Iranian Journal of Polymer Science and Technology

Iranian Journal of Polymer Science and Technology

Kinetics of High-Temperature Bulk Thermal Polymerization of Methyl Styrene

Document Type : Research Paper

Authors
Mohammad Reza Jozaghkar 1
farshid ziaee 1
Hamid Reza Heyran Ardakani 1
Samaneh Ashenagar 2
Mehrdad Jalilian 1
1 Iran Polymer and Petrochemical Institute, P.O. Box 14975-112, Tehran, Iran
2 Department of Chemistry, Faculty of Basic Sciences, Tarbiat Modares University, P.O. Box 14115-175, Tehran, Iran
10.22063/jipst.2019.1661
Abstract
Hypothesis: Methyl styrene monomer is a styrene derivative, created by the methyl group(s) substituted on the benzene ring. Polymethyl styrene has similar properties as with polystyrene (PS) but a lower density and higher glass transition than PS. The knowledge of polymerization kinetics allows us to construct complex polymeric architectures with different polymerization techniques and controlling their polymerization conditions. The aim of this study is to study the kinetics of free radical polymerization of methyl styrene (64% meta- and 36% para-methyl styrene isomers) in the temperature range of 80-140°C, using second- and third-order thermal initiation models and moment equations.
Method: All polymerization runs were carried out through the ampoule method. Bulk thermal polymerization of methyl styrene was established in the range of 80-140°C and conversions were measured gravimetrically. Modeling of methyl styrene polymerization was simulated by MATLAB and moment equations. Moment equations were obtained by using the polymerization reaction. The assumed models for the initiation step of polymerization included second- and third-order in the monomer.
Finding: The theoretical results obtained from both initiation methods showed good agreement with the experimental results acquired from the gravimetric method. Also, it was demonstrated that the third-order model has better adaptation with experimental results of conversion than the second-order model. The similar results were obtained for modeling of average molecular weights. It was revealed that the gel effect had stronger effect on the average molecular weight than monomer transfer. This effect was more significant for weight average molecular weight than number average molecular weight. On the other hand, an ideal polymerization model, with no gel effect assumptions and having the same rate constants throughout, does not make good agreement with the experimental results.

