A kinetic model was developed to describe the atom transfer radical polymerization (ATRP) of 2(N,N-dimethylarnino) ethyl methacrylate (DMAEMA). The model was based on a polymerization mechanism, which included the ato...A kinetic model was developed to describe the atom transfer radical polymerization (ATRP) of 2(N,N-dimethylarnino) ethyl methacrylate (DMAEMA). The model was based on a polymerization mechanism, which included the atom transfer equilibrium for primary radical, the propagation of growing polymer radical, and the atom transfer equilibrium for the growing polymer radical. An experiment was carried out to measure the conversion of monomer, the number-average molecular weight of polymer and molecular weight distribution for the ATRP process of DMAEMA. The experimental data were used to correlate the kinetic model and rate constants were obtained. The rate constants of activation and deactivation in the atom transfer equilibrium for primary radical are 1.0 x 10(4) L(.)mol(-1.)s(-1) and 0.04 L(.)mol(-1.)s(-1), respectively. The rate constant of the propagation of growing polymer radical is 8.50 L(.)mol(-1.)s(-1), and the rate constants of activation and deactivation in the atom transfer equilibrium for growing polymer radical are 0.045 L(.)mol(-1.)s(-1) and 1.2 x 10(5) L(.)mol(-1.)s(-1), respectively. The values of the rate constants represent the features of the ATRP process. The kinetic model was used to calculate the ATRP process of DMAEMA. The results show that the calculations agree well with the measurements.展开更多
Shirota's kinetic model and our kinetic model were used to treat the kinetic data of styrene (St) and N-phenylmaleimide (PMI) copolymerization in which charge-transfer complex (CTC) was formed. The results obtaine...Shirota's kinetic model and our kinetic model were used to treat the kinetic data of styrene (St) and N-phenylmaleimide (PMI) copolymerization in which charge-transfer complex (CTC) was formed. The results obtained by Shirota's kinetic model were disagreed with the experiments and the experimental phenomena could not be explained. The kinetic data of all feed fractions can be treated with our kinetic model, and the experimental phenomena can be explained from the propagation constants and reactivity ratios. Our kinetic model is also suitable for the kinetic data of methyl methacrylate (MMA) and PMI copolymerization in which CTC can not be formed.展开更多
Phthalate esters （PAEs）, which can disturb human endocrine system, have been widely detected in vegetable greenhouse agriculture in China. To investigate the effects of environmental factors on PAEs in soils, pollut...Phthalate esters （PAEs）, which can disturb human endocrine system, have been widely detected in vegetable greenhouse agriculture in China. To investigate the effects of environmental factors on PAEs in soils, pollution sources were identified, and the cumulative risks of PAEs to humans through vegetables in the diet were evaluated in this study. Ninety-eight vegetable samples were collected from 10 markets along with 128 vegetable and 111 soil samples from agricultural greenhouses and open field. All soil and vegetable samples were contaminated with PAEs, and the total concentrations of the 5 PAEs, including dimethyl phthalate （DMP）, diethyl phthalate （DEP）, di-iso-butyl phthalate （DiBP）, di-n-butyl phthalate （DnBP）, and di-2-ethylhexyl phthalate （DEHP）, were in the ranges of 0.26-2.53 mg kg-1 for soils and 0.95-8.09 mg kg-1 for vegetables. Three components extracted from principle component analysis could explain 51.2%, 19.8%, and 15.3% of the total variance of the 5 PAEs in soils, which may represent three major sources of PAEs, i.e., wastewater irrigation, application of fertilizers and pesticides, and plastic film. Long-term greenhouse cultivation could accumulate DEHP in soils, and a higher soil FeOx content reduced the DnBP concentration. Based on a survey of vegetables in the diet, the hazard index of PAEs was 〈 0.15 for individuals in different cities. The exposure of PAEs through vegetable intake was higher than the total exposure from other food stuffS, inhalation, and dermal absorption. More attention should be g!ven to controlling PAEs in greenhouse vegetables.展开更多
文摘A kinetic model was developed to describe the atom transfer radical polymerization (ATRP) of 2(N,N-dimethylarnino) ethyl methacrylate (DMAEMA). The model was based on a polymerization mechanism, which included the atom transfer equilibrium for primary radical, the propagation of growing polymer radical, and the atom transfer equilibrium for the growing polymer radical. An experiment was carried out to measure the conversion of monomer, the number-average molecular weight of polymer and molecular weight distribution for the ATRP process of DMAEMA. The experimental data were used to correlate the kinetic model and rate constants were obtained. The rate constants of activation and deactivation in the atom transfer equilibrium for primary radical are 1.0 x 10(4) L(.)mol(-1.)s(-1) and 0.04 L(.)mol(-1.)s(-1), respectively. The rate constant of the propagation of growing polymer radical is 8.50 L(.)mol(-1.)s(-1), and the rate constants of activation and deactivation in the atom transfer equilibrium for growing polymer radical are 0.045 L(.)mol(-1.)s(-1) and 1.2 x 10(5) L(.)mol(-1.)s(-1), respectively. The values of the rate constants represent the features of the ATRP process. The kinetic model was used to calculate the ATRP process of DMAEMA. The results show that the calculations agree well with the measurements.
基金Supported by the Doctoral Foundation of the Education Commission of China.
文摘Shirota's kinetic model and our kinetic model were used to treat the kinetic data of styrene (St) and N-phenylmaleimide (PMI) copolymerization in which charge-transfer complex (CTC) was formed. The results obtained by Shirota's kinetic model were disagreed with the experiments and the experimental phenomena could not be explained. The kinetic data of all feed fractions can be treated with our kinetic model, and the experimental phenomena can be explained from the propagation constants and reactivity ratios. Our kinetic model is also suitable for the kinetic data of methyl methacrylate (MMA) and PMI copolymerization in which CTC can not be formed.
基金supported by the National Basic Research Program of China (No. 2014CB441105)the National Natural Science Foundation of China (No. 21377136)+1 种基金the One Hundred Person Project of Chinese Academy of Sciences (No. 2012133)the 135 Research Program of Chinese Academy of Sciences
文摘Phthalate esters （PAEs）, which can disturb human endocrine system, have been widely detected in vegetable greenhouse agriculture in China. To investigate the effects of environmental factors on PAEs in soils, pollution sources were identified, and the cumulative risks of PAEs to humans through vegetables in the diet were evaluated in this study. Ninety-eight vegetable samples were collected from 10 markets along with 128 vegetable and 111 soil samples from agricultural greenhouses and open field. All soil and vegetable samples were contaminated with PAEs, and the total concentrations of the 5 PAEs, including dimethyl phthalate （DMP）, diethyl phthalate （DEP）, di-iso-butyl phthalate （DiBP）, di-n-butyl phthalate （DnBP）, and di-2-ethylhexyl phthalate （DEHP）, were in the ranges of 0.26-2.53 mg kg-1 for soils and 0.95-8.09 mg kg-1 for vegetables. Three components extracted from principle component analysis could explain 51.2%, 19.8%, and 15.3% of the total variance of the 5 PAEs in soils, which may represent three major sources of PAEs, i.e., wastewater irrigation, application of fertilizers and pesticides, and plastic film. Long-term greenhouse cultivation could accumulate DEHP in soils, and a higher soil FeOx content reduced the DnBP concentration. Based on a survey of vegetables in the diet, the hazard index of PAEs was 〈 0.15 for individuals in different cities. The exposure of PAEs through vegetable intake was higher than the total exposure from other food stuffS, inhalation, and dermal absorption. More attention should be g!ven to controlling PAEs in greenhouse vegetables.
