2-Benzamidoacrylic Acid의 자유라디칼 중합 및 공중합에 관한 연구

정판석; 이종광

Polymer(Korea), Vol.15, No.6, 749-758, December, 1991

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2-Benzamidoacrylic Acid의 자유라디칼 중합 및 공중합에 관한 연구

A Study on Free-Radical Homopolymerization and Copolymerization of 2-Benzamidoacrylic Acid

정판석, 이종광

초록

본 연구에서는 자유라디칼 메카니즘에 의한 2-benzamidoacrylic acid의 단독중합 반응속도와 공중합 반응성을 연구하였으며, DMF 용매를 사용하여 60±0.1℃에서 단독중합시켰을 때의 중합속도(R_p)는 단량체농도[M]와 개시제농도[I]에 대하여 R_p=k_p[M]^1.05[I]^0.52의 관계를 나타내었다. 이 단량체의 단독중합 총괄활성화 에너지는 20.9 Kcal/mol이었으며, 또한 poly(2-benzamidoacrylic acid)의 열분석도에 의하면 200℃에서 일차분해에 의한 흡열피이크가 나타났고 370℃에서 이차분해에 의한 발열피이크가 나타났다. 2-benzamidoacrylic acid를 스티렌 및 아크릴산 단량체와 공중합시켰을 때의 단량체 반응성비는 다음과 같다. r₁(2-benzamidoacrylic acid)=0.78, r₂(스티렌)=0.13 ; r₁(2-benzamidoacrylic acid)=2.08, r₂(아크릴산)=0.48. Alfrey-Price 식을 이용하여 계산한 2-benzamidoacrylic acid의 Q와 e값은 두 경우 모두 Q=2.30, e=0.72이었다.

The free radical polymerization and copolymerization of 2-benzamidoacrylic acid were investigated. From the result of kinetic investigation of 2-benzamidoacrylic acid in DMF at 60.0±0.1℃, a rate equation of R_p=k_p[M]^1.05[I]^0.52 was obtained. The overall activation energy for the polymerization was found to be 20.9 Kcal/mol within the temperature range 50∼70℃. The DTA thermogram of poly(2-benzamidoacrylic acid) showed an endothermic peak for the first degradation at about 200℃ and an exothermic peak for the second degradation at about 370℃. Copolymerization of 2-benzamidoacrylic acid with styrene and acrylic acid was carried out for the determination of monomer reactivity ratios. The monomer reactivity ratios for the monomer pairs determined at 60.0±0.1℃ using AIBN as an initiator are r₁(2-benzamidoacrylicacid)=0.78, r₂(styrene)=0.13 ; r₁(2-benzamidoacrylicacid)=2.08, r₂(acrylic acid)=0.48. The values of Alfrey-Price Q and e parameters for the 2-benzamidoacrylic acid were calculated to be 2.30 and 0.72 for the both systems.

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[2] Lenz RW, Saunders K, Balakrishnan J, J. Am. Chem. Soc., 12, 392 (1979)

[3] Miller A, Szafko J, J. Polym. Sci. A: Polym. Chem., 18, 1177 (1980)

[4] O'Brien JL, Gornick F, J. Am. Chem. Soc., 77, 4757 (1955)

[5] Tsuruta T, Chikanishi K, Makromol. Chem., 73, 231 (1964)

[6] Yamada B, Otsu T, J. Polym. Sci. A: Polym. Chem., 7, 2439 (1969)

[7] Furukawa J, Tsuruta T, J. Polym. Sci., 36, 275 (1959)

[8] Masuda S, J. Polym. Sci. A: Polym. Chem., 23, 2081 (1985)

[9] Madruga EL, Rodriguez MJ, J. Polym. Sci. A: Polym. Chem., 21, 2739 (1983)

[10] Funt BL, Pawelchak G, J. Polym. Sci. C: Polym. Lett., 13, 451 (1975)

[11] Perrin DD, Perrin DR, Purification of Laboratory Chemicals, Pergamon Press, Inc., N.Y., 87-406 (1980)

[12] Blout ER, Hohenstein WP, Monomers, Interscience Pub. N.Y., 35-45 (1949)

[13] Ponratnam S, Kapur SL, Makromol. Chem., 178, 1029 (1977)

[14] Wieland T, Eiegler W, Berichte, 90, 194 (1956)

[15] Kolar M, Seaman PM, J. Polym. Sci. A: Polym. Chem., 60, 1777 (1977)

[16] Braun D, Kern W, Techniques of Polymer Synthesis and Characterization, John Wiley and Sons, Inc., 64 (1972)

[17] Otsu T, Tanaka H, J. Polym. Sci., 13, 2605 (1975)

[18] Parth KJ, Philippovich N, J. Macromol. Sci.-Chem., A11, 1319 (1977)

[19] Sugiyama K, Lee SW, Makromol. Chem., 178, 421 (1977)

[20] Brandup J, Immergut EH, Polymer Handbook," Interscience Pub. N.Y. II, 1-67 (1966)

[21] Tsuda KT, Ichida T, Makromol. Chem., 178, 3221 (1977)

[22] Madruga EL, Roman JS, J. Polym. Sci. A: Polym. Chem., 19, 1101 (1981)

[23] Liaw DJ, Chung KC, Makromol. Chem., 184, 29 (1983)

[24] Ueda M, Pittman CU, J. Polym. Sci. A: Polym. Chem., 24, 3177 (1986)

[25] Diab MA, J. Polym. Sci. A: Polym. Chem., 21, 3249 (1983)

[26] Fineman M, Ross SD, J. Polym. Sci., 5, 259 (1950)

[27] Price CC, J. Polym. Sci., 3, 772 (1948)

[28] Alfrey T, Price CC, J. Polym. Sci., 2, 10 (1947)

[29] Young LJ, J. Polym. Sci., 54, 411 (1961)

[30] Dean JA, Lange's Handbook of Chemistry, McGraw-Hill, Inc., N.Y., 3-136 (1979)

[31] Chapin EC, J. Polym. Sci., 4, 597 (1949)