氯代铟卟啉末端功能化的PMMA活性自由基聚合材料制备及光学非线性研究(特邀)  

Preparation and optical nonlinearity of PMMA living radical polymerization materials functionalized with indium chloride porphyrin(Invited)

作　　者：徐超越 马鹏飞 刘大军[1] Xu Chaoyue;Ma Pengfei;Liu Dajun(School of Chemistry and Environmental Engineering,Changchun University of Science and Technology,Changchun 130022,China)

机构地区：[1]长春理工大学化学与环境工程学院,吉林长春130022

出　　处：《红外与激光工程》2020年第12期355-361,共7页Infrared and Laser Engineering

基　　金：吉林省重点科技研发项目(No.20180201083GX);长春理工大学科技创新基金(No.CX2015006)。

摘　　要：合成了5,10,15-三苯基-20-(4-羟基苯基)氯代卟啉铟,采用2-氯丙酰氯对其封端作为引发剂,以甲基丙烯酸甲酯为单体,CuCl/PMDETA为催化体系,通过原子转移自由基聚合得到了不对称卟啉铟末端功能化的线形聚甲基丙烯酸甲酯。通过UV-vis、FT-IR和1H-NMR进行结构表征。利用凝胶渗透色谱对聚合物的分子量及分子量分布指数进行测定,测试结果表明,聚合物的分散度范围为1.11~1.21,分子量分布较窄,聚合反应具有良好的可控性。采用倍频锁模Nd:YAG皮秒脉冲激光系统,在输出激光波长532 nm,脉冲宽度21 ps的条件下,利用Z-扫描对系列卟啉化合物的三阶非线性光学性质进行了测试分析,通过对实验数据的模拟和计算表明,聚合度为16,分子量为2414的聚合物三阶非线性极化率值最大,为1.144×10^(-12)esu。5,10,15-triphenyl-20-(4-hydroxyphenyl)chloroporphyrin indium was synthesized.Using 2-chloropropionyl chloride end-capped mono-hydroxy metalloporphyin as initiator,methyl methacrylate as monomer and CuCl/PMDETA as the catalyst system,a new linear polymethylmethacrylate(PMMA)with asymmetric indium porphyrin end functionalized was synthesized by atom transfer radical polymerization(ATRP)method.The structure of porphyrin compounds was characterized by Fourier transform infrared spectroscopy(FT-IR),ultraviolet-visible spectroscopy(UV-vis)and nuclear magnetic resonance hydrogen spectrum(1H NMR)techniques.Molecular weight and molecular weight distribution of the linear polymers were obtained by gel permeation chromatography(GPC).It indicated that the molecular weight distribution was narrow and the molecular weight distribution range was between 1.11 and 1.21.Meanwhile,the polymerization reaction had a good controllability.By Z-scan method,the third-order nonlinear optical properties of porphyrin compounds were tested using a frequency-doubled mode locked Nd:YAG picosecond laser system at wavelength of 532 nm with 21 ps pulse,the results showed that the third-order nonlinear polarizability(χ^((3)))of polymer with polymerization degree of 16 and molecular weight of 2414 is 1.144×10^(-12)esu.

关 键 词：三阶非线性 氯代铟卟啉 原子转移自由基聚合 

分 类 号：O437[机械工程—光学工程]