Kinetics of trifluorovinyl ether cyclopolymerization via Raman spectroscopy
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Polymerization kinetics of tris(trifluorovinyloxyphenyl)ethane (TVE) in the bulk are characterized by measuring the disappearance of the fluoro-olefin Raman signal at 1831 cm -1 normalized to an aromatic ring signal as an internal standard. The nth order kinetic model (dx/dt = k(1 -x) n) was applied to determine a reaction order of 2·0. Reaction rates below 85% conversion measured for various temperatures ranged from 2·2 × 10 -3 min -1 (t 1/2 = 454 min) to 3·1 × 10 -1 min -1 (t 1/2 = 3·3 min) for 130° C and 210° C, respectively. Above 85% olefin conversion, second order rate constants deviated from linearity as gelation ensued. An Arrhenius activation energy of 24·6 kcal mol -1 was determined. The non-destructive Raman technique was found to be an excellent method for measuring the cure kinetics in the bulk and may be applicable to 'on-line' needs for general application of perfluorocyclobutane (PFCB) polyarylether materials. © 1998 SCI.
author list (cited authors)
Cheatham, C. M., Lee, S., Laane, J., Babb, D. A., & Smith, D. W.