高分子化学浙江大学polymer23measurementofratecoefficients.pptxVIP

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高分子化学浙江大学polymer23measurementofratecoefficients.pptx

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HistoryUp to the late 1980s termination and propagation rate coefficients were accessible only in their coupled form, kp/kt0.5 or individually via combination with pseudo flickering techniques like the rotating sector or spatially intermittent polymerization methods in combination with stationary polymerization measurements.The situation has dramatically improved with the invention of the pulsed laser polymerization (PLP) technique in the late 1980s. Since then, this technique has been extensively used to collate propagation and termination rate coefficients for various homo- and copolymerizations.8.1 Methods for the Measurement of kdRd = fkd [I]The concentration can be measured via any quantity to which it is directly proportional, such as a spectroscopic infrared (红外光谱) absorption that can be easily followed with reaction time. Infrared spectroscopy has been used extensively in the past to study the decay of organic peroxides in various reaction media.L0L0+2L0L0+2L0+3L08.2 Methods for the Measurement of kpPulsed Laser Polymerization–Size-Exclusion Chromatography (PLP-SEC)MW of polymer produced by PLP: L0,n=nkp[M]t0Monomerphotoinitiator, (solvent transfer agents)irradiated by a pulsed laser beam (5-20ns)8.2 Methods for the Measurement of kpElectron Spin Resonance Spectroscopy-Stationary Polymerization (ESR)(电子自旋共振)8.2 Methods for the Measurement of kpQuenched Instationary Polymerization Systems (QUIPS)A photopolymerizable mixture passes through a capillary system, is irradiated at a specific location, and polymerizes in the capillary during a well-defined dark period until it drops into a quenching bath with an inhibitor(nitroxyl radicals).Measuring the chain length distribution by size-exclusion chromatography that allows determination of kp in accordance with the equation.L=kp[M]t08.3 Methods for the Measurement of ktrMayo methodThe usual procedure for measuring the chain transfer constant CT involves determination of Xn for a range of [T]/[M] values and plotti