Styrene Conversion Modeling and Estimation of Polydispersity Index
DOI:
https://doi.org/10.24949/njes.v7i1.132Abstract
In this study, the kinetics of free radical polymerization of styrene initiated by benzoyl peroxide in polar solvent are described. A model was developed based on set of elementary reactions by mass balance of the chemical species and method of moment analysis. The set of modeled equations were solved analytically using the Garg et al (G-model) approach for the estimation of polystyrene average properties such as weight and number average molecular weights and polydispersity which were found to vary with reaction conditions and styrene monomer conversion. Our earlier reported styrene monomer conversion model was improved upon by the incorporation of the Trommsdoff Norrish effect . The modified conversion model was found to give better prediction.
Key words: Kinetics, radical polymerization, G-model, polydispersity, method of moment, Trommsdoff Norrish effect.
References
Willemse ,R.X.E., (2005) New insights into free-radical (co)polymerization kinetics ,Ph.D Thesis , Technische Universiteit, Eindhoven.
Coatas,K., Krallis,A., Pladis, P., Kiparissides,C.(2003) A comprehensive kinetic model for the combined chemical and thermal polymerization of styrene up to high conversion, Macromolecular chemistry physics, 204, 1305-1314.
Frounchi,M., Farhadi,F.,Mohammadi,R.P (2002) Simulation of styrene radical polymerization
in batch Reactor: A modified kinetic model for high conversion,Science Iranica,9(1):86-92.
Cunha, F.R., Costa, J.M., Nele, R.O., Folly, M.B.,Souza Jr ,Pinto,J.C .(2013). Influence of
reaction operation conditions on the final properties of high impact polystyrene(HIPS),Brazilian
Journal of chemical engineering, vol.30, no. 3, pp.575-587.
Maafa,I.M.,Joao,B.P.S., Elkamel.,A. (2007) Prediction of chain length distribution of polystyrene made in batch reactors with bifunctional free radical initiators using dynamic Monte Carlo Simulation.Macromolecular Reaction Engineering. 1: 364-383.
Verros, G.D. (2003) Calculation of molecular weight distribution in non-linear free radical copolymerization, Polymer , 44: 7021–7032.
Suryaman, F.R., (2006) Mechanistic modeling and model-based studies in spontaneous solution polymerization of alkyl acrylate monomers ,Ph.D Thesis , Drexel University,U.S.A.
Garg,G.K., Serra, C.A., Hoarau,Y., Parida, D., Bouquey,M., Muller,R., .(2014). Analytical solution of free radical polymerization:Derivation and validation, Macromolecules, vol.47, no.14, pp.44567-4586
Baillagou, P.E., Song, D.S. (1985). Major factors contributing to the non-linear kinetics of free radical Polymerization. Chemical Engineering Science, vol. 40, no. 1, pp.75-86
Louie,B.M., Carrat,G.M., Soong,D.S. (1985) Modeling the free radical solution and bulk polymerization of Methyl-methacrylate,Journal of applied polymer science, vol.30, no.10, pp.3985-4012.
Dhib, N; Al-Nidawy, R; (2002) Modeling of free radical polymerization of ethylene using
difunctional initiators, Chemical Engineering Science, 57: 2735- 2746.
Kiparissides, C. (2006) Challenges in particulate polymerization reactor modeling and Optimization: A Population Balance Perspective. Journal of Process, 16: 205-224.
Zhu,S.,Gu,L.,Haymak,A.N.,Pelton,R.H. (2001) Kinetics and modeling of free radical polymerization of N-vinylformamide,polymer,42,3077-3086.
Konstadinidis,K.,Achilias,D.,Kiparissides,C.,(1992), Development of a Unified Mathematical Framework For Modeling Molecular and Structural Changes Free Radical Homopolymerization Reaction,Polymer,Vol.33,No.23,5019-5030.
Achilias ,D.S., and Kiparissides, C. (1992) Toward the development of a general framework for modeling molecular-weight and compositional changes in free-radical co-polymerization reactions, Journal of Macromolecular Science-Reviews in Macromolecular Chemistry and Physics, 32 (2):183-234.
Tobita,H and Zhu,S. (2014), Modeling and simulation of complex polymerization reactions,macromolecular theory and simulations,23:107-109.
