Polymer(Korea), Vol.36, No.1, 76-87, January, 2012
시아노아조벤젠을 함유한 히드록시프로필 셀룰로오스 및 그 광가교 필름들의 열방성 액정 거동
Thermotropic Liquid Crystalline Behavoir of Hydroxypropyl Celluloses Containing Cyanoazobenzene and Their Photocrosslinked Films
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초록
세 종류의 히드록시프로필 셀룰로오스(HPC) 유도체들, 즉 에테르화도(DET)가 0.4에서 3의 범위에 있는 [6-{4´-(4-시아노페닐아조)펜옥시}]헥실옥시프로필 셀룰로오스들(CAHPCs), 완전치환 HPC의 아크릴산 에스터(HPCA)와 CAHPC의 아크릴산 에스터들(CAHPCAs)을 합성하였다. 또한 HPCA와 CAHPCAs가 형성하는 열방성 액정 상에 UV 광을 조사시킴에 의해 가교된 HPCA(HPCAG)와 CAHPCAs(CAHPCAGs)를 제조하였다. HPC 그리 고 HPCA와 동일하게 DET ≤ 1.2인 CAHPCs와 CAHPCAs는 광학피치들(λm’s)이 온도상승에 의해 증가하는 양방성 콜레스테릭 상을 형성하는 반면 DET ≥ 1.4인 CAHPCs와 CAHPCAs는 단방성 네마틱 상을 형성하였다. DET ≤ 1.2인 CAHPCAs와 동일하게 DET ≤ 1.2인 CAHPCAGs는 넓은 온도범위에서 반사색깔을 나타냈다. 한편, DET ≥ 1.4인 CAHPCAs와 동일하게 DET ≥ 1.4인 CAHPCAGs는 네마틱 상의 전형적인 Schlieren 조직을 형성하
였다. 이러한 사실은 액정 조직이 광가교에 의해 거의 그대로 고정됨을 시사한다. CAHPCAs와 CAHPCAGs의 액정 상에서 액체 상으로의 전이온도들(Ti’s)은 DET가 증가함에 따라 낮아졌다. 그러나 DET가 동일할 경우, CAHPCAG가 CAHPCA에 비해 Ti는 높았다. 또한 CAHPCAGs가 CAHPCAs에 비해 λm의 온도의존성은 대단히 약하였다.
Three kinds of hydroxypropyl cellulose (HPC) derivatives, [6-{4-(4-cyanophenylazo)phenoxy}]hexyloxypropyl celluloses (CAHPCs) with degree of etherification (DET) ranging from 0.4 to 3, fully substituted acrylic acid esters of HPC (HPCA) and CAHPCs (CAHPCAs) were synthesized. The crosslinked HPCA (HPCAG) and CAHPCAs (CAHPCAGs) were also prepared by exposing thermotropic mesophases of HPCA and CAHPCAs to UV light. Both CAHPCs and CAHPCAs with DET ≤ 1.2, as well as HPC and HPCA, formed enantiotropic cholesteric phases whose optical pitches(λm’s) increase with temperature, wheras both CAHPCs and CAHPCAs with DET ≥ 1.4 showed monotropic nematic phases. CAHPCAGs with DET ≤ 1.2, as well as CAHPCAs with DET ≤ 1.2, exhibited reflection colors in a wide temperature range. On the other hand, CAHPCAGs with DET ≥ 1.4, as well as CAHPCAs with DET ≥ 1.4, showed Schileren textures typical of nematic phase, indicating that the liquid crystalline structure is virtually locked upon hotocrosslinking. The isotropization temperatures(Ti’s) of both CAHPCAs and CAHPCAGs
decreased with increasing DET. The Ti of CAHPCAG, however, was higher than that of CAHPCA at the same DET. Moreover, the temperature dependence of λm of CAHPCAGs was much weaker than that of CAHPCAs.
Keywords:hydroxypropyl cellulose;cyanoazobenzene;degree of etherification;photocrosslinking;nematic and cholesteric phases.
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