열방성 액정폴리에스터Poly(1-phenylethyl.p-phenyleneterephthalate)의 X-선 결정구조해석

X-ray Analys is of the Thermotropic Liquid Crystalline Copolyester Poly(1 -phenylethylpphenylene-tere phthalate)

50% terephthaloyl chloride(TPA)와 50%(1-phenylethyl) hydroquinone(PEHQ)으로부터 합성된 열 액정폴리에스터 poly(1-phenylethyl-p-phenylene-terephthalate)의 chalk conformation 및 packing 상태를 X-선 회절법을 이용하여 해석하였다. 단위세포상수는 a=12.77 A, b=10.17 A(unlque axis), c=12.58 A (fiber axis), β=90.1°, 그리고 공간군은 P2l 이고 단사정계이며 Z:4 이었다. 미세구조는 주쇄상의 Phenyl-COO 그리고 COO-Phenyl 평면간의 그리고 주축과 측쇄간의 torsion angle 들을 중심으로 37개의 회절반점에 대해 Linked Atom Least Square(LALS) 방법을 이용하여 해석하였으며, 1-phenylethyl 치환체는 ortho-와 met a위치에 각각 확률적으로 0.5의 가중치를 부여함에 의해 구조적으로 모델링 되었다. 주쇄상의 Phenyl-COO그리고 Phenyl-COO평면간의 torsion angle은 각각 -6.1°와 65.6°로 주어졌으며 결국 주축상의 Phenol 평면들은 서로 59.5°로 엇갈려 주축을 형성하고 있음을 알 수 있었다. (단 ester, COO-, 기는 평면으로 가정되었다.)

X-ray methods have been used to determine the chain conformation and packing of the thermotropic liquid crystalline copolyester prepared from 50% tarephthaloyl chloride(TPA) and 50% (1-phenylethyl) hydroquinone(PEHQ). The x-ray patterns of annealed melt-spun fibers contain a series of annealed melt-Pointing to a well ordered crystalline structure, despite the random sense(2 or 3-) of the 1-phenylethyl substiuttion on the TPA-hydroquinone backbone. The crystalline fiber is monoclinic with space group P2l and the unit cell has dimensions 11=12.77 A, b=10.17 A (upique axis), c=12.58 h (fiber axis). and β=90.1° and contains TPA-PEHO units of to or chains. The random substitution of 1-phenylethyl groups was modelled by placing these groups at both the 2and 3 positions and giving each a weight of one-hal(. T he structure has been refined by linked a rom least square methods(LALS) against 16 observed and 21 unobserved reflections. and had a final R value of 0.20. Packing of the side chains is effected by staggering adjacent chains along the b axis by approximately c/2, so that the side chains are interleaved. The phenyl-COO and COO-phenyl torsion angles are -6.1 and 65.6, respectively, such that the main chain phenyls are mutually inclined at 59.5 (the ester groups are assumed to be planar). These torsion angles compare very well with those for the model compounds, notably phenylbenzoate, and can be used in future analyses of the structures of more complex random sequence copolyesters.