Na/HMPA溶剂化电子引发MMA的聚合行为  

Polymerization of methyl methacrylate via initiation of the solvated electron from Na/HMPA solution

作　　者：李智[1] 鲁潇[1] 沈政[1] 夏逸尘 许平 黄健[1] LI Zhi;LU Xiao;SHEN Zheng;XIA Yicheng;XU Ping;HUANG Jian(College of Materials Science and Engineering,Nanjing Tech University,Nanjing 210009,China)

机构地区：[1]南京工业大学材料科学与工程学院,江苏南京210009

出　　处：《南京工业大学学报（自然科学版）》2019年第1期36-40,共5页Journal of Nanjing Tech University(Natural Science Edition)

基　　金：江苏高校优势学科建设工程

摘　　要：以Na/六甲基磷酰三胺(HMPA)的溶剂化电子溶液引发甲基丙烯酸甲酯(MMA)的聚合,研究聚合动力学及阻聚性质,采用傅里叶变换红外光谱(FT-IR)和核磁共振(NMR)方法表征聚合物的分子量和化学结构。结果表明:溶剂化电子引发MMA聚合的活性种具有长寿命性质。得到的聚甲基丙烯酸甲酯(PMMA)为无规结构,其全同、无规和间同结构的占比分别为10. 2%、41. 0%和48. 8%。1,1-二苯基-2-三硝基苯肼(DPPH)和O_2是强烈的阻聚剂,而H_2O不具有阻聚性能,排除了溶剂化电子引发MMA聚合的阴离子聚合机制。Poly(methyl methacrylate)(PMMA)was prepared via the chain initiation of the solvated electron from Na/hexamethylphosphoramide(HMPA)solution.Polymerization behaviors,such as kinetics,molecular weight dependence on the monomer conversion and the inhibition feature,were investigated.Chemical structures of PMMA were characterized by Fourier transform infrared spectrometry(FT-IR)and nuclear magnetic resonance(NMR).Results of polymerization kinetics and molecular weight dependence on the monomer conversion suggested that the long-living reactive species were in the chain propagation.The atactic configuration of PMMA was 10.2%of the isotactic,41.0%of atactic and 48.8%of syndiotactic contents,respectively.The polymerization was seriously retarded by the radical inhibitors of 1,1-diphenyl-2-picrylhydrazyl(DPPH)and oxygen,and not by water,a typical inhibitor for the ionic polymerization.It was assumed that the solvated electron initiated polymerization of MMA would not follow the anionic polymerization mechanism.

关 键 词：溶剂化电子 NA 六甲基磷酰三胺 聚甲基丙烯酸甲酯 长寿命活性种 

分 类 号：O631.5[理学—高分子化学]