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

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

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.

The copolymerization of glyceryl methacrylate （GMA） and methyl methacrylate （MMA） was conducted in a solution polymerization system resulting in the formation of copolymer P （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 （PTIR） 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.