Kinetic Study of Radical Copolymerization for Adhesives of Styrene with Alkyl Acrylate in a Continuous Stirred Tank Reactor

Young Ok Seo; Nam Seok Kim; Soo Duk Seul

Journal of Industrial and Engineering Chemistry, Vol.6, No.3, 174-181, May, 2000

Young Ok Seo, Nam Seok Kim, and Soo Duk Seul^†

Department of Chemical Engineering, Dona-A University, Pusan 604-714, Korea

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Copolymerizations of styrene (St.) with methyl acrylate (MA), ethyl acrylate (EA), and n-butyl acrylate (BA) were carried out in toluene at 80℃ in a continuous stirred tank reactor using benzoyl peroxide (BPO) as an initiator. The reaction volume and the residence time were 0.6 liters and 3 hours, respecitively. Copolymer composition was determined by an elemental analysis. Monomer reactivity ratios, r_St. and R_RA, were determined using both the Fineman-Ross and the Kelen-Tudos methods ; (r_St.=0.66, r_MA=0.17 (r_St.=0.87, r_MA=0.16) ; r_St.=0.73, r_EA=0.21 (r_St.=0.72, r_EA=0.18) ; r_St.=0.79, r_BA=0.20 (r_St.=0.62, r_BA=0.18). The cross-termination factor φ of the copolymer over the entire St. composition ranged from 0.5 to 1.0. The φ factors of the St.-RA copolymer increased with an increasing the St. content. The simulated results for conversion and copolymerization rate were compared with the experimental results. The average time to reach a dynamic steady-state was three and a half times that of the residence time.

Keywords:cstr;styrene;alkyl acrylate;adhesives

[References]

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Ray WH, Laurence RL, Polymerization Reactor Engineering in Chemical React of Theory, N.R. Amundson and Lapidus, Eds., Prentice-Hall, Eaglewood Cliffs, NJ (1977)
Hamer JW, Akramov TA, Ray WH, Chem. Eng. Sci., 36, 1897 (1981)
Balaraman KS, Kulkarni BD, Mashelkar RA, Chem. Eng. Commun., 16, 349 (1982)
Ziaee F, Nekoomanesh M, Polymer, 39(1), 203 (1998)
Finneman M, Ross SD, J. Polym. Sci., 66, 1594 (1944)
Kelen T, Tudos F, J. Macromol. Sci.-Chem., A9, 1 (1975)
Gruber E, Knell WL, Makromol. Chem., 179, 733 (1978)
Kaszas G, Foldes-Berezsnich T, Tudos F, Eur. Polym. J., 20, 395 (1984)
Kaszas G, Foldes-Berezsnich T, Tudos F, J. Macromol. Sci.-Chem., A22, 1571 (1985)
Davis TP, O'Driscoll KF, Pinto MC, Winik MA, Polym. Int., 24, 65 (1991)
Ma YD, Kim PS, Kubo K, Fukuda T, Polymer, 35(7), 1375 (1994)
Denbigh KG, Trans. Faraday. Soc., 43, 648 (1947)
Ray WH, Can. J. Chem. Eng., 47, 503 (1969)
Schmidt AD, Ray WH, Chem. Eng. Sci., 36, 1401 (1981)
Flory PJ, J. Am. Chem. Soc., 65, 372 (1943)
Fogler HS, Elements of Chemical Reaction Engineering, Chap. 5, Prentice-Hall, Englewood Cliffs, NJ (1986)
Walling C, Free Redicals in Solution, Chap. 4, Wiley, New York (1957)
Ito K, J. Polym. Sci. A-Polym. Chem., 16, 2725 (1978)
North AM, Polymer, 4, 134 (1963)
Atherton JN, North AM, Trans. Faraday Soc., 58, 2049 (1962)
O'Driscoll KF, Wertz W, Husar A, Polym. Prepr., 8, 380 (1967)
O'Driscoll KF, Wertz W, Husar A, J. Polym. Sci. A-Polym. Chem., 1, 2159 (1967)

[Referenced By]

[Related Articles]

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

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

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

[4] Wittmer P, Macromol. Chem. Suppl., 3, 129 (1979)

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

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

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

[8] Ziaee F, Nekoomanesh M, Polymer, 39(1), 203 (1998)

[9] Finneman M, Ross SD, J. Polym. Sci., 66, 1594 (1944)

[10] Kelen T, Tudos F, J. Macromol. Sci.-Chem., A9, 1 (1975)

[11] Gruber E, Knell WL, Makromol. Chem., 179, 733 (1978)

[12] Kaszas G, Foldes-Berezsnich T, Tudos F, Eur. Polym. J., 20, 395 (1984)

[13] Kaszas G, Foldes-Berezsnich T, Tudos F, J. Macromol. Sci.-Chem., A22, 1571 (1985)

[14] Davis TP, O'Driscoll KF, Pinto MC, Winik MA, Polym. Int., 24, 65 (1991)

[15] Ma YD, Kim PS, Kubo K, Fukuda T, Polymer, 35(7), 1375 (1994)

[16] Denbigh KG, Trans. Faraday. Soc., 43, 648 (1947)

[17] Ray WH, Can. J. Chem. Eng., 47, 503 (1969)

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

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

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

[21] Walling C, Free Redicals in Solution, Chap. 4, Wiley, New York (1957)

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

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

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

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

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