방향족 이미드의 특성관계 : 2. 고분자량의 폴리아믹산과 폴리 이미드 합성을 위한 최적조건

정중하; 황정민; 최환재; 최순자

Polymer(Korea), Vol.18, No.5, 677-685, September, 1994

Structure-Property Relationships in Aromatic Polyimide : 2. Optimum Conditions for High Molecular Weight Poly(amic acids) and Polyimides

정중하, 황정민, 최환재, 최순자

초록

방향족 dlanhydride [PMDA(pyromellitic dlanhydride). ODPA(4,4'-oxydiphthalic anhydride)]와 방향족 diamine[3,3'-DDSO₂(3,3'-diamino diphenyl sulfone), 4,4'-DDSO₂(4,4'-diamino diphenyl sulfone), DDM(4,4'-diamino diphenyl methane)]를 공용매 DMAc(N,N'-dimethy1 acetamide)에 용해시켜 용액 중합반응으로 폴리아믹을 제조한 후, 축합반응으로 고내열성 방향족 폴리이미드를 합성하였다.. 폴리아믹산의 대수 및 고유점도와 분자량 측정으로 (1)고 분자량을 위한 위한 최적조건과 (2)단량체의 순도와 제조형상(필름 및 분말)이 분자량에 미치는 영향 등을 조사하였다. 경화온도에 따른 이미드화도를 FT-IR분석으로, DSC와 DMA를 이용하여 유리전이온도를, 그리고 극성 및 비극성 용매에 대한 용해도 등을 조사하였다. TGA에 의한 열안정성은 정제된 단량체로 제조된 폴리이미드가 보다 높은 열안정성을 보여 열안정성의 분자량 의존도가 관찰되었는데, 이는 GPC 분석을 통한 분자량 조사에서도 확인되었다.

Poly(amic acids) (PAAs) prepared from the mixtures of aromatic dianhydrides [PMDA(pyromellitic dlanhydride) and ODPA(4,4'-oxydiphthalic anhydride)] with aromatic diamine[3,3'-DDSO₂(3,3'-diamino diphenyl sulfone), 4,4'-DDSO₂(4,4'-diamino diphenyl sulfone), DDM(4,4'-diamino diphenyl methane)] in cosolvent, DMAc(N,N'-dimethy1 acetamide), were thermally cured to convert polyimides (PIs). (1)The optimum condition of polymerization, (2)the effect of monomer purity and the type of PAAs(film or powder) on the molecular weight were investigated by measuring the intrinsic and inherent viscosity and molecular weight of the PAAs. The degree of imidization was obtained using FT-IR and the glass transition temperatures were measured using DSC or DMA. Solubilities of the fully imidized PIs were tested in polar and non-polar solvents. Thermal analysls using TGA revealed that thermal stabilities of the PIs depend on their molecular welghts and the shape of PAAs as well.

Keywords:aromatic polyimide;structure-property

[References]

Ebodon JR, "New Method of Polymer Synthesis," Blackie & Son Ltd., New York (1991)
Jeong HJ, Oishi Y, Kakimoto M, Imai Y, J. Polym. Sci. A: Polym. Chem., 29, 39 (1991)
Kim SK, Jung CH, Kim HS, Choe S, Polym.(Korea), 16(3), 249 (1992)
Kolesnikov G, Fedotova O, Hofbauer E, Shelgayaeva V, Vysokomol. Sodein, A9, 612 (1967)
Hoyle CE, Anzures ET, J. Appl. Polym. Sci., 43, 1 (1991)
Dine-Hart RA, Wright WW, J. Appl. Polym. Sci., 11, 609 (1967)
Clair AK, Clair TL, Slemp WS, Ezzell KS, NASA TM-87650, NASA, Washington, D.C. (1985)
Ginsberg R, Susko JR, "Polymides: Synthesis and Characterization," Ed. by K.L. Mittal, vol. 1, pp. 237 ~ 247, Plenum, New York (1984)
Navarre M, "Polyimides: Synthesis and Characterization," ed. by K.L. Mittal, vol. 1, pp. 259 ~ 271, Plenum, New York (1984)
Pryde CA, J. Polym. Sci. A: Polym. Chem., 27, 711 (1989)
Wallach ML, J. Polym. Sci. A: Polym. Chem., 5, 653 (1967)

[Referenced By]

[1] Ebodon JR, "New Method of Polymer Synthesis," Blackie & Son Ltd., New York (1991)

[2] Jeong HJ, Oishi Y, Kakimoto M, Imai Y, J. Polym. Sci. A: Polym. Chem., 29, 39 (1991)

[3] Kim SK, Jung CH, Kim HS, Choe S, Polym.(Korea), 16(3), 249 (1992)

[4] Kolesnikov G, Fedotova O, Hofbauer E, Shelgayaeva V, Vysokomol. Sodein, A9, 612 (1967)

[5] Hoyle CE, Anzures ET, J. Appl. Polym. Sci., 43, 1 (1991)

[6] Dine-Hart RA, Wright WW, J. Appl. Polym. Sci., 11, 609 (1967)

[7] Clair AK, Clair TL, Slemp WS, Ezzell KS, NASA TM-87650, NASA, Washington, D.C. (1985)

[8] Ginsberg R, Susko JR, "Polymides: Synthesis and Characterization," Ed. by K.L. Mittal, vol. 1, pp. 237 ~ 247, Plenum, New York (1984)

[9] Navarre M, "Polyimides: Synthesis and Characterization," ed. by K.L. Mittal, vol. 1, pp. 259 ~ 271, Plenum, New York (1984)

[10] Pryde CA, J. Polym. Sci. A: Polym. Chem., 27, 711 (1989)

[11] Wallach ML, J. Polym. Sci. A: Polym. Chem., 5, 653 (1967)