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非手性液晶聚合物中超分子手性结构的诱导与光照固定

郭玉权 贺子翔 程笑笑 张弓 缪腾飞 张伟

郭玉权, 贺子翔, 程笑笑, 张 弓, 缪腾飞, 张 伟. 非手性液晶聚合物中超分子手性结构的诱导与光照固定[J]. 功能高分子学报,2023,36(1):1-10 doi: 10.14133/j.cnki.1008-9357.20220723001
引用本文: 郭玉权, 贺子翔, 程笑笑, 张 弓, 缪腾飞, 张 伟. 非手性液晶聚合物中超分子手性结构的诱导与光照固定[J]. 功能高分子学报,2023,36(1):1-10 doi: 10.14133/j.cnki.1008-9357.20220723001
GUO Yuquan, HE Zixiang, CHENG Xiaoxiao, ZHANG Gong, MIAO Tengfei, ZHANG Wei. Induction and Photo-Locking of Supramolecular Chiral Structures in Achiral Liquid Crystalline Polymers[J]. Journal of Functional Polymers. doi: 10.14133/j.cnki.1008-9357.20220723001
Citation: GUO Yuquan, HE Zixiang, CHENG Xiaoxiao, ZHANG Gong, MIAO Tengfei, ZHANG Wei. Induction and Photo-Locking of Supramolecular Chiral Structures in Achiral Liquid Crystalline Polymers[J]. Journal of Functional Polymers. doi: 10.14133/j.cnki.1008-9357.20220723001

非手性液晶聚合物中超分子手性结构的诱导与光照固定

doi: 10.14133/j.cnki.1008-9357.20220723001
基金项目: 国家自然科学基金(21971180,92056111);江苏省高等学校自然科学研究重大项目(19 KJA360006)
详细信息
    作者简介:

    郭玉权(1997—),男,硕士生,主要研究方向为超分子手性的调控与固定。E-mail:1023091263@qq.com

    通讯作者:

    缪腾飞,E-mail:mtf0824@163.com

    张 伟,E-mail:weizhang@suda.edu.cn

  • 中图分类号: O631.2

Induction and Photo-Locking of Supramolecular Chiral Structures in Achiral Liquid Crystalline Polymers

  • 摘要: 超分子手性结构由于其形成所需的非共价相互作用力较弱,因此极易在外界条件刺激下发生解离,从而导致手性消失。在绝大多数情况下,以非手性单元为组装模块的组装体系中超分子手性结构在外部环境刺激下被破坏后无法回复。为了提高超分子手性结构的稳定性,克服其对原有手性源的依赖性,设计合成了一种侧链型非手性苯甲酸苯酯液晶聚合物,在聚合物侧链末端引入肉桂酸结构作为交联基团。将手性柠檬烯的手性诱导与简单的光照交联结合即可实现超分子手性的共价键固定,极大地简化了交联过程,为手性材料的制备与手性信息存储提供了新的策略。

     

  • 图  1  超分子手性在非手性聚合物中的构建与固定过程:(a) 聚合物与手性柠檬烯的化学结构式(未交联聚合物在干净的石英片上退火,随后用手性溶剂蒸气熏蒸进行手性诱导);(b) 紫外光照前后聚合物结构的变化;(c) 手性诱导与交联过程

    Figure  1.  The process of construction and fixation of supramolecular chirality in achiral polymer systems: (a) Chemical structures of the polymers and chiral limonene (the polymer before crosslinking was annealed on a clean quartz plate and then exposed to chiral vapor atmosphere for chiral induction); (b) The structure of the polymers before and after UV irradiation; (c) The process of chirality induction and crosslinking

    图  2  (a) 苯甲酸苯酯(Pe)单体与(b) 含肉桂酸结构的苯甲酸苯酯(PeCA)单体的合成路线

    Figure  2.  The synthetic route of the monomers of (a) phenyl benzoate (Pe) and (b) phenyl benzoate containing cinnamic acid (PeCA)

    图  3  (a)Pe与(b)PeCA的1H-NMR谱;PPex-r-PeCAy的(c)1H-NMR谱与(d)GPC曲线

    Figure  3.  1H-NMR spectra of (a) Pe and (b) PeCA; (c) 1H-NMR spectra and (d) GPC curves of PPex-r-PeCAy.

