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

来源 :Chinese Journal of Polymer Science | 被引量 : 0次 | 上传用户:xiertimer
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Confined thin film melt polymerization (CTFMP) of naphthalene chloride/hydroquinone (NCMQ, 1/1, molar)mixtures at polymerization temperatures (T_p) below ca. 300℃ resulted in relatively thick, elongated crystals. Polymerizationof NC/HQ above 300℃ between glass yielded well-formed lamellar crystals ca. 100 A thick. Phase Ⅰ and Ⅱ [001] EDpatterns were obtained for all T_p, the relative amount of phase Ⅰ increasing with T_p. Polymerization of naphthalenedicarboxylic acid/hydroquinione diacetate 1/1 mixtures at high T_p also yielded lamellar crystals that “curled up” off of thesubstrate. When the high temperature CTFMP polymerization was conducted between mica, aggregates of lamellae on-edgedeveloped but epitaxial growth did not occur. Epitaxial growth of lamellae between mica could be obtained, however, byconfined thin film solution polymerization, with both of the latter samples yielding apparently related ED patterns from adifferent unit cell than phase Ⅰ or Ⅱ. Fiber patterns, obtained from sheared samples, indicated considerably greater crystaldisorder than in the nascent crystals. Refinement of the phase Ⅰ unit cell parameters, based on the [001] and [01 1] EDpatterns, with modeling based on Cerius~2, suggests a monoclinic phase Ⅰ unit cell with a = 7.76, b = 5.71, c = 14.99 A, α = γ= 90°, β= 99.7°, ρ = 1.47 g/cm~3, space group P12_1/al. Confined thin film melt polymerization (CTFMP) of naphthalene chloride / hydroquinone (NCMQ, 1/1, molar) mixtures at polymerization temperatures (T_p) below ca. 300 ℃ resulted in relatively thick, elongated crystals. Polymerizationof NC / HQ above 300 ℃ between Phase Ⅰ and Ⅱ [001] EDpatterns were obtained for all T_p, the relative amount of phase Ⅰ increasing with T_p. Polymerization of naphthalenedicarboxylic acid / hydroquinione diacetate 1/1 mixtures at high T_p 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 depressed but epitaxial growth did not occur. Epitaxial growth of lamellae between mica could be obtained, However, byconfined thin film solution polymerization, with both of the latter samples yielding apparently related ED patterns from adifferent unit cell than phase I or II. Fiber pat Terns, obtained from sheared samples, showed considerably greater crystal disposition than in the nascent crystals. Refinement of phase I unit cell parameters, based on the [001] and [01 1] EDpatterns, with modeling based on Cerius ~ 2, suggests a monoclinic space group P12_1 / al. For phase Ⅰ unit cell with a = 7.76, b = 5.71, c = 14.99 A, α = γ = 90 °, β = 99.7 °,
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