大学化学 >> 2020, Vol. 35 >> Issue (4): 81-89.doi: 10.3866/PKU.DXHX201912030

所属专题: 全国大学生化学实验创新设计竞赛

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AIE荧光聚合物RAFT可控合成与表征及光物理性质研究

刘天瑞1, 赵伟光2, 张妍欣1, 冯凯旋1, 徐天驰2, 章文伟1,*(), 谌东中1,2,*()   

  1. 1 南京大学化学化工学院, 化学国家级实验教学示范中心, 南京 210023
    2 南京大学化学化工学院高分子科学与工程系, 高性能高分子材料与技术教育部重点实验室, 南京 210023
  • 收稿日期:2019-12-06 录用日期:2019-12-29 发布日期:2020-02-17
  • 通讯作者: 章文伟,谌东中 E-mail:wwzhang@nju.edu.cn;cdz@nju.edu.cn
  • 基金资助:
    南京大学"十三五"实验教学改革研究重点课题(SY201903);南京大学"科研融合型"高阶实验课程培育项目(20190806);南京大学"百"层次优课建设(020514911200);国家自然科学基金项目(21875098)

RAFT Controlled Synthesis, Characterization and Photophysical Properties of the Prepared AIE Fluorescent Polymers

Tianrui Liu1, Weiguang Zhao2, Yanxin Zhang1, Kaixuan Feng1, Tianchi Xu2, Wenwei Zhang1,*(), Dongzhong Chen1,2,*()   

  1. 1 National Demonstration Center for Experimental Chemistry Education, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, P. R. China
    2 Key Laboratory of High Performance Polymer Materials and Technology of Ministry of Education, Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, P. R. China
  • Received:2019-12-06 Accepted:2019-12-29 Published:2020-02-17
  • Contact: Wenwei Zhang,Dongzhong Chen E-mail:wwzhang@nju.edu.cn;cdz@nju.edu.cn

摘要:

聚集诱导发光(AIE)分子是与传统的聚集态荧光淬灭染料分子具有截然相反的光物理性质的新型有机发光材料,可广泛应用于化学/生物传感、生物探针与成像、诊疗一体化和光电子器件等诸多领域中。本论文通过可逆加成-断裂链转移(RAFT)聚合方法,可控合成了侧链型四苯乙烯TPE聚丙烯酸酯AIE聚合物。通过实验条件的优化与探索,尤其采用半衰期较短、活性更高的偶氮二异庚腈(ABVN)取代常规的偶氮二异丁腈(AIBN)引发剂,将原来超过12 h的过夜反应前沿科研实验,改造为较短的3–5 h聚合反应时间内即可达到中等收率和较好的聚合物产品质量,使其成为一个适合本科教学环境的新创实验。本实验融合了无水无氧操作技术、柱层析分离纯化、RAFT可控聚合和GPC分子表征技术、FTIR、NMR、UV-Vis、荧光光谱等多种现代实验技术和表征方法,考查了所合成四苯乙烯TPE侧基的AIE聚合物的光物理性质,测定其溶液中的相对荧光量子产率达17%。

关键词: 四苯乙烯, AIE聚合物, RAFT可控聚合, 光物理性质, 创新实验

Abstract:

The aggregation-induced emission (AIE) molecules are novel organic fluorescent materials that present distinct photophysical properties in contrast to conventional aggregation-caused quenching fluorescent dyes. In virtue of their unique properties, they can be widely used in many fields such as chemical/biological sensing, biological probing and imaging, diagnosis and treatment integration and optoelectronic devices. In this paper, based on innovative experimental competition, tetraphenylethylene (TPE) side-chain polyacrylate AIE polymers have been synthesized through reversible addition-fragmentation chain transfer (RAFT) polymerization. With the optimization and exploration of the experimental conditions, the initiator of 2, 2'-azobis-2, 4-dimethylvaleronitrile (ABVN) with shorter half-life and higher activity was adopted to replace the conventional azobisisobutyronitrile (AIBN). As a result, the frontier scientific research experiment, which would have required more than 12 hours reaction, was adapted into a shorter polymerization time of 3-5 hours with moderate yields and good polymer product quality. Thus, the research experiment was remoulded as an experiment suitable for undergraduate laboratory teaching. A range of modern laboratory techniques, such as the anhydrous oxygen-free operation, the column chromatography separation and purification operation, the RAFT controlled polymerization, the gel-permeation chromatography molecular characterization, FTIR, NMR, UV-Vis, and fluorescence emission spectroscopy, have been involved and practised. The photophysical properties of the synthesized TPE side-chain AIE polymers were investigated, with the relative fluorescence quantum yield in the THF/water mixture solution of high water fraction reached a high value of 17%.

Key words: Tetraphenylethylene (TPE), AIE polymer, RAFT controlled polymerization, Photophysical properties, Innovation experiment

MSC2000: 

  • G64