物理化学学报 >> 2009, Vol. 25 >> Issue (02): 341-346.doi: 10.3866/PKU.WHXB20090225

研究论文 上一篇    下一篇

在共聚物P(GMA-co-MMA)侧链实现卟啉化合物的同步合成与键合

王飞宇; 高保娇; 王蕊欣   

  1. 中北大学化学工程系, 太原 030051
  • 收稿日期:2008-08-15 修回日期:2008-10-10 发布日期:2009-01-16
  • 通讯作者: 高保娇 E-mail:gaobaojiao@126.com

Simultaneous Synthesis and Linkage of Porphyrin onto Side Chain of Copolymer P(GMA-co-MMA)

WANG Fei-Yu; GAO Bao-Jiao; WANG Rui-Xin   

  1. Department of Chemical Engineering, North University of China, Taiyuan 030051, P. R. China
  • Received:2008-08-15 Revised:2008-10-10 Published:2009-01-16
  • Contact: GAO Bao-Jiao E-mail:gaobaojiao@126.com

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摘要： 采用溶液聚合的方法, 先合成了甲基丙烯酸缩水甘油酯(GMA)与甲基丙烯酸甲酯(MMA)的线型共聚物P(GMA-co-MMA); 然后通过环氧基团的开环成醚反应, 将对羟基苯甲醛(HBA)键合于共聚物的侧链上, 形成键合有苯甲醛(BA)的聚合物BA-P(GMA-co-MMA); 最后采用Adler方法, 以BA-P(GMA-co-MMA)、苯甲醛及吡咯为反应物, 在均相反应体系中, 成功地实现了苯基卟啉(PP)在共聚物P(GMA-co-MMA)侧链的同步合成与键合, 制得了卟啉功能化的线型大分子PP-P(GMA-co-MMA). 通过FTIR及1H-NMR对功能大分子PP-P(GMA-co-MMA)的化学结构进行了表征, 对其谱学性能进行了研究, 较为深入地分析了其光物理行为. 实验结果表明, 大分子PP-P(GMA-co-MMA)具有与四苯基卟啉(TPP)相同的电子吸收光谱与荧光发射光谱. 随着侧链上PP键合量的增大, 大分子PP-P(GMA-co-MMA)的Soret与Q吸收带的峰强均不断增强, 而Q发射带的强度则呈现先增大后有所减弱的规律, 这是由大分子内的能量转移所致.

关键词: 苯基卟啉, 甲基丙烯酸缩水甘油酯, 卟啉功能化的聚合物, 同步合成与键合, 光谱性能

Abstract: The copolymerization of glyceryl methacrylate (GMA) and methyl methacrylate (MMA) was conducted in a solution polymerization systemresulting in the formation of copolymerP (GMA-co-MMA). Parahydroxybenzaldehyde was then bound to the side chains of P(GMA-co-MMA) via ring-opening and ether-forming reactions of the epoxy groups on P(GMA-co-MMA). A benzaldehyde (BA)-bound copolymer BA-P(GMA-co-MMA) was thus prepared. The simultaneous synthesis and linkage of the porphyrin onto the side chains of P(GMA-co-MMA) was realized successfully using the Adler method in a homogeneous system. Benzaldehyde, BA-P(GMA-co-MMA), and pyrrole were used as reactants, resulting in the porphyrin (PP)-functionalized line-type macromolecule PP-P(GMA-co-MMA). The chemical structure of PP-P(GMA-co-MMA) was characterized by Fourier transform infrared (FTIR) spectroscopy and nuclear magnetic resonance (1H-NMR) spectroscopy. The spectral properties of PP-P(GMA-co-MMA) were studied and its photophysical behavior was investigated in depth. Experimental results show that PP-P(GMA-co-MMA) has the same electronic absorption spectrum and fluorescence emission spectrum as tetraphenyl porphyrin. In the electronic absorption spectra of PP-P(GMA-co-MMA) both the Soret absorption band and the Q absorption band strengthen as the amount of bound porphyrin increaseds. The Q emission band intensity of PP-P(GMA-co-MMA) also first increases with the increase of the amount of bound porphyrin until to a maximum, and then decreases if more porphyrin units are present. Intramolecular energy transfer of the macromolecule PP-P(GMA-co-MMA) should be responsible for this behavior.

Key words: Phenyl porphyrin, Glyceryl methacrylate, Porphyrin-functionalized polymer, Synchronistic synthesis and linkage, Spectrumproperty