Catalyst-free copolymerization of ethyl diazoacetate（EDA） with carbethoxycarbene（CEC） has been achieved through two approaches：microwave irradiation and enzyme-assisted（Novozyme-435）system.The structure of the ...Catalyst-free copolymerization of ethyl diazoacetate（EDA） with carbethoxycarbene（CEC） has been achieved through two approaches：microwave irradiation and enzyme-assisted（Novozyme-435）system.The structure of the copolymer was characterized by MALDI-TOF MS（m/z from 2000 to 2450）,which suggested that the main chain of the copolymer consisted of-CH（COOEt）- and-N=NCH（COOEt）- frameworks.Fourier transform infrared（FT1R） spectrometry,elemental analysis,and Raman spectrometry proved the incorporation of azo group in the copolymer.The results indicated that the CEC radicals were generated under microwave irradiation（with or without Novozyme-435） from EDA.The mechanism study described that the generation speed of CEC radical was faster than its polymerization,and the excess CEC radicals improved the activity of the N2C1 group,thus inducing some EDA molecules as radicals.The two kinds of radicals co-coupled to result in poIy（CEC-co-EDA） through the C1/N2C1 copolymerization,but the homopolymerization of CEC radical occurred quicker than its cocoupling with activated EDA.展开更多
基金supported by the National Natural Science Foundation of China(Nos.21074097 and 21274112)
文摘Catalyst-free copolymerization of ethyl diazoacetate（EDA） with carbethoxycarbene（CEC） has been achieved through two approaches：microwave irradiation and enzyme-assisted（Novozyme-435）system.The structure of the copolymer was characterized by MALDI-TOF MS（m/z from 2000 to 2450）,which suggested that the main chain of the copolymer consisted of-CH（COOEt）- and-N=NCH（COOEt）- frameworks.Fourier transform infrared（FT1R） spectrometry,elemental analysis,and Raman spectrometry proved the incorporation of azo group in the copolymer.The results indicated that the CEC radicals were generated under microwave irradiation（with or without Novozyme-435） from EDA.The mechanism study described that the generation speed of CEC radical was faster than its polymerization,and the excess CEC radicals improved the activity of the N2C1 group,thus inducing some EDA molecules as radicals.The two kinds of radicals co-coupled to result in poIy（CEC-co-EDA） through the C1/N2C1 copolymerization,but the homopolymerization of CEC radical occurred quicker than its cocoupling with activated EDA.
