PMDA/MDA-Phenylene diamine 계열의 공중합체막에서의 산소, 질소 투과 특성의 정성적 고찰

이경록; 나성순; 김종표; 민병렬

Journal of the Korean Industrial and Engineering Chemistry, Vol.9, No.1, 13-19, February, 1998

Export Citation

PMDA/MDA-Phenylene diamine 계열의 공중합체막에서의 산소, 질소 투과 특성의 정성적 고찰

A Qualitive Research of N₂, O₂ Permeation Property in PMDA/ MDA- Phenylene Diamine Copolyimide

이경록, 나성순, 김종표, 민병렬

초록

Pyromellitic dianhydride(PMDA)와 methylenedianiline(MDA)을 기본으로 하고 이에 meta-phenylendiamine(MPD), para-phenylendiamine(PPD), 2,4,6-trimethyl-1,3-phenylenediamine(TriMeMPD)을 첨가하여 열적 이미드화법으로 서로 다른 화학적 구조를 갖는 폴리이미드 공중합체막을 합성하여 제조된 막들의 물성치들을 극정하고, 산소와 질소의 투과 특성을 막의 물성과 관련시켜 정성적으로 고찰하였다. PMDA-MDA막을 기준으로 PPD, MPD의 첨가는 막의 밀도를 증가시켰고, 이에 따라 막의 자유용적과 d-spacing 값의 감소를 나타내어 산소, 질소의 투과량을 감소시켰으며, TriMeMPD의 첨가는 반대의 경향을 나타내었다. 따라서 d-spacing값과 자유용적은 질소, 산소의 투과특성과 정성적 상관성을 가짐을 알 수 있었다. 모든 막에서 압력에 상관없이 투과 계수는 거의 일정한 값을 나타내었고, 막의 기체 투과계수가 증가하면 산소/질소의 이상분리인자는 감소하였다. 온도가 증가하면 투과량도 증가하였으며 이상분리인자는 감소하였으며, 질소 투과량의 상승비가 산소보다 더 크게 나타났다.

Copolyimide membranes of different chemical structure based on pyromellitic dianhydride (PMDA)/methylendianiline(MDA) were prepared by varying their chemical compositions with adding meta-phenylendiamine (MPD), para- phenylendiamine (PPD), 2,4,6- trimethyl-1,3-phenylenediamine(TriMeMPD) as a co-monomer. The N₂ and O₂ permeation properties are qualitatively correlated to specific free volume and intersegmental distance of membrane. The partial replacement of MDA with MPD or PPD caused in the PMDA/MDA based membranes increase in density, and decrease in free volume, d-spacing, consequently resulted in decreased permeability coefficient. In the case of TriMeMPD, opposite results were observed. In all membranes, the permeability coefficients were pressure independent, and membranes which have high permeability coefficient showed low N₂/O₂ ideal separation factor as an usual manner. The permeability coefficient also increased with temperature and N₂/O₂ ideal separation factor decreased. The increase ratio of the N₂ permeability coefficient was larger than that of O₂

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[18] Matsmoto K, Xu P, J. Membr. Sci., 81, 23 (1993)

[19] Robeson LM, J. Membr. Sci., 62, 165 (1991)