis of multiple MMA/MI gradient copolymers [15]

    图  4  (a)endo-exo-两种休眠单体的高温“激活”原理及序列控制四元RAFT共聚示意图;(b)endo-exo-两种立体构型的rDA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 rDA reactions of endo- and exo- latent monomers; (c) Sequence-controlled RAFT ternary polymerization of endo-FMI, exo-FHMI, and St [16]

    图  5  (a)二噻吩基呋喃保护的马来酰亚胺D-A加合物rDA反应的光热双重控制原理示意图;(b)光热双重控制下的BMA、FHMI和DTFMMI-c的RAFT三元共聚;(c)动力学曲线图;(d)聚合物链中HMI和MMI的瞬时组成(Finst)和累积组成(Fcum)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 rDA reaction of dithienylfuran-protected maleimide D-A adduct; (b) Photo-thermal dual-regulated RAFT ternary polymerization of BMA, FHMI, and DTFMMI-c; (c) Kinetic plots; (d) Instantaneous (Finst) and cumulative (Fcum) contents of HMI and MMI in polymer chains as a function of normalized chain length [18]

    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]

    图  7  (a)序列可控聚合物的后修饰示意图;(b)后修饰前后1H-NMR谱对比;(c)后修饰前后FT-IR谱对比[20]

    Figure  7.  (a) Schematic illustration of the post-modified polymers with controlled sequence; (b) 1H-NMR spectra of post-modified polymers; (c) FT-IR spectra of post-modified polymers [20]

    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]

    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]

    图  10  (a)序列控制NIPAM与AN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 AN; (b) Thermo-responsive behavior of polymers with different sequences [23]

