Novel Access to Propagation Rate Coefficients of Radical Polymerization by the SP-PLP-EPR Method

被引:25
作者
Kattner, Hendrik [1 ]
Drawe, Patrick [1 ]
Buback, Michael [1 ]
机构
[1] Univ Gottingen, Inst Phys Chem, D-37077 Gottingen, Germany
关键词
ESR/EPR; kinetics (polym); laser-induced polymerizations; radical polymerization; propagation rate coefficient; LENGTH-DEPENDENT TERMINATION; FLASH-INITIATED POLYMERIZATION; SIZE-EXCLUSION-CHROMATOGRAPHY; INTRAMOLECULAR CHAIN TRANSFER; INDIVIDUAL KINETIC CONSTANTS; PULSED-LASER POLYMERIZATION; TERT-BUTYL METHACRYLATE; BETA-SCISSION REACTIONS; AQUEOUS-SOLUTION; ACRYLIC-ACID;
D O I
10.1002/macp.201500191
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
A novel method for k(p) measurement is presented, in which time-resolved electron paramagnetic resonance detection of radical concentration after applying a single laser pulse (SP-PLP-EPR) is carried out in conjunction with measuring monomer conversion induced by the laser pulse. The method is particularly useful for the study of fully ionized monomers, as will be outlined by experiments on trimethylaminoethyl methacrylate chloride (TMAEMA, 2-(methacryloyloxy)-N,N,N-trimethylethan-1-aminium chloride, 20 wt% in aqueous solution) at 60 degrees C. In addition to k(p), the method provides termination rate coefficient data. The reliability of the so-obtained rate coefficients is demonstrated by chemically induced experiments and by measuring TMAEMA conversion after single-pulse initiation via near-infrared (NIR) spectroscopy.
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页码:1737 / 1745
页数:9
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