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Kinetics and modeling of the diffusion‐controlled diallyl terephthalate polymerization
Author(s) -
Hace Iztok,
Golob Janvit,
Krajnc Matjaž
Publication year - 2004
Publication title -
polymer engineering and science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.503
H-Index - 111
eISSN - 1548-2634
pISSN - 0032-3888
DOI - 10.1002/pen.20204
Subject(s) - polymerization , materials science , reaction rate constant , diffusion , kinetics , fourier transform infrared spectroscopy , differential scanning calorimetry , polymer chemistry , thermodynamics , bulk polymerization , kinetic energy , polymer , radical polymerization , chemistry , chemical engineering , composite material , physics , quantum mechanics , engineering
Free radical polymerization kinetics of diallyl terephthalate in bulk was investigated in a wide temperature range from 50°C to 150°C with four different peroxide initiators. Conversion points were measured using Fourier Transform Infrared (FTIR) measurements. The initiator efficiencies and the initiator decomposition rate constants were evaluated from special experiments, applying the theory of dead end polymerization . In addition, the ratios between the degradative and the effective kinetic rate constants to propagation rate constants were obtained from molecular weight measurements at various initiator concentrations. The ratio of chemically controlled termination and propagation rate constant k pc 2 / k tc of the polymerization system was obtained using the initial rates of polymerization and the number average molecular weight data between 0.25 · 10 −3 and 15.7 · 10 −3 L mol −1 s −1 . The glass transition temperature of the polymer, 191°C, was measured by the Alternating Differential Scanning Calorimetry (ADSC) technique. Computed conversions from the developed kinetic model were in good agreement with the conversion and molecular weight measured data. The values of diffusion controlled propagation and termination rate constants k td 0 and k pd 0 with clear and physical meaning were the only two parameters obtained from the developed kinetic model fitting. Polym. Eng. Sci. 44:2005–2018, 2004. © 2004 Society of Plastics Engineers.