Kinetics of trifluorovinyl ether cyclopolymerization via Raman spectroscopy

• Published in: Polymer international 1998-08, Vol.46 (4), p.320-324
• Main Authors: Cheatham, C. Michael, Lee, Soo-No, Laane, Jaan, Babb, David A., Smith Jr, Dennis W.
• Format: Article
• Language: English
• Subjects: Applied sciences; Exact sciences and technology; Organic polymers; perfluorocyclobutane polymers; Physicochemistry of polymers; Polymerization; polymerization kinetics; Preparation, kinetics, thermodynamics, mechanism and catalysts; Raman spectroscopy; trifluorovinyl ether cyclopolymerization
• ISSN: 0959-8103; 1097-0126
• DOI: 10.1002/(SICI)1097-0126(199808)46:4<320::AID-PI23>3.0.CO;2-Y

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 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 2·2×10‐3min‐1 (t1/2 = 454 min) to 3·1×10‐1min‐1 (t1/2 = 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.