Kinetic behavior of atom transfer radical polymerization of dimethacrylates

被引:42
作者
Yu, Q [1 ]
Zhang, JZ
Cheng, ML
Zhu, SP
机构
[1] Jiangsu Polytech Univ, Dept Mat Sci & Engn, Changzhou 213016, Jiangsu, Peoples R China
[2] McMaster Univ, Dept Chem Engn, Hamilton, ON L8S 4L7, Canada
关键词
activation/deactivation equilibrium; atom transfer radical polymerization (ATRP); crosslinking; diffusion control; kinetics; poly(ethylene glycol) dimethacrylate;
D O I
10.1002/macp.200500378
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
The reaction behavior and kinetics of the atom transfer radical polymerization (ATRP) of poly(ethylene I glycol) dimethacrylates (PEGDMA) were studied with respect to polymerization rate, vinyl conversion and the development of a crosslinked network. The polymerization rates were much slower than the corresponding conventional free radical polymerizations with the ATRP systems exhibiting milder autoacceleration. The linear relationship of the semilogarithmic kinetic plot of ln([M-o/[M]) vs. time did not provide good evidence for any living nature of the system because of the combined effects of diffusion controlled radical deactivation and diffusion controlled monomer propagation. The influence of the spacer length (CH2CH2O)(x) between the vinyl moieties of the dimethacrylates on the polymerization kinetics was examined. The polymerization rate and final vinyl conversion increased as value of x decreased from 14 to 9 to 4. These increases in rate and conversion were caused by a more rigid network structure with shorter spacer lengths, and thus more restricted diffusion of the catalyst/ ligand complexes that impeded the radical deactivation. The effect of temperature on the polymerization rate and final vinyl conversion were also investigated.
引用
收藏
页码:287 / 294
页数:8
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