SUN Yan, ZHAN Yan, JIANG Qiong, SHI Yuanyuan, WANG Qiang, KONG Lizhi, ZHAI Guangqun. MECHANISTIC STUDY OF CATALYTIC OXIDATIVE COPOLYMERIZATION OF 2-(N,N-DIMETHYLAMINO)ETHYL METHACRYLATE AND METHYL METHACRYLATE. [J]. Acta Polymerica Sinica (10):1218-1224(2010)
DOI:
SUN Yan, ZHAN Yan, JIANG Qiong, SHI Yuanyuan, WANG Qiang, KONG Lizhi, ZHAI Guangqun. MECHANISTIC STUDY OF CATALYTIC OXIDATIVE COPOLYMERIZATION OF 2-(N,N-DIMETHYLAMINO)ETHYL METHACRYLATE AND METHYL METHACRYLATE. [J]. Acta Polymerica Sinica (10):1218-1224(2010) DOI: 10.3724/SP.J.1105.2010.09406.
MECHANISTIC STUDY OF CATALYTIC OXIDATIVE COPOLYMERIZATION OF 2-(N,N-DIMETHYLAMINO)ETHYL METHACRYLATE AND METHYL METHACRYLATE
The CuX/pentamethyldi-ethylenetriamine(PMDETA)catalyzed oxidative copolymerization of 2-(N
N-dimethylamino)ethyl methacrylate (DMAEMA) and methyl methacrylate (MMA) was investigated.The kinetics were compared by varying the monomer ratio
catalyst concentration and the reaction temperature.The results showed that the copolymerization could proceed under the monomer ratio ([DMAEMA]∶[MMA]=10∶0~5∶5)
catalyst concentration ([CuCl/PMDETA3]= 3.1×10-5 mol/L ~6×10-3 mol/L) and the reaction temperature (30~80℃) which were investigated in the paper
and the molecular weight increased with the reaction time
while the molecular weight distribution maintained rather broad.It was showed from the 1HNMR that there were DMAEMA units and MMA units in the copolymer
while the DSC indicated that the system of copolymer was partially compatible.The CuCl/PMDETA-catalyzed atom transfer radical polymerization (ATRP) of MMA using the so-obtained PDMAEMA as the macroinitiator was successful
confirming the presence of the C-Cl terminal functionality.Thus
the following mechanism might operate: 1) O2 oxidized CuCl into [Cu(Ⅱ)Cl]+ species; 2) [Cu(Ⅱ)Cl]+ oxidized dimethylamino moiety into N—CH2・radicals; 3) N—CH2・radicals and[Cu(Ⅱ)Cl]+ formed the reverse ATRP system.The above processes finally led to polymer with C—Cl end group.