연속 반응기(CSTR)에서 Methyl Methacrylate와 Styrene의 라디칼 공중합 반응 속도론

신봉섭; 빈병권; 설수덕

Polymer(Korea), Vol.17, No.4, 452-462, July, 1993

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연속 반응기(CSTR)에서 Methyl Methacrylate와 Styrene의 라디칼 공중합 반응 속도론

The Kinetics of Radical Copolymerization of Methyl Methacrylate and Styrene in a continuous Stirred Tank Reactor(CSTR)

신봉섭, 빈병권, 설수덕

초록

메틸 메타크릴레이트(MMA)와 스티렌(St)을 등온하에서 라디칼 공중합에 대한 반응속도론적 고찰에 대하여 연속반응기(CSTR)를 사용하여 연구하였다. 톨루엔 중에서 BPO를 개시제로 사용하였으며, 반응몰부피, 체류시간 및 중합온도는 각각 0.3L, 3시간 및 80℃로 하였다. 중합은 반응성비를 결정하기 위하여 적절히 높은 전환율에 도달될때 까지 수행되었다. 공중합체의 전환율은 FTIR, EA, GPC, DSC 및 TGA,등으로 분석 되었으며, 단량체의 반응성비 r₁(MMA)과 r₂(St)는 KelenT d s법으로 결정하였다. r₁=0.59, r₂=0.61. 공중합체의 φ값은 St의 전체조성에 걸쳐 0.46에서 0.55의 범위였으며, St의 조성이 증가할수록 증가 하였다. MMA와 St의 공중합 반응은 2차 반응속도론에 따랐으며, 시뮬레이션 한 전환율과 종중합속도를 실험결과와 비교하였다. 동적인 정상상태에 도달되는 평균시간은 체류시간의 3배였으며, 반응기내에서 정상상태에 접근하는 특성이 주어졌다. φ의 단일값으로 실험값과 시뮬레이션 값과의 좋은 일치점을 얻는 것은 어려웠다.

The kinetics of isothermal and radical copolymerization of methyl methacrylate(MMA) with styrene(St) has been investigated suing a continuous stirred tank reactor(CSTR). Solvent and initiator used were toluene and benzoyl perroxide. Reaction volum, residence time and polymerization temperature were 0.3 liters, 3 hours and 80℃, respectively. Polymerizations were carried out to reach moderarely high conversions to determine the reactivity ratios. The copolymerization conversions were analyzed by FT-IR, EA, GPC, DSC and TGA. The monomer reactivity ratios, r₁(MMA) and r₂(St) were determined by the Kelen-T d s method : r₁=0.59, r₂=0.61. The φ factors of the copolymer over the entire St compositions ranged from 0.46 to 0.55 and increased with increasing St compositions. The copolymerization if MMA and St followed the second order kinetics. The simulated conversions and copolymerization rates were compared with the experimental results. The average time to reach dynamic steady-state was three times of the residence time. The approach to steady-state in the reactor was characterized. It was not possible to obtain good agreement between experiment and simulation with a single value of the φ factor.

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[1] Kim KJ, Choi KY, Polym. Eng. Sci., 30, 279 (1990)

[2] Das S, Rodriguez F, J. Appl. Polym. Sci., 32, 5981 (1986)

[3] Schintuch M, Schmit ZRA, Catal. Rev.-Sci. Eng., 15, 107 (1977)

[4] Slinko MG, Slinko MM, Catal. Rev.-Sci. Eng., 17, 119 (1978)

[5] Knorr RS, O'Driscoll KF, J. Appl. Polym. Sci., 14, 2683 (1970)

[6] Balaraman KS, Kulkarni BD, Mashelkar RA, Chem. Eng. Commun., 16, 349 (1982)

[7] Ogorkiewicz RH, "Engineering Properties of Thermoplastics," Wiley-Interscience, New York, 215 (1970)

[8] Fogler HS, "Elements of Chemical Reaction Engineering," Chap. 5, Prentice-Hall, Englewood Cliffs, NJ (1986)

[9] Smith WV, J. Am. Chem. Soc., 71, 4077 (1949)

[10] Bevington JC, Harris DO, J. Polym. Sci. B: Polym. Phys., 5, 799 (1967)

[11] Ray WH, Laurence RL, "Polymerization Reactor Engineering in Chemical Reactor Theory," N.R. Amundson and Lapidus, Eds., Prentice-Hall, Englewood Cliffs, NJ (1977)

[12] Walling C, "Free Radicals in Solution," Chap. 4, Wiley, New York (1957)

[13] Hamer JW, Akramov TA, Ray WH, Chem. Eng. Sci., 36, 1897 (1981)

[14] Flory PJ, J. Am. Chem. Soc., 65, 372 (1943)

[15] North AM, Polymer, 4, 134 (1963)

[16] Ito K, J. Polym. Sci. A: Polym. Chem., 16, 2725 (1978)

[17] Atherton JN, North AM, Trans. Faraday Soc., 58, 2049 (1962)

[18] O'Driscoll KF, Wertz W, Husar A, Polym. Prepr., 8(1), 380 (1967)

[19] O'Driscoll KF, Wertz W, Husar A, J. Polym. Sci. A: Polym. Chem., 1(5), 2159 (1967)

[20] Plate NA, Ponomarenko AG, Polym. Sci. USSR, 16, 3067 (1974)

[21] Ito K, Kodaira K, Polym. J., 18, 667 (1986)

[22] Matheson MS, Auer EE, Bevilacqua EB, Hart EJ, J. Am. Chem. Soc., 73, 1700 (1951)

[23] Ham GE, J. Polym. Sci., 14, 87 (1954)

[24] Schmidt AD, Ray WH, Chem. Eng. Sci., 36, 1401 (1981)

[25] Das S, Rodriguez F, J. Appl. Polym. Sci., 39, 1309 (1990)

[26] Stolzenberg K, Kirchner K, Die Angewandte Makromolekulare Chemie, 95(1498), 185 (1981)

[27] Kirchner K, Rintelen T, Die Angewandte Makromolekulare Chemie, 141(2292), 85 (1986)

[28] Adebekun AK, Kwalik KM, Schork FJ, Chem. Eng. Sci., 44, 2269 (1989)

[29] Adebekun AK, Kwalik KM, Schork FJ, Chem. Eng. Sci., 44, 2281 (1989)

[30] Hamer JW, Akramov TA, Ray WH, Chem. Eng. Sci., 36, 1897 (1981)

[31] Yokota K, Kani M, Ishii Y, J. Polym. Sci. A: Polym. Chem., 6, 1325 (1968)