The initiation mechanism of methyl methacrylate (MMA) polymerization by organic peroxide and polymerizable aromatic tertiary amine such as N-methacryloyloxyethyl-N-methyl aniline (MEMA) binary system has been studied....The initiation mechanism of methyl methacrylate (MMA) polymerization by organic peroxide and polymerizable aromatic tertiary amine such as N-methacryloyloxyethyl-N-methyl aniline (MEMA) binary system has been studied. The kinetics of polymerization of MMA and the ESR spectra of organic peroxide/MEMA system were determined. Based on the ESR study and the end-group analysis by UV spectra of the polymer formed, the initiation mechanism is proposed.展开更多
A new carbon bridged cyclopentadienyl chromium complex of the type [(C5H4)C(CH3)2 CH2(C5H4N)]CrCl2 was prepared by treatment of CrCl3·(THF)3 in THF solution with the lithium salt of ligand containing cycl...A new carbon bridged cyclopentadienyl chromium complex of the type [(C5H4)C(CH3)2 CH2(C5H4N)]CrCl2 was prepared by treatment of CrCl3·(THF)3 in THF solution with the lithium salt of ligand containing cyclopentadienyl and pyridyl groups. The chromium complex was characterized by 1H NMR and elemental analysis(EA), and the crystal structure was determined by X-ray diffraction analysis. Activated by Al(i-Bu)3, the chromium complex displayed a very high activity for methyl methacrylate(MMA) polymerization. After 24 hours,more than 95.5% MMA was converted to polymethyl methacrylate(PMMA) with a viscosity average molecular weight(Wη) of 416000 g·mol-1 at 60 ℃ for MMA/ Al(i-Bu)3 /chromium catalyst molar ratio of up to 2000:20:1. Effects of temperature, molar ratios of MMA/catalyst and catalyst/cocatalyst on the polymerization have been studied. The high conversion of MMA and high molecular weight of PMMA with narrow molecular weight distribution is caused by the unique stable active site formed by the new chromium complex and aluminum cocatalyst.展开更多
The polymerization of methyl methacrylate (MMA) initiated by organic peroxide and polymerizable aromatic tertiary amine such as N, N-di (2-α-methylacryloyloxy propyl)-p-toluidine (MP)_2PT binary system has been studi...The polymerization of methyl methacrylate (MMA) initiated by organic peroxide and polymerizable aromatic tertiary amine such as N, N-di (2-α-methylacryloyloxy propyl)-p-toluidine (MP)_2PT binary system has been studied. It was found that the (MP)_2PT promotes MMA polymerization, and the kinetics of MMA polymerization fits the radical polymerization rate equation. Based on the ESR studies and the end-group analysis the initiation mechanism is proposed.展开更多
基金Project supported by the National Natural Science Foundation of China
文摘The initiation mechanism of methyl methacrylate (MMA) polymerization by organic peroxide and polymerizable aromatic tertiary amine such as N-methacryloyloxyethyl-N-methyl aniline (MEMA) binary system has been studied. The kinetics of polymerization of MMA and the ESR spectra of organic peroxide/MEMA system were determined. Based on the ESR study and the end-group analysis by UV spectra of the polymer formed, the initiation mechanism is proposed.
基金Funded by the National Natural Science Foundation of China(No.51204125)the Natural Science Foundation of Hubei Province(Nos.2014CFB812 and 2014CFB810)the Open Fund Project Funded by the Key Laboratory of Coal Conversion and New Carbon Materials of Hubei Province in China(No.WKDM201302)
文摘A new carbon bridged cyclopentadienyl chromium complex of the type [(C5H4)C(CH3)2 CH2(C5H4N)]CrCl2 was prepared by treatment of CrCl3·(THF)3 in THF solution with the lithium salt of ligand containing cyclopentadienyl and pyridyl groups. The chromium complex was characterized by 1H NMR and elemental analysis(EA), and the crystal structure was determined by X-ray diffraction analysis. Activated by Al(i-Bu)3, the chromium complex displayed a very high activity for methyl methacrylate(MMA) polymerization. After 24 hours,more than 95.5% MMA was converted to polymethyl methacrylate(PMMA) with a viscosity average molecular weight(Wη) of 416000 g·mol-1 at 60 ℃ for MMA/ Al(i-Bu)3 /chromium catalyst molar ratio of up to 2000:20:1. Effects of temperature, molar ratios of MMA/catalyst and catalyst/cocatalyst on the polymerization have been studied. The high conversion of MMA and high molecular weight of PMMA with narrow molecular weight distribution is caused by the unique stable active site formed by the new chromium complex and aluminum cocatalyst.
文摘The polymerization of methyl methacrylate (MMA) initiated by organic peroxide and polymerizable aromatic tertiary amine such as N, N-di (2-α-methylacryloyloxy propyl)-p-toluidine (MP)_2PT binary system has been studied. It was found that the (MP)_2PT promotes MMA polymerization, and the kinetics of MMA polymerization fits the radical polymerization rate equation. Based on the ESR studies and the end-group analysis the initiation mechanism is proposed.