Article
  • Syntheses and Properties of Polyphosphazene Containing p-(tert-Butyloxycarbonyloxy)aniline
  • Park YC, Gong MS, Ahn KD
  • p-(tert-Butyloxycarbonyloxy)aniline을 포함하는 포스파젠 고분자의 합성 및 물성조사
  • 박영철, 공명선, 안광덕
Abstract
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.

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.

References
  • 1. Allcock HRPhosphrous-Nitrogen Compound, Academic Press, New York, N.Y. (1972)
  •  
  • 2. Allcock HR, Chem. Rev., 72, 315 (1972)
  •  
  • 3. Allcock HR, Chemtech, 5, 552 (1975)
  •  
  • 4. Jho I, Ahn KD, Polym.(Korea), 2(3), 105 (1978)
  •  
  • 5. Gleria M, Minto F, Bortolus P, Porzio W, Meille SV, Eur. Polym. J., 26, 315 (1990)
  •  
  • 6. Minto F, Gleria M, Bortolus P, Daolio S, Facchin B, Pagura C, Bolognesi A, Eur. Polym. J., 25, 49 (1989)
  •  
  • 7. Gleria M, Minto F, Bortolus P, Porzio W, Bolognesi A, Eur. Polym. J., 25, 1039 (1989)
  •  
  • 8. Allcock HR, Kim C, Macromolecules, 23, 3881 (1990)
  •  
  • 9. Allcock HR, Chem. Eng. News, 63(11), 22 (1985)
  •  
  • 10. Willson CG, Ito H, Frechet JMJ, Tessier TG, Houlihan FM, J. Electrochem. Soc., 29(14), 181 (1989)
  •  
  • 11. Frechet JMJ, Kallman N, Kryczka B, Eichler E, Houlihan FM, Willson CG, Polym. Bull., 20, 417 (1988)
  •  
  • 12. Houlihan FM, Bouchard F, Frechet JMJ, Willson CG, Can. J. Chem., 63, 153 (1985)
  •  
  • 13. Singler RE, Schneider NS, Hagnauer GL, Polym. Eng. Sci., 15, 321 (1975)
  •  
  • 14. Allcock HR, Kugel RL, Inorg. Chem., 5, 1716 (1966)
  •  
  • Polymer(Korea) 폴리머
  • Frequency : Bimonthly(odd)
    ISSN 0379-153X(Print)
    ISSN 2234-8077(Online)
    Abbr. Polym. Korea
  • 2023 Impact Factor : 0.4
  • Indexed in SCIE

This Article

  • 1991; 15(5): 522-530

    Published online Oct 25, 1991