Abstract: | Electric‐field‐induced molecular alignments of side‐chain liquid‐crystalline polyacetylenes ? {HC?C(CH2)mOCO‐biph‐OC7H15]}? , where biph is 4,4′‐biphenylyl and m is 3 (PA3EO7) or 9 (PA9EO7)] were studied with X‐ray diffraction and polarized optical microscopy. An orientation as high as 0.84 was obtained for PA9EO7. Furthermore, the molecular orientation of PA9EO7 was achieved within a temperature range between the isotropic‐to‐smectic A transition temperature and 115 °C, and this suggested that the orientational packing was affected by the thermal fluctuation of the isotropic liquid and the mobility of the mesogenic moieties. The maximum achievable orientation for PA9EO7 was much greater than that for PA3EO7. This was the first time that the electric‐field‐induced molecular orientation of a side‐chain liquid‐crystalline polymer with a stiff backbone was studied. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1333–1341, 2004 |