    图  4  (a)聚合物的DSC曲线;(b)PPe1-r-PeCA1聚合物的SAXS图案;(c)PPe1-r-PeCA1聚合物的XRD图案;(d)PPe1-r-PeCA1薄膜在向列相温度下退火12 h后的POM图案;(e)PPe1-r-PeCA1薄膜在手性诱导后的CD和UV-vis吸收光谱;(f)浸泡不同时间后甲醇溶液中的残余柠檬烯的1H-NMR谱

    Figure  4.  (a) DSC curves of the polymers; (b) SAXS pattern recorded for the polymer PPe1-r-PeCA1; (c) XRD pattern recorded for the polymer PPe1-r-PeCA1; (d) POM images of PPe1-r-PeCA1 films recorded after annealing at nematic phase for 12 h; (e) CD and UV-vis spectra of PPe1-r-PeCA1 films after chiral induction; (f) 1H-NMR spectra of residual limonene in methanol solution for different immersing time

    图  5  (a)交联过程中聚合物薄膜随光照时间变化的UV-vis吸收光谱;(b)聚合物交联前后的1H-NMR谱;(c)聚合物交联前后的R/S手性薄膜的CD和UV-vis吸收光谱;(d)聚合物交联前(左)、后(右)薄膜分别在THF中放置5 min后的效果图;(e)交联前的聚合物薄膜在THF中放置5 min后的CD光谱;(f)交联后的聚合物薄膜在THF中放置30 min及升、降温处理的CD光谱

    Figure  5.  (a) UV irradiation time-dependent UV-vis spectra of the chiral polymer films corresponding to the cross-linking process; (b) 1H-NMR spectra of the uncross-linked and cross-linked polymer; (c) CD and UV-vis absorption spectra of the uncross-linked and cross-linked R/S chiral polymer films; (d) Pictures of the uncross-linked (left) and cross-linked (right) chiral polymer film immersed in THF solution for 5 min; (e) CD spectra of the uncross-linked chiral polymer film immersed in THF solution for 5 min; (f) CD spectra of the cross-linked chiral polymer film immersed in THF solution for 30 min and heating-cooling process

    图  6  (a)PPe1-r-PeCA1未交联薄膜在升、降温后的CD光谱;(b)PPe1-r-PeCA1交联薄膜在100 ℃下退火不同时间后冷却至室温的CD光谱;(c)PPe1-r-PeCA1交联薄膜加热至Ti以上后冷却至室温的CD光谱;(d)手性结构破坏与自修复行为(通过gCD值的变化来考察)的循环过程

    Figure  6.  (a) CD spectra of the uncross-linked PPe1-r-PeCA1 films after heating-cooling process; (b) CD spectra of the cross-linked PPe1-r-PeCA1 films measured at 100 ℃ for different time and then cooled down to room temperature; (c) CD spectra of the cross-linked PPe1-r-PeCA1 films after heating beyond clearing temperature and then cooling down to room temperature; (d) Destruction and chiral self-recovery behavior (as shown by gCD values) switches during the above process

    图  7  (a)手性存储与手性自修复的机制示意图;(b)不同交联位点含量聚合物的手性自修复性能

    Figure  7.  (a) Mechanism of chiral storage and self-recovery; (b) Chiral self-recovery properties of the polymers with different mole fraetion of cross-linkable

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出版历程
  • 收稿日期:  2022-07-23
  • 录用日期:  2022-08-31
  • 网络出版日期:  2022-09-30

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