폴리(이미드-아라미드-설폰)의 합성과 그들의 열적성질

Abstract

이미드/아라미드/설폰기가 교대로 도입된 poly(imide-aramid-sulfone)s을 divinyl sulfone(DVS)과 <TEX>$N^1,N^4$</TEX>-bis(4-(vinylsulfonyl)phenyl)terephthalamide (2)를 pyromellitic diimide와 반응하여 높은 수율로 제조하였다. 또한 고분자를 닮은 3가지 모델 화합물인 N-[2-(p-aminophnenylsulfonyl)ethyl]phthalimide (3), 2,2'-(2,2'-sulfonylbis(ethane-2,1-diyl))diisoindoline-1,3-dione (4), 및 N,N-bis(4-(2-(1,3-dioxoisoindolin-2-yl)ethylsulfonyl)phenyl)terephthalamide (5)을p-aminophenyl vinyl sulfone, DVS, 2와 phthalimide와 반응하여 얻었다. 축합 중합은 phthalimide 기와 DVS의 마이클 첨가 반응에 의하여 균일 용액으로 진행되며 tetrabutylammonium hydroxide (TBAH)가 촉매로 작용하여 poly(imide-aramid-sulfone)s 6-12의 분자량이 큰 중합체를 얻을 수 있었다. DVS/2의 구성비는 1/0, 3/1, 2/1, 1/1, 1/2, 1/3, 및 0/1이다. 얻어진 고분자들은 극성 용매인 N,N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidinone 및 tetrahydrofuran에 잘 용해하였다. 그 밖에 분자량, 점도 그리고 열적 성질을 평가하였다. A series of poly(imide-aramid-sulfone)s with alternatingly introduced imide/aramid groups were prepared by reacting divinyl sulfone (DVS) and <TEX>$N^1,N^4$</TEX>-bis(4-(vinylsulfonyl)phenyl)terephthalamide (2) with pyromellitic diimide. Three model compounds, N-[2-(p-aminophnenylsulfonyl)ethyl]phthalimide (3), 2,2'-(2,2'-sulfonylbis(ethane-2,1-diyl))diisoindoline-1,3-dione (4), and N,N-bis(4-(2-(1,3-dioxoisoindolin-2-yl)ethylsulfonyl)phenyl)terephthalamide (5), resembling polymers were prepared with good yields by reacting p-aminophenyl vinyl sulfone, DVS, and 2 with phthalimide. Condensation polymerization was carried out by Michael-type addition reaction of the difunctional phthalimide group with the DVS group in the presence of tetrabutylammonium hydroxide (TBAH), resulting in poly(imide-aramid-sulfone)s 6-12 with moderate molecular weights and good yields. They were highly soluble in polar solvents such as N,N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidinone and tetrahydrofuran. The ratios of DVS/2 were 1/0, 3/1, 2/1, 1/1, 1/2, 1/3, and 0/1. Molecular weight and physical properties such as solubility, viscosity, and thermal properties of the polymers were examined.