PHASE-TRANSITIONS IN NARROW-MOLAR-MASS SAMPLES OF SIDE-CHAIN LIQUID-CRYSTALLINE POLYMERS - MOLAR-MASS DEPENDENCE

The molar-mass dependence of phase transitions in narrow-molar-mass samples of smectic side-chain poly(vinyl ether)s is discussed with reference to earlier data by Stevens et al. and Percec et al. on narrow fractions of smectic side-chain polysiloxanes and polymethacrylates. The constant heat of isotropization (DELTAh(i)) and the proportionality between the glass transition temperature (T(g)) and the reciprocal degree of polymerization (DP) observed for polysiloxanes and polymethacrylates indicate that the order within the smectic layers and the penetration of the flexible main chains of the smectic layers was not appreciably affected by changes in DP. The poly(vinyl ether)s on the other hand exhibited a pronounced decrease in DELTAh(i) with increasing DP and a more complex correlation between T(g) and DP indicative of an increasing disturbance by the flexible main chains of the smectic layers with increasing DP. These differences between polysiloxanes/polymethacrylates and poly(vinyl ether)s were also found to have profound effects on the DP dependence of the isotropization temperature.