Preparation of novel cyclic olefin copolymer with high glass transition temperature

A series of novel cyclic olefin copolymers (COCs), including ethylene/tricyclo[4.3.0.12,5]deca-3-ene (TDE), ethylene/tricyclo[4.4.0.12,5]undec-3-ene (TUE), and ethylene/tricyclo[6.4.0.19,12]tridec-10-ene (TTE) copolymers, have been synthesized via effective copolymerizations of ethylene with bulk cyclic olefin comonomers using bis(-enaminoketonato) titanium catalysts (1a [PhNC(CH3)CHC(CF3)O]2TiCl2; 1b: [PhNC(CF3)CHC(Ph)O]2TiCl2). With modified methylaluminoxane as a cocatalyst, both catalysts exhibit high catalytic activities, producing high molecular weight copolymers with high comonomer incorporations and unimodal molecular weight distributions. The microstructures of obtained ethylene/COCs are established by combination of 1H, 13C NMR, 13C DEPT, HSQC 1H13C, and 1H1H COSY NMR spectra. DSC analyses indicate that the glass transition temperature (Tg) increases with the enhancement of comonomer volume (TDEethylene/TTE copolymer with the low content of 35.8 mol %. TGA analyses reveal that these copolymers all possess high thermal stability with degradation temperatures (Td) higher than 370 degrees C in N2 and air. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3144-3152