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Synthesis and Thermal Properties of Aromatic Poly(o-hydroxyamide)s Containing Phenylene Diimide Unit

Phenylene Diimide 단위를 포함한 방향족 Poly(o-hydroxyamide)s의 합성 및 열적 특성

  • Lee, Eung-Jae (Dept. of Bioenvironmental & Chemical Engineering, Chosun College of Science & Technology) ;
  • Yoon, Doo-Soo (Dept. of Bioenvironmental & Chemical Engineering, Chosun College of Science & Technology) ;
  • Choi, Jae-Kon (Dept. of Polymer Science & Engineering, Chosun University)
  • 이응재 (조선이공대학교 생명환경화공과) ;
  • 윤두수 (조선이공대학교 생명환경화공과) ;
  • 최재곤 (조선대학교 응용화학소재공학과)
  • Received : 2013.09.11
  • Accepted : 2013.11.07
  • Published : 2013.11.30

Abstract

In this study we attempt to modify the backbone structure and improve processibility of PBO having high melting and glass transition temperature. A series of aromatic poly(o-hydroxyamide)s(PHAs) were synthesized by direct polycondensaton of diacides containing diimide unit with two types of bis(o-aminophenol)s including 3,3'-dihydroxybenzidine and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane. PHAs were studied by FT-IR, $^1H$-NMR, DSC and TGA. PHAs exhibited inherent viscosities in the range of 0.34~0.65 dL/g at $35^{\circ}C$ in DMAc solution. The PHA 1 and 6F-PHA 6, introducing o-phenylene unit in the main chain showed excellent solubilities in aprotic solvents such as NMP etc. However, the PHA 3, having p-phenylene unit was not even dissolved perfectly with LiCl salt. 6F-PHAs were readily soluble at room temperature in aprotic solvents except 6F-PHA 3. But they showed better solubility than that of PHAs. The polybenzoxazoles(PBOs) were quite insoluble in other solvents except partially soluble in sulfuric acid. PBOs exhibited relatively high glass transition temperatures(Tg) in the range of 306~$311^{\circ}C$ by DSC. The maximum weight loss temperature and char yields of PHA3 and 6F-PHA3 showed the highest values of $658^{\circ}C$ and $653^{\circ}C$, 62.6 % and 62.1 %, respectively.

본 연구에서는 높은 용융점과 유리 전이 온도를 갖는 PBO의 구조 변화를 통해 가공성을 향상시키고자 한다. 일련의 방향족 poly(o-hydroxyamide)s(PHAs)가 3,3'-dihydroxybenzidine과 2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane을 포함하는 두 타입의 bis(o-amino-phenol)s과 diimide 단위를 갖는 이염기산들과의 직접 중축합에 의해서 합성되었다. PHAs의 특성은 FT-IR, $^1H$-NMR, DSC, TGA 등을 이용하여 조사하였다. PHAs 고유 점도는 $35^{\circ}C$ 의 DMAc 용액에서 측정하였으며 0.34~0.75 dL/g의 값을 보였다. o-phenylene 단위가 도입된 PHA 1과 6F-PHA 1은 NMP 등 비양자성 용매에 잘 용해되었지만, p-phenylene 단위가 도입된 PHA 3은 LiCl의 첨가에도 완전히 용해되지 않았다. 6F-PHAs은 6F-PHA 3을 제외하고 실온에서 비양자성 용매에 잘 용해되었고, PHAs 보다 더 좋은 용해도를 보였다. PBOs은 황산에 부분적으로 용해될 뿐 다른 용매에는 전혀 용해되지 않았다. DSC에 의해 측정된 PBOs의 유리전이온도(Tg)는 비교적 높은 306~$311^{\circ}C$의 범위를 보였다. PHA 3과 6F-PHA 3의 최대분해온도와 Char 수득률은 $658^{\circ}C$$653^{\circ}C$, 62.6%와 62.1%로 가장 높은 값들을 보였다.

Keywords

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