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Poly [6-[4-(4-methoxy-/3-methylstyryl) phenoxy] hexyl methacrylate](4-6-PMA) with different molecular weights and molecular weight distributions was synthesized by group transfer and radical polym-erization of the corresponding monomer. The phase behavior of liquid crystalline 4-6-PMA with varying molecular weights was compared to that of its monomeric and dimeric model compounds. The number and nature (ie, virtual, monotropic, or enantiotropic) of phase transitions were determined by a combination of thermodynamicand kinetic factors. Since the rate of formation of highly ordered phases (crystalline and smectic) decreases with increasing polymer molecular weight, the number and nature of the liquid crystalline phases exhibited by 4-6-PMA vary with increasing molecular weight according to the following trend: monotropic nematic, enantiotropic nematic and enantiotropic smectic, enantiotropic nematic …