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Thermotropic Liquid Crystalline Behavior of [4-{4′-(Nitrophenylazo)phenoxycarbonyl}]alkanoated Celluloses
Jeong SY, Ma YD
[4-{4′-(니트로페닐아조)펜옥시카보닐}]알카노화 셀룰로오스들의 열방성 액정 거동
정승용, 마영대

Abstract

The thermotropic liquid crystalline behavior of the homologous series of cellulose tri[4-{4′- (nitrophenylazo)phenoxycarbonyl}]alkanoates(NACEn, n=2∼8,10, the number of methylene units in the spacer) have been investigated. All of the homologoues formed monotropic nematic phases. The isotropicnematic transition temperature(TiN) decreased when n is increased up to 7, but it became almost constant when n is more than 7. The plot of transition entropy at TiN against n had a sharp negative inflection at n=7. The sharp change at n=7 may be attributed to the difference in arrangement of the side groups. The melting temperature(Tm) and associated entropy change at Tm, in contrast with TiN and associated entropy change at TiN, exhibited a distinct odd-even effect, suggesting that the average shape of the side chains in the crystalline phase is different from that in the nematic phase. The thermal stability and degree of order of the nematic phase observed for NACEn were significantly different from those reported for the homologous series of side-chain and combined type liquid crystal polymers bearing azobenzene or biphenyl units in the side chains. The results were discussed in terms of the differences in the chemical structure, the flexibility of the main chain, the mode of chemical linkage of the side group with the main chain, and the number of the mesogenic units per repeating unit.

셀룰로오스 트리[4-{4′-(니트로페닐아조)펜옥시카보닐}]알카노에이트들(NACEn, n＝2~8,10, 유연격자중의 메틸렌 단위들의 수)의 동족체들의 열방성 액정 특성을 검토하였다. 모든 동족체들은 단방성 네마틱 상들을 형성하였다. 액체 상에서 네마틱 상으로의 전이온도(TiN)는 n이 증가함에 따라 낮아지나 n이 7이상에서 거의 일정하게 되었다. TiN에서의 엔트로피 변화와 n의 관계를 나타낸 그림상에는 n=7에서 급격한 엔트로피의 감소가 관찰되었다. n=7에서 급격한 변화는 곁사슬 그룹의 배열의 차이에 의해 초래되는 것으로 생각된다. 용융온도(Tm)와 Tm에서의 엔트로피 변화는 TiN과 TiN에서의 엔트로피 변화와 판이하게 뚜렷한 홀수-짝수 효과를 나타냈다. 이러한 사실은 네마틱 상과 결정 상에서의 곁사슬 그룹들의 평균적인 형태가 판이함을 시사한다. NACEn에서 관찰되는 네마틱 상의 열적 안정성과 질서도는 아조벤젠 혹은 바이페닐 단위들을 곁사슬로 지닌 곁사슬형 그리고 복합형 액정 고분자 동족체들에 대해 보고된 결과들과 현저히 달랐다. 이들의 결과를 주사슬의 화학구조와 유연성, 주사슬과 곁사슬 그룹의 결합양식 그리고 반복단위당의 mesogenic 단위들의 수의 차이들의 견지에서 검토하였다.

Keywords: cellulose; nitroazobenzene; spacer length; nematic phase.

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This Article

2009; 33(1): 58-66

Published online Jan 25, 2009
Received on Aug 26, 2008
Accepted on Nov 6, 2008

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