CRYSTAL STRUCTURE AND MORPHOLOGY OF NASCENT SAMPLES OF SYMMETRIC AROMATIC POLYESTERS Ⅱ.POLY(p-PHENYL

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Confined thin film melt polymerization (CTFMP) of naphthalene chloride/hydroquinone (NC/HQ, 1/1, molar)mixtures at polymerization temperatures (Tp) below ca. 300℃ resulted in relatively thick, elongated crystals. Polymerization of NC/HQ above 300℃ between glass yielded well-formed lamellar crystals ca. 100 A thick. Phase Ⅰ and Ⅱ [001] ED patterns were obtained for all Tp, the relative amount of phase Ⅰ increasing with Tp. Polymerization of naphthalene dicarboxylic acid/hydroquinione diacetate 1/1 mixtures at high Tp also yielded lamellar crystals that "curled up" off of the substrate. When the high temperature CTFMP polymerization was conducted between mica, aggregates of lamellae on-edge developed but epitaxial growth did not occur. Epitaxial growth of lamellae between mica could be obtained, however, by confined thin film solution polymerization, with both of the latter samples yielding apparently related ED patterns from a different unit cell than phase Ⅰ or Ⅱ. Fiber patterns, obtained from sheared samples, indicated considerably greater crystal disorder than in the nascent crystals. Refinement of the phase Ⅰ unit cell parameters, based on the [001] and [011] ED patterns, with modeling based on Cerius2, suggests a monoclinic phase Ⅰ unit cell with a = 7.76, b = 5.71, c = 14.99 A, α = γ= 90°, β= 99.7°, p = 1.47 g/cm3, space group P121/al.
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