Almeida, A.S., Wada, K., and Secchi, A,R. (2008) Simulation of styrene polymerization reactors: kinetic and thermodynamic modeling, Brazilian Journal of Chemical Engineering, 25 (2): 337 – 349.
Mohammad,A.H., Mohd, A.Z., Farouq,S.M 2011. Hybrid modelling and kinetic estimation for polystyrene batch reactor using Artificial Neutral Network (ANN) approach , Asia-Pacific Journal of Chemical Engineering ,6 (2): 274–287.
Chen, C., (2000) Continuous production of solid polystyrene in back-mixed and linear-flow reactors, Polymer Engineering and Science,40 (2): 441-464.
Pladis, P., and Kiparissides, C. (1998) A comprehensive model for the calculation of molecular weight-long-chain branching distribution in free-radical polymerizations, Chemical Engineering Science, 53(18): 3315–3333.
Penlidis,A., Ponnuswamy, S.R., Kiparissides, C and O’Driscoll, K.F.(1992) Polymer reaction engineering:modeling consideration for control studies,The chemical engineering journal,50:95-107.
Kee, J.K.M., Kyu,Y.C., (1988),Steady state behaviour of a continuous stirred tank reactor
for styrene polymerization with bifunctional free radical initiators,chemical engineering
science,43(4):965-977.
Ogo,Y., (1984) Polymerization at High Pressures, Journal of Macromolecular Science - Reviews in Macromolecular Chemistry & Physics., 24 (1):1-48
Goto, S., Yamamoto, K., Furui, S., and Sugimoto, M. (1981) Computer model for commercial high pressure polyethylene reactor based on elementary reaction rates obtained experimentally. Journal of Applied Polymer Science, 36: 21–40.
Wu ,G.Z.A., Denton, L.A and Laurence ,(1982) R.L Batch polymerization of styrene-optimal temperature histories , Polymer Engineering & Science, 22, (1): 1–8.
Yamamoto,K.and Sugimoto.M.(1979) Rate constants for long chain branch formation in free radical polymerization of ethylene, Journal of Macromolecular Science: Part A – Chemistry 13 (8):1067-1080.
Friis, N.,and Hamielec, A.E.(1976), Gel effect in emulsion polymerization of vinyl monomers.ACS Symposium series, 24: 82-91.
Hui , A.W., and Hamielec , A.E. (1972) Thermal polymerization of styrene at high conversions and temperatures. An experimental study Journal of Applied Polymer Science ,16 (3), 749–769.
Ehrlich, P. and Mortimer, G. A. (1970) Fundamentals of the Free-Radical Polymerization of Ethylene. Advanced Polymer Science. 7: 386-448.
Oskada, K., and Fan, L.T., (1970). Computation of near optimal control policies for free radical polymerization reactors. Applied Polymer Science,14: 3065-3082.
Hamielec,A.E., and J.W Hodgins,(1967) Polymer reactors and molecular weight distribution:part II.Free radical polymerizationin a batch reactor, American Institute of Chemical, Engineers. 13(6):1087-1091.
Kiparissides, C., Verros, G., and Mcgregor, J. (1993). Mathematical Modeling,
Optimization and Quality Control of High-Pressure Ethylene Polymerization Reactors. Journal
of Macromolecular Science — Reviews in Macromolecular Chemistry and physics, vol.33, no.
, 437–527.
Arriola, D.J. (1989), Ph.D. Thesis ,Department of Chemical Engineering, University of
Wisconsin, Madison.
Westerhout, R. W. J. , Waanders, . J., . Kuipers, J. A. M and. van Swaaij , W. P. M ,(1997) Kinetics of the low-temperature pyrolysis of polyethene, polypropene, and polystyrene modeling, experimental determination, and comparison with literature models and data, Industrial & Engineering Chemistry Research 36 (6):1955-1964.
Hamer.,J.W., Akramov,T.A.,Ray,W.A.(1981),The dynamic behaviour of continuous polymerization reactors-II Chemical Engineering Science.36:1897-1914.
Gupta, S. K., A. Kumar and M.V.G. Krishnamurthy (1985).Simulation of Tubular low density Polyethylene.Polymer Engineering Science, 25 (1): 37-47.
Lee, K.H. and J.P. Marano (1979). High pressure polymerization of ethylene and rheological
behaviour of polyethylene products. American chemical society symposium. 104, 221.