  • [1] HIBI Y, TOKUOKA S, TERASHIMA T, OUCHI M, SAWAMOTO M. Design of AB divinyl “template monomers” toward alternating sequence control in metal-catalyzed living radical polymerization [J]. Polymer Chemistry,2011,2(2):341-347.
    [2] HIBI Y, OUCHI M, SAWAMOTO M. Sequence-regulated radical polymerization with a metal-templated monomer: Repetitive ABA sequence by double cyclopolymerization [J]. Angewandte Chemie: International Edition,2011,50(32):7434-7437.
    [3] IDA S, TERASHIMA T, OUCHI M, SAWAMOTO M. Selective radical addition with a designed heterobifunctional halide: A primary study toward sequence-controlled polymerization upon template effect [J]. Journal of the American Chemical Society,2009,131(61):10808-10809.
    [4] SATOH K, MATSUDA M, NAGAI K, KAMIGAITO M. AAB-sequence living radical chain copolymerization of naturally occurring limonene with maleimide: An end-to-end sequence-regulated copolymer [J]. Journal of the American Chemical Society,2010,132(29):10003-10005.
    [5] MATSUDA M, SATOH K, KAMIGAITO M. 1: 2-Sequence-regulated radical copolymerization of naturally occurring terpenes with maleimide derivatives in fluorinated alcohol [J]. Journal of Polymer Science Part A: Polymer Chemistry,2013,51(8):1774-1785.
    [6] OJIKA M, SATOH K, KAMIGAITO M. BAB-random-C monomer sequence via radical terpolymerization of limonene(A), maleimide(B), and methacrylate(C): Terpene polymers with randomly distributed periodic sequences [J]. Angewandte Chemie: International Edition,2017,56(7):1789-1793.
    [7] PFEIFER S, LUTZ J F. A facile procedure for controlling monomer sequence distribution in radical chain polymerizations [J]. Journal of the American Chemical Society,2007,129(31):9542-9543.
    [8] NAKATANI K, OGURA Y, KODA Y, TERASHIMA T, SAWAMOTO M. Sequence-regulated copolymers via tandem catalysis of living radical polymerization and in situ transesterification [J]. Journal of the American Chemical Society,2012,134(9):4373-4383.
    [9] NAKATANI K, TERASHIMA T, SAWAMOTO M. Concurrent tandem living radical polymerization: Gradient copolymers via in situ monomer transformation with alcohols [J]. Journal of the American Chemical Society,2009,131(38):13600-13601.
    [10] XU C R, ZHANG Z, PAN C Y, HONG C Y. A strategy combining quantitative reactions and reversible-covalent chemistry for sequential synthesis of sequence-controlled polymers with different sequences [J]. Polymer,2019,172:294-304.
    [11] DENG X X, LI L, LI Z L, LV A, DU F S, LI Z C. Sequence regulated poly(ester-amide)s based on passerini reaction [J]. ACS Macro Letters,2012,1(11):1300-1303.
    [12] COULEMBIER O, LOHMEIJER B G G, DOVE A P, PRATT R C, MESPOUILLE L, CULKIN D A, BENIGHT S J, DUBOIS P, WAYMOUTH R M, HEDRICK J L. Alcohol adducts of N-heterocyclic carbenes: Latent catalysts for the thermally-controlled living polymerization of cyclic esters [J]. Macromolecules,2006,39(17):5617-5628.
    [13] KAMMIYADA H, KONISHI A, OUCHI M, SAWAMOTO M. Ring-expansion living cationic polymerization via reversible activation of a hemiacetal ester bond [J]. ACS Macro Letters,2013,2(6):531-534.
    [14] JI Y X, ZHANG L Q, GU X, ZHANG W, ZHOU N C, ZHANG Z B, ZHU X L. Sequence-controlled polymers with furan-protected maleimide as a latent monomer [J]. Angewandte Chemie: International Edition,2017,56(9):2328-2333.
    [15] GU X, ZHANG L Q, LI Y, ZHANG W, ZHU J, ZHANG Z B, ZHU X L. Facile synthesis of advanced gradient polymers with sequence control using furan-protected maleimide as a comonomer [J]. Polymer Chemistry,2018,9(13):1571-1576.
    [16] HAN F F, SHI Q N, ZHANG L Q, LIU B L, ZHANG Y J, GAO Y, JIA R, ZHANG Z B, ZHU X L. Stereoisomeric furan/maleimide adducts as latent monomers for one-shot sequence-controlled polymerization [J]. Polymer Chemistry,2020,11(9):1614-1620.
    [17] ERNO Z, ASADIRAD A M, LEMIEUX V, BRANDA N R. Using light and a molecular switch to 'lock' and 'unlock' the Diels-Alder reaction [J]. Organic & Biomolecular Chemistry,2012,10(14):2787-2792.
    [18] ZHANG L Q, SONG Y Y, CAO Y H, WANG Z, HUANG Z H, XUAN S T, ZHANG Z B. A photo-thermal dual-regulated latent monomer strategy for sequence control of polymers [J]. Polymer Chemistry,2021,12(35):4996-5002.
    [19] ZHANG L Q, JI Y X, GU X, ZHANG W, ZHOU N C, ZHANG Z B, ZHU X L. Synthesis of sequence-controlled polymers with pendent “clickable” or hydrophilic groups via latent monomer strategy [J]. Reactive & Functional Polymers,2019,138:96-103.
    [20] MENG F Y, ZHANG Y J, DING K S, LIU B L, HAN F F, HE Y Y, ZHOU N C, ZHANG Z B, ZHU X L. One-shot synthesis of sequence-controlled polymers with versatile succimide motifs for post-modifications [J]. Reactive & Functional Polymers,2019,134:67-73.
    [21] ZHANG L Q, GAO Y, HUANG Z H, ZHANG W, ZHOU N C, ZHANG Z B, ZHU X L. Controllably growing topologies in one-shot RAFT polymerization via macro-latent monomer strategy [J]. Chinese Journal of Polymer Science,2021,39(1):60-69.
    [22] ZHANG Y J, CAO X H, GAO Y, XIE Y J, HUANG Z H, ZHANG Z B, ZHU X L. Bridging from the sequence to architecture: Graft copolymers engineering via successive latent monomer and grafting-from strategies(dagger) [J]. Chinese Journal of Chemistry,2021,39(5):1273-1280.
    [23] GAO Y, ZHANG L Q, JIA R, HUANG Z H, XIE Y J, XUAN S T, ZHOU N C, ZHANG Z B, ZHU X L. 2, 5-Dimethylfuran/acrylonitrile as latent monomer for sequence-controlled copolymer and sequence-dependent thermo-responsivity [J]. Macromolecular Rapid Communications,2021,42(18):2000724.
  • 加载中
图(10)
计量
  • 文章访问数:  300
  • HTML全文浏览量:  206
  • PDF下载量:  104
  • 被引次数: 0
出版历程
  • 收稿日期:  2022-03-07
  • 网络出版日期:  2022-04-06
  • 刊出日期:  2022-09-23

目录

    /

    返回文章
    返回