Keywords
kinetic
methyl styrene
free radical polymerization
bulk thermal polymerization
modeling
  1. Carraher Jr. C.E., Introduction to Polymer Chemistry, USA, CRC, Chapt. 7, 2017.
  2. Akira H., Goseki R., and Ishizone T., Advances in Living Anionic Polymerization: From Functional Monomers, Polymerization Systems, to Macromolecular Architectures, Macromolecules, 47, 1883-1905, 2014.
  3. Braun C., Dohlen S., Ilg Y., Brodkorb F., Fischer B., Heindirk P., Kalbfleisch K., Richter T., Robers O., and Kreyenschmidt M., Antimicrobial Activity of Intrinsic Antimicrobial Polymers Based on Poly((tert-butyl-amino)-methyl-styrene) Against Selected Pathogenic and Spoilage Microorganisms Relevant in Meat Processing Facilities, J. Antimicrob. Agents, 3, 2017. DOI: 10.4172/2472-1212.1000136
  4. Physical Properties of Polymers Handbook, Mark J.E. (Ed.), New York, Springer, 2007.
  5. Hu S., Sun W., Fu J., Zhang L., Fan Q., Zhang Z., Wu W., and Tang Y., Reactive Molecular Dynamics Simulations on the Thermal Decomposition of Poly(a-methyl styrene), J. Mol. Model., 23, 179-, 2017.
  6. Gies A.P., Ellison S.T., Vergne M.J., Orndorff R.L., and Hercules D.M., MALDI-TOF/TOF CID Study of Poly(α-methylstyrene) Fragmentation Reactions, Anal. Bioanal. Chem., 392, 627-642, 2008.
  7. Kempf M., Barroso V.C., and Wilhelm M., Anionic Synthesis and Rheological Characterization of Poly(p-methylstyrene) Model Comb Architectures with a Defined and Very Low Degree of Long Chain Branching, Macromol. Rapid Comm., 31, 2140-2145, 2010.
  8. Banerjee S., Paira T.K., and Mandal T.K., Control of Molecular Weight and Tacticity in Stereospecific Living Cationic Polymerization of α-Methylstyrene at 0°C Using FeCl3-Based Initiators: Effect of Tacticity on Thermal Properties, Macromol. Chem. Phys., 214, 1332-1344, 2013.
  9. Karim T.B. and McKenna G.B., Unusual Surface Mechanical Properties of Poly(α-methylstyrene): Surface Softening and Stiffening at Different Temperatures, Macromolecules, 45, 9697-9706, 2012.
  10. Biryan F. and Demirelli K., Characterization, Thermal Behavior, and Electrical Measurements of Poly[4-(2-bromoisobutyroyl methyl) styrene], Adv. Polym. Technol., 37, 1994-2012, 2018.
  11. Kobayashi S., Kataoka H., Goseki R., and Ishizone T., Living Anionic Polymerization of 4-(1-Adamantyl)-α-Methylstyrene, Macromol. Chem. Phys., 219, 1700450, 2018.
  12. Ayat M., Belbachir M., and Rahmouni A., Selective Synthesis, Characterization and Kinetics Studies of Poly(α-Methylstyrene) Induced by Maghnite-Na+ Clay (Algerian MMT), B. Chem. Eng. Cat., 11, 376-388, 2016.
  13. Meille V., de Bellefon C., and Schweich D., Kinetics of α-Methylstyrene Hydrogenation on Pd/Al2O3, Ind. Eng. Chem. Res., 41, 1711-1715, 2002.
  14. Phiong H.S., Cooper C.G., Adesina A.A., and Lucien F.P., Kinetic Modelling of the Catalytic Hydrogenation of CO2-Expanded α-Methylstyrene, J. Supercrit. Fluid., 46, 40-46, 2008.
  15. Liao C., Duh Y., Shu C., and Tzeng J., Novel Determination of the Dimerization Mechanism for Thermal Polymerization of α-Methylstyrene, J. Therm. Anal. Calorim. 83, 75-78, 2006.
  16. Patel H., Ein-Mozaffari F., and Dhib R., CFD Analysis of Mixing in Thermal Polymerization of Styrene, Comput. Chem. Eng., 34, 421-429, 2010.
  17. Russell K. and Tobolsky A., Thermal Initiation of Styrene Polymerization, J. Am. Chem. Soc., 75, 5052-5054, 1953.
  18. Biesenberger J.A. and Sebastian D.H., Principles of Polymerization Engineering, New York, John Weily and Sons, Chapt. 2, 1983.
  19. Chiantore O. and Hamielec A., Thermal Polymerization of Methyl Styrene at High Conversions and Temperatures, Polymer, 26, 608-614, 1985.
  20. Mayo F.R., Chain Transfer in the Polymerization of Styrene: The Reaction of Solvents with Free Radicals, J. Am. Chem. Soc., 65, 2324-2329, 1943.
  21. Hui A.W. and Hamielec A.E., Thermal Polymerization of Styrene at High Conversions and Temperatures. An Experimental Study, J. Appl. Polym. Sci., 16, 749-769, 1972.
  22. Mahdavian A.R. and Zandi M., Thermal and Kinetic Study of Radical Polymerization I. Melt State Bulk Polymerization of Acrylamide by DSC, J. Appl. Polym. Sci., 87, 2335-2340, 2003.
  23. Mahdavian A.R., Abdollahi M., and Bijanzadeh H.R., Kinetic Study of Radical Polymerization. III. Solution Polymerization of Acrylamide by 1H-NMR, J. Appl. Polym. Sci., 93, 2007-2013, 2004.
  24. Buback M., Kowollik C., Kurz C., and Wahl A., Termination Kinetics of Styrene Free-Radical Polymerization Studied by Time-Resolved Pulsed Laser Experiments, Macromol. Chem. Phys., 201, 464-469, 2000.
  25. Beuermann S., Buback M., Hesse P., Junkers T., and Lacík I., Free-radical Polymerization Kinetics of 2-Acrylamido-2-Methylpropanesulfonic Acid in Aqueous Solution, Macromolecules, 39, 509-516, 2006.
  26. Mortamet A.C. and Pethrick R.A., Redox Initiated Free Radical Polymerization of 4-Methylstyrene, J. Appl. Polym. Sci., 123, 1539-1547, 2012.
  27. Cavin L., Rouge A., Meyer T., and Renken A., Kinetic Modeling of Free Radical Polymerization of Styrene Initiated by the Bifunctional Initiator 2,5-Dimethyl-2, 5-Bis (2-ethyl hexanoyl peroxy) Hexane, Polymer, 41, 3925-3935, 2000.
  28. Benbachir M. and Benjelloun D., Investigation of Free Radical Polymerization Using Diperoxyesters as Bifunctional Initiators, Polymer, 42, 7727-7738, 2001.
  29. Mao R. and Huglin M.B., A New Linear Method to Calculate Monomer Reactivity Ratios by Using High Conversion Copolymerization Data: Terminal Model, Polymer, 34, 1709-1715, 1993.
  30. Travas-Sejdic J. and Easteal A., Study of Free-Radical Copolymerization of Acrylamide with 2-Acrylamido-2-Methyl-1-Propane Sulphonic Acid, J. Appl. Polym. Sci., 75, 619-628, 2000.
  31. Selvaraj V., Sakthivel P., and Rajendran V., Effect of Ultrasound in the Free Radical Polymerization of Acrylonitrile under a New Multi-Site Phase-Transfer Catalyst-A Kinetic Study, Ultrason. Sonochem., 22, 265-271, 2015.
  32. Qiu L., Wang K., Zhu S., Lu Y., and Luo G., Kinetics Study of Acrylic Acid Polymerization with a Microreactor Platform, Chem. Eng. J., 284, 233-239, 2016.
  33. Mastan E., Li X., and Zhu S., Modeling and Theoretical Development in Controlled Radical Polymerization, Prog. Polym. Sci., 45, 71-101, 2015.
  34. Husain A. and Hamielec A.E., Thermal Polymerization of Styrene, J. Appl. Polym. Sci., 22, 1207-1223, 1978.

 

Iranian Journal of Polymer Science and Technology
Volume 32, Issue 3 - Serial Number 161
September and October 2019
Pages 225-238