Polymer(Korea) (폴리머)

The Polymer Society of Korea (한국고분자학회)
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Thermal and Optical Properties of Poly{1-(Cholesteryloxycarbonylalkanoyloxy)ethylene}s

폴리{1-(콜레스테릴옥시카보닐알카노일옥시)에틸렌}들의 열 및 광학 특성

  • Jeong, Seung-Yong (Department of Polymer Science and Engineering, Dankook University) ;
  • Ma, Yung-Dae (Department of Polymer Science and Engineering, Dankook University)
  • 정승용 (단국대학교 고분자공학과) ;
  • 마영대 (단국대학교 고분자공학과)
  • Published : 2009.03.25
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Abstract

The thermal and optical properties of poly {1-(cholesteryloxycarbonylalkanoyloxy) ethylene}s (PCALEn, n=2$\sim$8,10, the number of methylene units in the spacer) were investigated. All of the homologues formed monotropic cholesteric phases with left-handed helical structures. PCALEn with n=2 or 10, in constrast with PCALEn with $3{\leq}n{\leq}8$, did not display reflection colors over the full cholesteric range, suggesting that the helical twisting power of the cholesteryl group highly depends on the length of the spacer connecting the cholesteryl group to the polyethylene chain. The glass transition temperatures decreased with increasing n. The isotropic-cholesteric phase transition temperatures decreased with increasing n up to 7 and showed an odd-even effect. However it became almost constant when n is more than 7. This behavior is rationalized in terms of the change in the average shape of the side chain on varing the parity of the spacer. This rationalization also accounts for the observed variation of the entropy gain for the clearing transition. The thermal stability and degree of order in the mesophase and the temperature dependence of the optical pitch observed for PCALEn were significantly different from those reported for cellulose tri(cholesteryloxycarbonyl)alkanoates. The results were discussed in terms of the differences in the chemical structure and flexibility of main chain and the number of the mesogenic units per repeating unit.

폴리{1-(콜레스테릴옥시카보닐알카노일옥시)에틸렌}들(PCALEn, n=2$\sim$8,10, 유연격자중의 메틸렌 단위들의 수)의 열 및 광학 특성을 검토하였다. 모든 동족체들은 좌측방향의 나선구조를 지닌 단방성 콜레스테릭 상들을 형성하였다. n=2 혹은 10인 PCALEn은 $3{\leq}n{\leq}8$인 PCALEn과 달리 콜레스테릭 상의 전 온도구간에서 반사색깔을 나타내지 않았다. 이러한 사실은 콜레스테릴 그룹에 의한 나선의 비틀림력은 콜레스테릴 그룹과 폴리에틸렌 사슬을 연결하는 유연격자의 길이에 민감하게 의존함을 시사한다. 유리전이온도들은 n이 증가함에 따라 낮아졌다. 액체 상에서 콜레스테릭 상으로의 전이온도들은 n이 7까지는 낮아지며 홀수-짝수 효과를 나타냈다. 그러나, n>7인 동족체들의 전이온도는 거의 일정하게 되었다. 이러한 거동은 유연격자의 홀수-짝수의 변화에 기인한 곁사슬 그룹의 평균적인 형태변화의 견지에서 설명된다. 전이온도에서 관찰되는 엔트로피 증가의 변화도 동일한 관점에서 설명된다. PCLAEn에서 관찰되는 액정 상의 열적 안정성과 질서도 그리고 광학피치의 온도의존성은 셀룰로오스 트리(콜레스테릴옥시카보닐)알카노에이트들에 대해 보고된 결과들과 현저히 달랐다. 이들의 결과를 주사슬의 화학구조와 유연성 그리고 반복단위당의 메조겐 단위들의 수의 차이들의 견지에서 검토하였다.

Keywords

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