Perfluorocyclobutyl (PFCB) polymers have emerged as promising materials for a variety of lens structures, polymer optical fiber, and planar waveguide applications including thermo-optic and electro-optic devices.1-2 PFCB polymers are prepared by the free-radical mediated thermal cyclodimerization of aryl trifluorovinyl ether monomers (Scheme 1) from which a variety of thermally stable thermoplastic and thermosetting materials have been obtained with tailored optical properties. Recently we have focused on the random reactivity and stereorandom nature of the cyclodimerization mechanism to develop PFCB optical copolymers in an effort to optimize thermomechanical stability (Tg = 130-350 °C), processability, variable refractive index (1.45-1.6) and low loss (< 0.2 dB/cm) at 1550 nm. A versatile modular approach has been established which allows a wide-ranging choice of solution viscosity, thermal cure schedule, and ultimate molecular weight and degree of branching for linear versions or crosslink density for network systems. Copolymerization conversion, and thus viscoelastic properties and solubility, are precisely controlled by simple heating to a desired oligomeric architecture.

© 2003 Optical Society of America

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