Dispersion polymerization of N-vinyl caprolactam in supercritical carbon dioxide

Jungin Shin; Dong Woo Cho; Won Bae; Hwayong Kim

Korean Journal of Chemical Engineering, Vol.27, No.5, 1613-1620, September, 2010

DOI10.1007/s11814-010-0255-y Export Citation

Dispersion polymerization of N-vinyl caprolactam in supercritical carbon dioxide

Jungin Shin, Dong Woo Cho, Won Bae¹, and Hwayong Kim^†

School of Chemical and Biological Engineering and Institute of Chemical Processes, Seoul National University, 559, Gwanang-ro, Gwanak-gu, Seoul 151-744, Korea
¹R&D Institute, Miwon Specialty Chemical Co., Ltd., 405-3, Moknae-dong, Ansan-si, Gyeonggi-do 425-100, Korea

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Dispersion polymerization of N-vinyl caprolactam (NVCL) was carried out in supercritical carbon dioxide (scCO2) using three surfactants. The polymerization was performed in the presence of fluorine-based poly(heptadecafluorodecyl acrylate) (PHDFDA), poly(heptadecafluorodecyl methacrylate) (PHDFDMA) or siloxane-based PDMSg-pyrrolidonecarboxylic acid (Monasil PCA) as a surfactant. FE-SEM and image analyzer were used to characterize particle morphology, size, and size distribution. When fluorine-based surfactants were used, spherical PVCL particles were obtained. Using Monasil PCA resulted in agglomerated and irregular polymer particles. The effect of concentration of surfactants, initiators, and monomer, and reaction pressure on the particle morphology, average particle size and particle size distribution (PSD) was also investigated with fluorine-based surfactant, PHDFDA or PHDFDMA.

Keywords:Supercritical Carbon Dioxide;N-vinyl Caprolactam;Dispersion Polymerization;Fluorine-based Surfactant

[References]

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DeSimone JM, Tumas W, Green chemistry using liquid and supercritical carbon dioxide., Oxford University Press, Inc. (2003)
McHugh MA, Krukonis VJ, Supercritical fluid extraction:principle and practice., 2nd Ed., Butterworth-Heinemann, Boston (1994)
Cooper AI, J. Mater. Chem., 10, 207 (2000)
Beckman EJ, J. Supercrit. Fluids, 28(2-3), 121 (2004)
Markvicheva EA, Bronin AS, Kudryavtseva NE, Rurnsh LD, Kirsh YE, Zubov VP, Biotechnol. Technol., 8, 143 (1994)
Verbrugghe S, Bernaerts K, Filip E, Macromol. Chem. Phys., 204, 1217 (2003)
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Hinkley JA, Morgret LD, Gehrke SH, Polymer, 45(26), 8837 (2004)
Shin J, Oh KS, Bae W, Lee YW, Kim H, Ind. Eng. Chem. Res., 47(15), 5680 (2008)
Shin J, Bae W, Lee YW, Kim H, J. Chem. Eng. Data., 51, 1571 (2006)
Shin J, Bae W, Kim H, Lee YW, J. Chem. Eng. Data., 53, 1523 (2008)
Kwon S, Lee K, Bae W, Kim H, J. Supercrtit. Fluids., 30, 127 (2008)
Kwon S, Bae W, Kim H, J. Chem. Eng. Data., 50, 1560 (2005)
Paine AJ, Luymes W, McNulty J, Macromolecules., 23, 3104 (1990)
Ober CK, Hair ML, J. Polym. Sci.: Part A: Polym. Chem. Ed., 25, 1395 (1987)
Shen S, Sudol ED, El-Aasser MS, J. Polym. Sci.: Part A:Polym. Chem. Ed., 31, 1393 (1993)
Horak D, Krystufek M, Spevacek J, J. Polym. Sci. A: Polym. Chem., 38(3), 653 (2000)
Hsiao YL, Maury EE, Desimone JM, Mawson S, Johnston KP, Macromolecules, 28(24), 8159 (1995)
Carson T, Lizotte J, Desimone JM, Macromolecules, 33(6), 1917 (2000)

[Related Articles]

[1] Kawaguchi S, Ito K, J. Adv. Polym. Sci., 175, 299 (2005)

[2] Saenx JM, Asua JM, J. Polym. Sci.: Part A: Polym. Chem., 33, 1511 (2000)

[3] Tseng CM, Lu YY, El-Aasser MS, Vanderhoff JW, J.Polym. Sci.: Part A: Polym. Chem. Ed., 24, 2995 (1986)

[4] Kendall JL, Canelas DA, Young JL, DeSimone JM, Chem. Rev., 99(2), 543 (1999)

[5] Canelas DA, Betts DE, Desimone JM, Macromolecules, 29(8), 2818 (1996)

[6] Shiho H, DeSimone JM, J. Polym. Sci. A: Polym. Chem., 37(14), 2429 (1999)

[7] DeSimone JM, Tumas W, Green chemistry using liquid and supercritical carbon dioxide., Oxford University Press, Inc. (2003)

[8] McHugh MA, Krukonis VJ, Supercritical fluid extraction:principle and practice., 2nd Ed., Butterworth-Heinemann, Boston (1994)

[9] Cooper AI, J. Mater. Chem., 10, 207 (2000)

[10] Beckman EJ, J. Supercrit. Fluids, 28(2-3), 121 (2004)

[11] Markvicheva EA, Bronin AS, Kudryavtseva NE, Rurnsh LD, Kirsh YE, Zubov VP, Biotechnol. Technol., 8, 143 (1994)

[12] Verbrugghe S, Bernaerts K, Filip E, Macromol. Chem. Phys., 204, 1217 (2003)

[13] Kirsh YE, Yanul NA, Kalninsh KK, Eur. Polym. J., 35, 305 (1999)

[14] Mikheeva LM, Grinberg NV, Mashkevich AY, Grinberg VY, Thanh LT, Makhaeva EE, Khokhlov AR, Macromolecules, 30(9), 2693 (1997)

[15] Shtankon I, Lequieu W, Goethals EJ, Du Prez FE, Polym.Int., 52, 1605 (2003)

[16] Hinkley JA, Morgret LD, Gehrke SH, Polymer, 45(26), 8837 (2004)

[17] Shin J, Oh KS, Bae W, Lee YW, Kim H, Ind. Eng. Chem. Res., 47(15), 5680 (2008)

[18] Shin J, Bae W, Lee YW, Kim H, J. Chem. Eng. Data., 51, 1571 (2006)

[19] Shin J, Bae W, Kim H, Lee YW, J. Chem. Eng. Data., 53, 1523 (2008)

[20] Kwon S, Lee K, Bae W, Kim H, J. Supercrtit. Fluids., 30, 127 (2008)

[21] Kwon S, Bae W, Kim H, J. Chem. Eng. Data., 50, 1560 (2005)

[22] Paine AJ, Luymes W, McNulty J, Macromolecules., 23, 3104 (1990)

[23] Ober CK, Hair ML, J. Polym. Sci.: Part A: Polym. Chem. Ed., 25, 1395 (1987)

[24] Shen S, Sudol ED, El-Aasser MS, J. Polym. Sci.: Part A:Polym. Chem. Ed., 31, 1393 (1993)

[25] Horak D, Krystufek M, Spevacek J, J. Polym. Sci. A: Polym. Chem., 38(3), 653 (2000)

[26] Hsiao YL, Maury EE, Desimone JM, Mawson S, Johnston KP, Macromolecules, 28(24), 8159 (1995)

[27] Carson T, Lizotte J, Desimone JM, Macromolecules, 33(6), 1917 (2000)