스티렌 중합에 있어서 방향족 니트로 화합물의 억제 반응 속도에 관한 연구

박동규; 조의제

Polymer(Korea), Vol.16, No.2, 131-137, March, 1992

Export Citation

스티렌 중합에 있어서 방향족 니트로 화합물의 억제 반응 속도에 관한 연구

Retardation Kinetics of Aromatic Nitro Compounds in Styrene Polymerization

박동규, 조의제

초록

방향족 니트로 화합물을 2,2'-azobisisobutyronitrile(AIBN)을 개시제로 하여 스티렌 중합의 엑제제로 사용하였다. 중합 억제 반응 실험은 진공(∼102^-5mmHg)하에서 조심스럽게 용액중의 기체를 제거한 후 vacuum dilatometer로써 반응 속도를 측정하였다. 사용된 5개의 니트로 화합물은 모두 억제 효과를 보였다. 스티렌 중합시 얻어진 실험 결과는 Fukui의 frontier electron density법으로 고찰하였다. 그 결과는 다음과 같다. 1) 45℃에서 억제제를 넣지 않고 AIBN과 스티렌만의 반응속도는 - dln[M]/dt=R_o=8.855×10^-3[AIBN]^1/2 percent per sec로 표시할 수 있었다. 2) dinitrotoluene의 K_χ값은 mononitrotoluene 보다 모두 큰 값을 나타내었다. 3) 2,6-, 2,3-, 3,4-dinitrotoluene의 K_χ값은 비슷하지만 2,4-dinitrotoluene 값보다 적었다. 4) 방향족 니트로 화합물의 S_r(또는 S_r') 값은 0.83과 0.86(또는 0.30과 0.39) 사이의 값을 나타내었다.

The aromatic nitro compounds have been used as retarders for the 2,2'-azobisisobutyronitrile(AIBN) catalyzed polymerization of styrene. All retardation experiments were carried out under vacuum(∼10_-5mmHg) with a carefully degassed solution. The rate was measured dilatometrically. All of aromatic nitro compounds tested showed retardation effects. The obtained reactivity data of styrene polymerization were examined in the light of the Fukui's frontier electron density method. The results are follows : 1) The unretarded rate was determined as : - dln[M]/dt=R_o=8.855×10^-3[AIBN]^1/2 percent per sec at 45℃. 2) The K_χ value of dinitrotoluene is larger than that of mononitrotoluene. 3) The K_χ values of 2,6-, 2,3-, 3,4-dinitrotoluene are similar but are smaller than that of 2,4-dinitrotoluene. 4) The S_r(or S_r') values of the aromatic nitrotoluene compounds showed between 0.83 and 0.86(or 0.30 and 0.39).

[References]

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[1] Bartlett PD, Kwart H, J. Am. Chem. Soc., 72, 1051 (1950)

[2] Kice JL, J. Am. Chem. Soc., 76, 6274 (1954)

[3] Kice JL, J. Polym. Sci., 19, 123 (1956)

[4] Kubin K, Zirkmund L, Coll. Czec. Chem. Comm., 32, 535 (1956)

[5] Caldwell RG, Ihrig JL, J. Polym. Sci., XLVI, 507 (1960)

[6] Yates WR, Ihrig JL, J. Am. Chem. Soc., 87, 710 (1965)

[7] Yates WR, "The Reactivity of Aromatic Amines toward Free Radicals," Ph.D. Dissertation, University of Hawaii (1964)

[8] Kim Y, J. Sci., 16, 47 (1973)

[9] Kim Y, J. Sci., 16, 63 (1973)

[10] Nobashi K, Yokota T, "Inhibitory Effects of Phenols on the Polymerization of Methylmethacrylate," S140A, Mem Coll Agric Kyoto Univ., 106, 45 (1974)

[11] Raetzsch M, Plaste Kautsch, 23(12), 896 (1976)

[12] Szakacs S, Bereznich T, Tados F, Jokay L, Makromol. Chem., 176(11), 3211 (1975)

[13] Tanczos I, Folders B, Tados F, Magy. Kem. Foly., 84(12), 557 (1978)

[14] Tomczos I, Folders B, Tados F, Magy. Kem. Foly., 88(9), 399 (1982)

[15] Park DK, Kim Y, Polym.(Korea), 12(8), 710 (1988)

[16] Fukui K, Yonezawa T, Shingu H, J. Chem. Phys., 20, 1247 (1957)

[17] Fukui K, Yonezawa T, Nagata C, J. Chem. Phys., 27, 1247 (1957)

[18] Fox TG, Loshaek S, J. Polym. Sci., 15, 371 (1955)

[19] Bamford CH, Barb WG, Jenkins AD, Onyon PF, "The Kinetics of Vinyl Polymerization by Radical Mechanism," Academic Press Inc., New York, 1958, Chapter 6 (1958)

[20] Bagdasar KHS, The Theory of Free Radical Polymerization, Israel Program for Scientific Translation, Jerusalem, 1968, Chapter V (1968)

[21] Matheson MS, Bevilacoya EB, Hart EJ, J. Am. Chem. Soc., 73, 1700 (1951)