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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 16, Number 5
JKCSEZ 16(5)
October 20, 1972 

The Mechanism to Oxidative Polymerization of N-Methyl-p-Aminophenol and Thermal Characteristics of the Polymer Formed

N-Methyl-p-Aminophenol의 산화중합기구 및 생성중합체의 열특성
Kyu Suck Choi

N-methyl-p-aminophenol은, 산소존재하, 철-킬레이트(Fe(III)-EDTA) 수용액중에서 산화중합하여 무색의 Oligo-(N-methyl-p-aminophenol)을 정량적으로 생성한다. 이 산화중합과정에서 단량체중의 N에 결합된 CH3 group이 일부 탈리되는데, 이것은 oligo-(N-methyl-p-aminophenol)을 아세톤처리하여 얻은 아세톤 가용부와 부용부의 적외선스펙트럼에서 δasymCH3 1460 cm-1 및 δsymCH3 1380 cm-1의 흡수가 후자의 경우 현저히 약화된 것으로 명백하다. N2기류중에서 매분 2℃의 상승속도로 행한 TGA분석결과, 600℃에서 약 40%의 중량손상을 나타내며, CH3 치환기가 없는 p-aminophenol보다 내열성이 떨어진다. 또한 이 생성올리고머의 He 기류중에서 행한 열분해반응에서의 생성물은 단량체인 N-methyl-p-aminophenol과 물이 확인되었고 분해가스로부터는 gas chromatography에서 H2, CO, CO2등이 확인되었다. 생성올리고머의 열처리에서는 일부는 1차원적인 구조가 절단되어 단량체로 분해되지만, 대부분은 melt polycondensation이 일어나 더 큰 중합체로 변함과 동시에 열에 안정한 환식구조로 변하여 감이 확인되었다.

N-Methyl-p-aminophenol was polymerized by oxidative couplng in the aqueous iron chelate solution in the presence of oxygen, and black precipitate of oligo-(N-methyl-p-aminophenol) was formed quantitatively. In this oxidative polymerization reaction, methyl group attached to N in the monomer was partly eliminated, and it was clarified by the infrared spectra from the fact that the absorption of δasymCH3 1460 cm-1 and δsymCH3 1380 cm-1 in acetone insoluble fraction was much weaker than that in acetone soluble fraction. From Thermo-gravimetric analysis, oligo-(N-methyl-p-aminophenol) showed about 40% weight loss at 600℃ and it was less heat-resistant than oligo (p-aminophenol) that methyl group was not contained. In pyrolysis of oligo-(N-methyl-p-aminophenol) in He atmosphere, monomer N-methyl-p-aminophenol and water were formed, and in the pyrolytic gases, H2, CO, CO2 were detected by gas chromatography. From the above facts, to the structural change on oligo-(N-methyl-p-aminophenol) when it was heat-treated, it was considered that original linear structure was partly degraded, and the most of the oligomer was to go in with melt polycondensation to form polymer, and heat-resistant cyclic structure was formed at a time.

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