로진-말레산 부가물과 디이소시아네이트로부터 폴리아미드이미드의 합성시 용제의 효과

김점식; 최병오; 최형기

Journal of the Korean Industrial and Engineering Chemistry, Vol.1, No.1, 73-82, October, 1990

Export Citation

로진-말레산 부가물과 디이소시아네이트로부터 폴리아미드이미드의 합성시 용제의 효과

The Effect of Solvents on the Synthesis of Polyamideimides from Rosin-Maleic Anhydride Adduct and Diisocyanate

김점식, 최병오, 최형기

초록

로진과 말레산무수물로부터 rosin-maleic anhydride adduct (RMA)를 합성하고 이를 방향족디이소시아네이트와 반응시켜서 폴리아미드이미드를 합성하였다. 반응촉매로는 Sodium methoxide (CH₃ONa)를 사용하였고 반응용제로는 N-메틸-2-피롤리돈 (이하 NMP)을 사용하였다. NMP는 방향족디이소시아네이트와 부반응을 하기 때문에 중합체의 수율과 점성도가 낮았다. 부반응을 줄이기 위하여 NMP에 방향족용제인 크실렌, 아세토페논, 벤조니트릴 및 니트로벤젠을 공용제로 혼합, 사용하였다. 극성이 비교적 작은 공용제의 혼합시 공용제 혼합비율이 60%인 경우 약 70%정도, 극성이 비교적 큰 공용제의 혼합계에서는 혼합비율이 40%인 경우 90% 이상의 수율로서 높은 수율을 얻을 수 있었다. 중합체는 무정형이거나 약간의 결정성을 갖는 구조였으며 고극성용제에서만 용해하였다. 중합체의 점성도는 0.12-0.26dl/g의 범위였다. 열분석 결과 중합체의 초기분해온도는 330℃ 이상으로서 양호한 열안정성을 나타내었다.

Rosin-maleic anhydride adduct (RMA) was synthesized from rosin and maleic anhydride. The polyamideimides were obtained by reacting the adduct with two aromatic diisocyanates using sodium methoxide as catalyst. The yield and the inherent viscosity of polymers obtained by the reaction in NMP solvent were low because of the possible reaction of NMP solvent with diisocyanate monomer. The polymers were synthesized in solvent mixture of NMP and cosolvents such as xylene, acetophenone, benzonitrile, and nitrobenzene in order to minimize the side reaction of NMP with diisocyanates. The yield of polymer obtained by the reaction in NMP-nonpolar cosolvent mixtures was about 70% and that obtained by the reaction in NMP-polar cosolvent mixtures was over 90%, respectively. The polymers were either amorphous or poorly cystalline, and soluble only in highly polar solvents. The inherent viscosity of polymers ranges from 0.12-0.26dl/g. The results of thermal analysis showed that the polymer had good thermal stability with initial decomposition temperature over 330℃.

[References]

Alvino WM, Frost LW, J. Polym. Sci. A: Polym. Chem., 9, 2209 (1971)
Sroog CE, Endrey AL, Abramo SV, Beer CE, Edwards WM, Olivier KL, J. Polym. Sci. A: Polym. Chem., 3, 1373 (1965)
Dine-Hart RA, Wright WW, Macromol. Chem., 143, 189 (1971)
Maiti M, Maiti S, J. Macromol. Sci.-Chem., 20, 109 (1983)
Ray SS, Kundu AK, Maiti M, Ghosh M, Maiti S, Angew. Makromol. Chem., 122, 153 (1984)
Ray SS, Kundu AK, Ghosh M, Maiti S, Eur. Polym. J., 21, 131 (1985)
Ray SS, Kundu AK, Maiti S, J. Macromol. Sci.-Chem., A23, 271 (1986)
Ulrich H, J. Polym. Sci. Polym. Rev., 11, 93 (1976)
Terney S, Keating J, Zielinski L, Hakala J, Sheffer H, J. Polym. Sci. A: Polym. Chem., 8, 683 (1970)
Richter R, Ulrich H, J. Org. Chem., 38, 2614 (1973)
Ulrich H, Tucker B, Stuber FA, Sayigh AAR, J. Org. Chem., 33, 3928 (1968)
Farrissey WJ, Rose JS, Carleton PS, J. Appl. Polym. Sci., 14, 1093 (1970)
Saksena SC, Panda H, Rakhshinda A, J. Oil Col. Chem. Assoc., 64, 299 (1981)
Saksena SC, Panda H, Rakhshinda A, J. Oil Col. Chem. Assoc., 65, 317 (1982)
Kim JS, Choi HK, Polym.(Korea), 13(8), 692 (1989)
Hoy HL, J. Paint Technol., 42, 76 (1970)
Burrel H, "Polymer Handbook," 2nd Ed., Ed. by J. Brandrup and E.H. Immergut, IV-337, Wiley-Interscience, N.Y. (1975)

[1] Alvino WM, Frost LW, J. Polym. Sci. A: Polym. Chem., 9, 2209 (1971)

[2] Sroog CE, Endrey AL, Abramo SV, Beer CE, Edwards WM, Olivier KL, J. Polym. Sci. A: Polym. Chem., 3, 1373 (1965)

[3] Dine-Hart RA, Wright WW, Macromol. Chem., 143, 189 (1971)

[4] Maiti M, Maiti S, J. Macromol. Sci.-Chem., 20, 109 (1983)

[5] Ray SS, Kundu AK, Maiti M, Ghosh M, Maiti S, Angew. Makromol. Chem., 122, 153 (1984)

[6] Ray SS, Kundu AK, Ghosh M, Maiti S, Eur. Polym. J., 21, 131 (1985)

[7] Ray SS, Kundu AK, Maiti S, J. Macromol. Sci.-Chem., A23, 271 (1986)

[8] Ulrich H, J. Polym. Sci. Polym. Rev., 11, 93 (1976)

[9] Terney S, Keating J, Zielinski L, Hakala J, Sheffer H, J. Polym. Sci. A: Polym. Chem., 8, 683 (1970)

[10] Richter R, Ulrich H, J. Org. Chem., 38, 2614 (1973)

[11] Ulrich H, Tucker B, Stuber FA, Sayigh AAR, J. Org. Chem., 33, 3928 (1968)

[12] Farrissey WJ, Rose JS, Carleton PS, J. Appl. Polym. Sci., 14, 1093 (1970)

[13] Saksena SC, Panda H, Rakhshinda A, J. Oil Col. Chem. Assoc., 64, 299 (1981)

[14] Saksena SC, Panda H, Rakhshinda A, J. Oil Col. Chem. Assoc., 65, 317 (1982)

[15] Kim JS, Choi HK, Polym.(Korea), 13(8), 692 (1989)

[16] Hoy HL, J. Paint Technol., 42, 76 (1970)

[17] Burrel H, "Polymer Handbook," 2nd Ed., Ed. by J. Brandrup and E.H. Immergut, IV-337, Wiley-Interscience, N.Y. (1975)