Takahaski, T. and P. Ehrlich (1982). Absolute rate constants for the free radical polymerization of ethylene in the supercritical phase ,Macromolecules, 15, 714.
Thies, J. and K. Schoenemann (1970). 1st International symposium chemical. reaction
Engineering ,Washington, DC.
Fogler, H. S. (1999) Elements of Chemical Reaction Engineering. Prentice Hall
International Series in the Physical and Chemical Engineering Sciences, 3ed.
Kehinde ,A.J, Usman,M.A, and Owolabi ,R.U. (2013).Solvent –initiator compatibility and sensitivity of conversion of styrene homo-polymerization, Journal of Polymer Engineering ,33 (9):775-783.
Christophe S., Nicolas S., Guy S., Georges H. and Volker H. (2005) Numerical simulation of polymerization in interdigital multilamination micromixers, The Royal Society of Chemistry, 5: 966–973.
Kiparissides,C., Kotoulas.C, Krallis, A Pladis,P (2003) A Comprehensive Kinetic Model for the Combined Chemical and Thermal Polymerization of Styrene up to High Conversions, Macromol. Chem. Phys. , 204, 1305–1314
Gao, J.; Penlidis, A. (1998) A comprehensive simulator database package for reviewing free-radical copolymerizations" Journal of Macromolecular Science-Reviews in Macromolecular Chemistry and Physics, C38, 651-780.
Brown, William H.; Foote, Christopher S.; Iverson, Brent L.; Anslyn, Eric V. (2012). Organic chemistry (6 ed.). Cengage Learning. p. 1161. ISBN 978-0-8400-5498-2
Rogosic,M.,Mencer,H.J.,Gomzi,Z.,(1996) Polydispersity index and molecular weight distributions of polymers, European polymer journal ,32. (2) 1337-1344.
Mencer,H.J.,(1988) Efficiency of polymer fractionation—A review, Polymer Engineering & Science,28, (8), 497–505.
Pinto,J.M., Guidici,R.,(2001) Optimization of a cocktail of initiators for suspension polymerization of vinyl chloride in batch reactors , Chemical Engineering Science 56, 1021-1028
Wen-Yan, H., Dan L, Bi-Biao J, Dong-Liang, Z., Yang Y.,Jian-Hai, C., Guang-Qun, Z., Lizhi, K., Chun-Lin, L.,Fang-Hong G., and Ai-Qing, L. (2010). Branching Copolymerization of Styrene and Methyl Methacrylate with Divinylbenzene, Iranian Polymer Journal, vol.19, no. 8, pp.589-598.
Noro, A. Cho, D. Takano, A. Matsushita, Y.(2005). Effect of molecular weight distribution on microphase-separated structures from block copolymers, Macromolecules, vol.38, no.10, pp. 4371-4376.
Lynd, N. A., Hamilton, B. D. Hillmyer, M . A. (2007).The Role of Polydispersity in the Lamellar Mesophase of Model Diblock Copolymers. Journal of Applied Polymer. Physics, vol.45, no.24, 3386 – 3393.
Tefera, N., Weickert,G., Westerterp,K.R., (1997) Modeling of free radical polymerization up to high conversion. II. Development of a mathematical model, Journal of Applied Polymer Science ,63(12):1663-1680
Kissin,Y.V., Robert I. M., Thomas E. N., Anita J. B.(1999).Kinetics and mechanism of ethylene homopolymerization and copolymerization reactions with heterogeneous Ti-based Ziegler–Natta catalysts. Topics in Catalysis, vol.7, no.1, pp.69-88.
Hakim,S., Nekoomanesh, M., Nieat, M.A.(2008). Investigating the behaviour of a Bi-supported SiO2/TiCl4/THF/MgCl2 catalyst in slurry ethylene polymerization: Activity and molecular weight. Iranian Polymer Journal, vol.17, no.3, pp.209-216.
Amarjit, S., Decheng, M., David, K. (2000). Enzyme-Mediated Free Radical Polymerization of Styrene. Biomacromolecules, vol.1, no.4, pp. 592-596.
Ivanchev,S.S., Badaev,V.K., Ivanchev,N.I., Khaikun,S.Y (2004). Diklady Physical Chemsitry, vol. 46, pp.394.