화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Polymer(Korea), Vol.15, No.5, 522-530, October, 1991
Export Citation
p-(tert-Butyloxycarbonyloxy)aniline을 포함하는 포스파젠 고분자의 합성 및 물성조사
Syntheses and Properties of Polyphosphazene Containing p-(tert-Butyloxycarbonyloxy)aniline
박영철, 공명선, 안광덕
초록
용해성 polydichlorophosphazene과 과량의 p-(tert-butyloxycarbonyloxy)aniline[(t-BOC-oxy)aniline]을 반응시켜 (t-BOC-oxy)anilino 치환체가 측쇄에 결합된 polyphosphazene, [NP(NHCH3)x(NHC6H4O-t-BOC]n[III] 및 [IV]를 합성하였다. 또한 hexachlorocyclotriphosphazene(HCTPZ)과 (t-BOC-oxy)aniline의 반응으로 모델 화합물 hexakis[(t-BOC-oxy)anilino]cyclotriphosphazene[II]을 합성하여, 모델 포스파젠 화합물[II]와 고분자[III]과 [IV]의 열적 성질 및 용해성을 관찰하였다. tert-butyloxycarbonyl(t-BOC)기가 보호된 폴리포스파젠은 열분해로 t-BOC기의 탈보호가 165℃ 이상에서 나타났으며 측쇄의 구조가 페놀 유도체로 변하였다. t-BOC기로 보호된 포스파젠 고분자는 보호/탈보호에 따라 용해도에서 큰 차이를 보여, t-BOC 치환체가 88% 결합된 poly[p-(t-BOC-oxy)anilino]phosphazene[III]은 유기용매에 잘 용해되었고, 메탄올, 1% KOH 수용액에서는 불용성을 나타내었으나 열분해 후 페놀 유도체의 폴리포스파젠은 보다 극성용매인 DMF, 1% KOH 수용액에는 용해되었다. 포스파젠 고분자의 열분해에 의한 t-BOC 보호기 이탈 반응은 열분석과 분광분석으로 해석하였다.
The t-BOC protected polyphosphazenes with the p-(tert-butyloxycarbonyloxy)anilino [p-(t-BOC-oxy)anilino] substituent in side-chains were synthesized by the reaction of soluble linear polydichlorophosphazene with p-(t-BOC-oxy)aniline. As a model compound, hexakis[p-(t-BOC-oxy)anilino]cyclotriphosphazene[II] was synthesized by the reaction of hexachlorocyclotriphosphazene(HCTPZ) and (t-BOC-oxy)aniline. Thermal deprotection reaction of the t-BOC protected model compound [II] , poly[p-(t-BOC-oxy)anilino]phosphazene and poly[methylamino[p-(t-BOC-oxy)anilino]phosphazene], [NP(NHCH3)x(NHC6H4O-t-BOC)y]n[III], [IV] were investigated by thermal analysis. In the case of the model compound [II] and the t-BOC protected polymer[III], the deprotection of tert-butyloxycarbonyl (t-BOC) groups occurred with evolution of carbon dioxide and isobutene above 165℃. The structure of the p-(t-BOC-oxy)anilino substituent was transformed to the p-hydroxyanilino group after the deprotection. Accordingly the solubility of the polyphosphazenes was drastically changed after thermolysis. The protected poly[p-(t-BOC-oxy)anilino]phosphazene [III] and [IV] show good solubility in common organic solvents such as acetone and THF, but they are insoluble in methanol and 1% aqueous KOH. Instead the deprotected polyphosphazenes with phenolic side-chains are soluble in 1% aqueous KOH but insoluble in THF, acetone, etc.
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