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Received June 8, 2006
Accepted November 16, 2006
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Kinetics for free radical solution polymerization of heptadecafluorodecyl (meth)acrylate in supercritical carbon dioxide
School of Chemical and Biological Engineering and Institute of Chemical Processes, Seoul National University, Seoul 151-744, Korea 1R&D Institute, Miwon Commercial Co., Ltd., 405-3, Moknae-Dong, Ansan-Si, Kyonggi 425-100, Korea
Korean Journal of Chemical Engineering, July 2007, 24(4), 664-669(6), 10.1007/s11814-007-0022-x
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Abstract
Free radical solution polymerization of heptadecafluorodecyl acrylate (HDFDA) and heptadecafluorodecyl methacrylate (HDFDMA) was carried out by using 2,2'-azobisisobutyronitrile (AIBN) as the initiator in supercritical carbon dioxide (scCO2). We performed solution polymerization with changing initiator concentration, temperature and polymerization time to study the polymerization kinetics. A nonlinear least square method and dead-end theory were used to determine the constant, K (K=(kp√f )/√fdkt) and initiator decomposition rate constant (kd) from experimental data. kd was measured as 3.77×10-5 s-1 at 62.7 ℃ for poly(HDFDA) and 2.71×10-5 s-1 at 62.5 ℃ for poly(HDFDMA), respectively, by nonlinear least square method.
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References
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Ajzengerg N, Trabelsi F, Recasens F, Chem. Eng. Technol., 23, 10 (2000)
Cooper AI, J. Mater. Chem., 10, 207 (2000)
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McHugh MA, Krukonis VJ, Supercritical fluid extraction principles and practice, 2nd ed., Butterworth-Heinemann, Boston, NA (1994)
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Kendall JL, Canelas DA, Young JL, Desimone JM, Chem. Rev., 99(2), 543 (1999)
Guan Z, Combes JR, Menceloglu YZ, DeSimone JM, Macromolecules, 29, 2663 (1993)
Odian G, Principles of polymerization, 3rd ed., JOHN WILEY & SONS (1991)
DeSimone JM, Guan Z, Elsbernd CS, Science, 257, 945 (1992)
Ryan J, Erkey C, Shaw N, Polym. Prepr, 38, 428 (1997)
