화학공학소재연구정보센터
Journal of the Korean Industrial and Engineering Chemistry, Vol.20, No.6, 603-611, December, 2009
펜타-O-4-{4'-(시아노페닐아조)펜옥시}알킬-D-글루코피라노오스들의 열방성 액정 거동
Thermotropic Liquid Crystalline Behavior of Penta-O-4-{4'-(cyanophenylazo)phenoxy} alkyl-D-glucopyranoses
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초록
펜타-O-4-{4'-(시아노페닐아조)펜옥시}알킬-D-글루코피라노스 동족체들(CAGETn, n = 2∼10, 유연격자 중의 메틸렌 단위들의 수)의 열방성 액정 특성을 검토하였다. n = 2, 7인 CAGETn은 쌍방성 네마틱 상들을 형성하는 반면 나머지 유도체들은 단방성 네마틱 상들를 형성하였다. 이것이 글루코오스 유도체가 네마틱 상들을 형성한다고 하는 최초의 보고이다. CAGETns의 액체 상에서 네마틱 상으로의 전이온도들(T(iNS)) 그리고 T(iN)에서의 엔트로피 변화는 n의 함수로서 홀수-짝수 효과를 나타냈다. 이러한 거동은 유연격자의 홀수-짝수의 변화에 기인한 곁사슬들의 평균적인 형태변화의 견지에서 합리적으로 설명된다. CAGETns에서 관찰되는 네마틱 상에서 결정 상으로의 전이온도들(T(NkS)) 그리고 T(Nk)에서의 엔트로피 변화도 동일한 관점에서 설명된다. T(iN) 혹은 T(Nk)에서의 엔트로피 변화는 n = 4에서 재차 증가하기 전에 n = 3에서 최소를 나타냈다. 이러한 사실은 곁사슬 그룹들의 배열의 차이에 의해 초래되는 것으로 생각된다. CAGETns의 액정 상의 특성은 글루코오스에 알킬 그룹을 에테르 결합으로 부분적으로 혹은 완전치환시켜 얻은 유도체들에 대해 보고된 결과와 전혀 달랐다. 본 연구결과는 치환기들의 치환도와 화학구조가 액정들의 구조형성에 있어서 중요한 역할을 함을 시사한다.
Thermotropic liquid crystalline behavior of a homologous series of penta-O-4-{4'-(cyanophenylazo)phenoxy}alkyl-D-glucopyranoses (CAGETn, n = 2∼10, the number of methylene units in the spacer) has been investigated. The CAGETn with n of 2 and 7 exhibited enantiotropic nematic phases whereas other derivatives showed monotropic nematic phases. This is the first report of glucose derivatives that form thermotropic nematic phases. The isotropic-nematic transition temperatures (T(iNS)) of CAGETns and their entropy variation at T(iN) showed the odd-even effect as a function of n. This behavior was rationalized in terms of the change in the average shape of the side chains as the parity of the spacer is varied. This rationalization also accounts for the observed variation of nematic-crystalline phase transition temperatures (T(NkS)) and associoated entropy change at T(Nk). The entropy change at T(iN) or T(Nk) reaches a mininum at n = 3, before it increases again for n = 4. This may be attributed to the difference in the arrangement of the side groups. The mesophase properties of CAGETns were entirely different from those reported for partially or fully alkylated glucopyranoses. This result suggests that the degree of substitution and chemical structure of the substituents play an important role in the formation of the mesophase structures in the liquid crystals.
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