Dynamics of Poly(cyclohexene carbonate) as a Function of Molar Mass

Stereoregular poly(cyclohexene carbonate) (PCHC) homopolymers were prepared via copolymerization of cyclohexene oxide and carbon dioxide (CO2) using (R,R)-(salcy)-CoCl and bis(triphenylphosphine)iminium chloride as a catalyst. The homopolymers had molar masses in the range of 4800–33,000 g mol–1 and relatively narrow dispersity after careful fractionation, as required for the molecular dynamics investigation. We employed differential scanning calorimetry and dielectric spectroscopy, the latter as a function of temperature and pressure, for investigating the thermal properties and the molecular dynamics, respectively. The segmental dynamics in the vicinity of the liquid-to-glass temperature was very complex. The dual segmental processes were inseparable by decreasing the temperature or by increasing the pressure. Based on DFT calculations of the dipole moment, they were ascribed to different stereo sequences of the PCHC backbone. The limiting glass temperature, Tg, for very high molar masses was ∼125 °C. The high Tg value obtained herein well justifies its application as a CO2-based alternative for polystyrene (PS) in a variety of materials based on block copolymers. Moreover, fragility increased with increasing molar mass with values intermediate to poly(styrene) and poly(cyclohexyl methacrylate). The flexible cyclohexyl group in PCHC undergoing intramolecular chair-to-chair conversion increases the packing ability and consequently decreases the fragility. PCHC is a brittle material because it lacks entanglements even for the higher molar masses investigated herein, which is relevant for application as a PS substitute. Within the investigated range of molar masses, the dependences of the terminal relaxation times, τΝΜ, and of the zero-shear viscosity, ηο, on the molar mass, M, are τΝΜ/τSM ∼ M3.2 and ηο ∼ M1.4, revealing an intermediate behavior between Rouse and entangled chains.