화학공학소재연구정보센터
Journal of the Korean Industrial and Engineering Chemistry, Vol.9, No.2, 185-192, April, 1998
폴리이미드의 구조에 따른 방향족 PBI/PI 블렌드의 상용성 및 상호작용의 세기
Miscibility and Specific Intermolecular Interaction Strength of PBl/Pl Blends Depending on Polyimide Structures
초록
네 종류의 폴리아믹산(PPA)은 서로 다른 구조의 디아민들인 3,3′-diaminodiphenyl sulfone(3,3′-DDSO2), 4,4′-diaminodiphenyl sulfone(4,4′-DDSO2), 4,4′-methylene dianiline(4,4′-MDA) 및 4,4′-oxydianiline(4,4′-ODA)와 디안하이드라이드인 3,3′, 4,4′-benzophenone tetracarboxylic dianhydride (BTDA)를 용매인 DMAc를 이용하여 합성되었다. 이들의 폴리아믹산(PAA)을 이용하여 poly[2,2-(m-phenylene)-5,5′-bibenzimidazole](PBI)와 용액 블렌딩하여 Blend-Ⅰ,Ⅱ,Ⅲ, 그리고 Ⅳ로 칭하였으며, 이에 대한 시료를 필름이나 분말로 제조한 PBI/PAA 시스템을 예상된 Tg 보다 높은 온도에서 열경화시켜 PBI/PI 블렌드로 전환시킨후 PI 합성시 사용된 디아민의 분자구조 변화에 따른 블렌드의 상용성과 그 상호작용의 상대적인 세기를 살폈다. 이로부터 본 연구에서 이용된 네 개의 블렌드들은 상용성을 보였으며, 이들 상용성을 가져다주는 상호작용의 세기는 Blend-Ⅲ와 Blend-Ⅳ가 Blend-Ⅰ와 Blend-Ⅱ보다 큼을 보였다. 이와 같이 블렌드에 사용된 PI의 구조변화에 따라 상호작용이 다른 것은 PI합성시에 사용된 디아민의 구조에서 페닐링 사이에 존재하는 linkage인 O나 CH2보다는 SO2가 존재할 때 블렌드를 이루는 두 고분자사이의 상호작용인 수소결합력을 약화시키는 spacer로 작용하였다고 판단된다.
Four kinds of polyamicacids(PAAs) were prepared by the condensation reaction of four diamines with defferent linkages, 3,3′-diaminodiphenyl sulfone(3,3′-DDSO2), 4,4′-diaminodiphenyl sulfone(4,4′-DDSO2), 4,4′-methylene dianiline(4,4′-MDA) and 4,4′-oxydianiline(4,4′-ODA), and dianhydride, 3,3′, 4,4′-benzophenone tetracarboxylic dianhydride (BTDA) using the solvent, dimethylacetamide(DMAc). These four PAAs were blended with poly[2,2-(m-phenylene)-5,5′-bibenzimidazole](PBI) from the solution blending. Then called as Blend-Ⅰ,Ⅱ,Ⅲ, and Ⅳ, respectively. Cast films or precipitated powders of the PBI/PAA blends were cured at a higher temperature than expected Tg to transform into PBI/PIs blends. Miscibility, specific intermolecular interaction for miscibility and their relative strength as a function of polyimide chemical structure with different four diamines in the PBI/PI systems were investigated. Four blends used in this study were all miscible, and the specific intermolecular interactions existing in these blends was thought to be the hydrogen bonding between the N-H of PBI and the C=O of PIs. The hydrogen bonding in the blends were shown to be stronger in the Blend-Ⅲ and Blend-Ⅳ than Blend-Ⅰand Blend-Ⅱ. It is speculated that the differences of hydrogen bonding strength of PBI/PI blends are dependent upon chemical structures of PIs, that is,PIs consisting of SO2 group have a weaker hydrogen bonding strength than those of O or CH2 group because the former has a larger spacer than the latter.
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