Article
  • The Synthesis and Properties of Nonlinear Optical Polyquinonediimine Containing Mono-Azobenzene Group in the Side Chain
  • Lee SB, Yang JS, Park DK
  • 곁사슬에 모노-아조벤젠기를 갖는 비선형 광학 폴리퀴논디이민의 합성과 성질에 관한 연구
  • 이상배, 양정성, 박동규
Abstract
Polyquinonediimines(PQDI) which have stable structure on heat and contains mono-azobenzene in the side chain were synthesized by means of condensation polymerization under TiCl4. The synthesized monomers and polymers were identified by FT-IR, 1H-NMR, and elementary analysis. Especially, PQDI was comfirmed by the double-bonding peak of >C=N appeared near 1625 cm-1 by means of FT-IR spectrum. PQDI containing mono-azobenzene group in both side chains was not soluble on non-polar solvents at all but partially soluble in the polar solvents having small dielectric constant, and dissolved in the strong acid such ax sulfuric acid and CH3SO3H. Molecular weight distribution of PQDI measured by GPC showed 1.74. It was confirmed through X-ray diffraction analysis that the polymer was partially crystalline at the low angle region, but amorphous after heat treatment at 125℃. The glass transition temperature(Tg) of synthesized polymer was measured as 125℃ by differential scanning calorimetry. The SHG value for χ(2) after poling at 125℃ was 8.6 pm/V (λ=1.542 ㎛). The SHG value slowly decreased with time from the start but appeared temporal stability after 100 hours.

본 연구에서는 곁사슬에 mono-azobenzene 그룹을 갖는 polyquinonediimine(PQDI)을 TiCl4 존재 하에서 축합 중합법으로 합성하였다. 합성된 단량체와 고분자는 FT-IR과 1H-NMR로 확인하였으며, 특히 적외선 스펙트럼에 의하여 고분자의 특성 피크인 1625cm-1 부근에서 >C=N 이중결합이 형성되었음을 보여 주었다. Mono-azobenzene이 양쪽 측쇄에 붙어있는 PQID는 유전상수가 작은 극성용배에는 극히 부분적으로 용해성을 가졌으며 비극성 용매에는 거의 녹지 않았으나 황산과 CH3SO3H와 같은 강산에는 좋은 용해성을 보여주었다. GPC에 의한 분자량 분포는 1.74로 제법 넓은 분포를 가졌고, X-ray분석으로부터 낮은 각도의 영역에서 부분적 결정성을 보였으며, 125℃로 열처리 후에는 무정성 고분자임을 확인하였다. 고분자의 열 분석에 의하면, TGA측정에서는 308℃에서 분해온도가 나타나므로 열적으로 안정한 고분자임을 알 수 있으며, DSC에 의한 Tg값은 125℃이었고, mono-azobenzene이 유도체로 결합된 PQDI를 이 온도에서 분극 처리시킨 NLO-active한 PQDI의 SHG값은 8.6pm/V 값은 가졌고, 경시 안정성의 측정 겨과 초기 상태에서는 서서히 감소하는 경향을 보이나 100시간 후에는 안정성을 나타내었다.

Keywords: nonlinear optical; polyquinonediimine; mono-azobenzene group; NLO-PQDI

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  • Polymer(Korea) 폴리머
  • Frequency : Bimonthly(odd)
    ISSN 0379-153X(Print)
    ISSN 2234-8077(Online)
    Abbr. Polym. Korea
  • 2022 Impact Factor : 0.4
  • Indexed in SCIE

This Article

  • 2000; 24(6): 737-743

    Published online Nov 25, 2000