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Kinetics of trifluorovinyl ether cyclopolymerization via Raman spectroscopy
Author(s) -
Cheatham C. Michael,
Lee SooNo,
Laane Jaan,
Babb David A.,
Smith Dennis W.
Publication year - 1998
Publication title -
polymer international
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.592
H-Index - 105
eISSN - 1097-0126
pISSN - 0959-8103
DOI - 10.1002/(sici)1097-0126(199808)46:4<320::aid-pi23>3.0.co;2-y
Subject(s) - raman spectroscopy , kinetics , arrhenius equation , activation energy , ether , polymerization , order of reaction , reaction rate constant , olefin fiber , polymer chemistry , materials science , chemical kinetics , chemistry , analytical chemistry (journal) , organic chemistry , catalysis , polymer , physics , quantum mechanics , optics
Polymerization kinetics of tris(trifluorovinyloxyphenyl)ethane (TVE) in the bulk are characterized by measuring the disappearance of the fluoro‐olefin Raman signal at 1831cm ‐1 normalized to an aromatic ring signal as an internal standard. The n th order kinetic model (d x /d t = 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 kcalmol ‐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.