Citation: Yan Sun, Guang-qun Zhai. CuSO4-CATALYZED SELF-INITIATED RADICAL POLYMERIZATION OF 2-(N,N-DIMETHYLAMINO)ETHYL METHACRYLATE AS AN INTRINSICALLY REDUCING INIMER[J]. Chinese Journal of Polymer Science, ;2013, 31(8): 1161-1172. doi: 10.1007/s10118-013-1317-5 shu

CuSO4-CATALYZED SELF-INITIATED RADICAL POLYMERIZATION OF 2-(N,N-DIMETHYLAMINO)ETHYL METHACRYLATE AS AN INTRINSICALLY REDUCING INIMER

Yan Sun ,
Guang-qun Zhai

Received Date: 8 October 2012
Revised Date: 11 December 2012

Fund Project: This work was financially supported by the National Natural Science Foundation of China (No. 20674033), Natural Science Foundation of Jiangsu Province (No. BK2008142) and Scientific Research Foundation for the Returned Overseas Chinese Scholars (State Education Ministry).

Since tertiary amines (C-H) can be oxidized by peroxides and transition metal cations in high oxidation states into C radicals to initiate vinylic polymerizations of methacrylates, Cu2+ and 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA) form a polymerizable redox initiating pair, in which DMAEMA serves as an intrinsically reducing inimer. CuSO4-catalyzed aqueous self-initiated radical polymerizations of DMAEMA were successfully performed at ambient temperature via a continuous Cu2+-tertiary amine redox initiation based on catalyst regeneration in the presence of O2. The polymerization kinetics was monitored by gas chromatography and the structure of PDMAEMA was characterized by gel-permeation chromatography, nuclear magnetic resonance spectroscopy, laser light scattering and online intrinsic-viscosity analysis. Both the monomer conversion and the molecular weight of PDMAEMA increase with the reaction while the molecular weight distribution maintains rather broad, as the Cu2+-DMAEMA redox-initiation leads to linear PDMAEMA chains with terminal methacryloxyl moieties, and the Cu2+-PDMAEMA redox-initiation results in branched chains. The branched topology forms and develops only for the high-MW components of the PDMAEMA. Our results provide a facile strategy to prepare branched polymers from such commercially available intrinsically reducing inimers using a negligible concentration of regenerative air-stable catalysts.
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