Radical Polymerization Kinetics of Hexyl Methacrylate in Dimethylsulfoxide Solution
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Abstract
In this study, we conducted a series of polymerization studies of hexyl methacrylate in dimethyl sulfoxide with (0.1 - 0.4) mol dm-3 of monomer and (1 10-3 – 4 10-3) mol dm-3 of benzoyl peroxide as initiators at 70 °C. Using the well-known conversion vs. time technique, the effects of initiator and monomer concentration on the rate of polymerization (Rp) were studied. An initiator of order 0.35 was obtained in accordance with theory and a divergence from normal kinetics was detected with an order of 1.53 with respect to monomer concentration. The activation energy was determined to be (72.90) kJ mol-1, which does not correspond to the value of most thermally initiated monomers. The observed value of activation energy suggests that propagation and termination reactions have equal activation energy and the difference between them is nearly zero. The average degree of polymerization (DPn) decreased as benzoyl peroxide concentration increase whereas an increase in solvent polarity has slightly increased rate of polymerization value.
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References
Chmela, Š.; Fiedlerová, A.; Liptaj, T.; Catel, Y.; Moszner, N. Synthesis and
homopolymerization kinetics of 7-(methacroyloxy)-2-oxo-heptylphosphonic acid and its
copolymerization with methyl methacrylate. Designed monomers and polymers 2019, 20, 70-90.
Victoria‐Valenzuela, D.; Herrera‐Ordonez. J.; Luna‐Barcenas, G. Toward a General
Methodology for Modeling Diffusive‐Controlled Reactions in Free Radical
Polymerization. Macromole cular Theory and Simulations 2016, 25, 28-44.
Barner-Kowollik, C.; Russell, T. Chain-length-dependent termination in radical polymerization:
Subtle revolution in tackling a long-standing challenge. Progress in polymer science 2012, 34,
-1259. .
Cao, Z.H.; Shan, G.R.; Fevotte, G.; Sheibat-Othman, N.; Bourgeat-Lami, E. Miniemulsion
copolymerization of styrene and γ-methacryloxypropyltrimethoxysilane: kinetics and
mechanism. Macromolecules 2012, 41, 5166-5173.
IHJPAS. 36(2)2023
Ali, A.; Muhammad, N.; Hussain. S.; Jamil. M. I.; Uddin. A.; Aziz. T.; & Guo. L. Kinetic and
thermal study of ethylene and propylene homo polymerization catalyzed by ansa-zirconocene
activated with alkylaluminum/borate: Effects of alkylaluminum on polymerization kinetics and
polymer structure. Polymers. 2021 13(2), 268.
Chmela, Š.; Fiedlerová, A.; Liptaj, T.; Catel, Y.; Moszner, N. Determination of
homopolymerization kinetics and copolymerization with methyl methacrylate of diethyl 9-
(methacryloyloxy)-2-oxo-nonylphosphonate, 9-(methacryloyloxy)-2-oxo-nonylphosphonic acid
and diethyl 9-(methacryloyloxy)-nonylphosphonate e-Polymers. 2018, 18, 205-216.
Pardal, F.; Lapinte, V.; Robin, J.J. Kinetics of cotelomerization of 3-(trimethoxysilyl) propyl
methacrylate and perfluorodecylacrylate. European Polymer Journal 2009, 45, 1198-207.
Cao, Z.H.; Shan, G.R.; Fevotte, G.; Sheibat-Othman, N.; Bourgeat-Lami, E. Miniemulsion
copolymerization of styrene and γ-methacryloxypropyltrimethoxysilane: kinetics and mechanism.
Macromolecules 2018, 41, 5166-73.
Du, J.; Chen, Y.; Atom-transfer radical polymerization of a reactive monomer: 3-
(trimethoxysilyl) propyl methacrylate. Macromolecules 2004, 37, 6322-8.
Christian, P.; Giles, M.R.; Griffiths, R.M.; Irvine, D.J.; Major, R.C.; Howdle, S.M. Free radical
polymerization of methyl methacrylate in supercritical carbon dioxide using a pseudo-graft
stabilizer: effect of monomer, initiator, and stabilizer concentrations. Macromolecules 2000 33,
-7.
Victoria‐Valenzuela, D.; Herrera‐Ordonez, J.; Luna‐Barcenas, G.; Verros, G.D.; Achilias, D.S.
Bulk Free Radical Polymerization of Methyl Methacrylate and Vinyl Acetate: A Comparative
Study. Macromolecular Reaction Engineering 2016, 10, 577-87.
Dharmendira Kumar, M.; Konguvel Thehazhnan, P.; Umapathy, M.J.; Rajendran M. Free
radical polymerization of methyl methacrylate in the presence of phase transfer catalyst—a kinetic
study. International Journal of Polymeric Materials 2004, 53, 95-103.
Mohammed, A.H. Studying Reactivity Relationships of Copolymers N-naphthylacrylamide
with (Acrylicacid and Methylacrylate). Baghdad Science Journal 2019, 16, 0345-0345.
Mohammed, K.M.; Abdalla, I.K.; Mohammed, A.H.; Khairuddin, F.H.; Ibrahim, A.N.H.;
Rosyidi, S.A.P.; Yusoff, N.I.M. Determining the Effects of RH-WMA on the Engineering
Properties of Bitumen. Jurnal Teknologi 2020, 81, 2-10.
Edmondson, S.; Gilbert, M. The Chemical Nature of Plastics Polymerization. InBrydson's
Plastics Materials (Eighth Edition) 2017, 19-37.
Giap, S.G. The hidden property of arrhenius-type relationship: viscosity as a function of
temperature. Journal of Physical Science 2010, 21, 9-39.
Wu, G.; Wang, C.; Tan, Z. Zhang, H. Effect of temperature on emulsion polymerization of nbutyl acrylate. Procedia Engineering 2012, 18, 353-7.
Yu, X.; Pfaendtner, J.; Broadbelt, L.J. Ab initio study of acrylate polymerization reactions:
Methyl methacrylate and methyl acrylate propagation. The Journal of Physical Chemistry A. 2008,
, 772-82.
Masuda, S.; Minagawa, K.; Ogawa, H.; Tanaka, M. Polymerization and copolymerization of
methyl α‐acetylaminoacrylate. Macromolecular Chemistry and Physics 2000, 201, 787-92.
Mohammed, A.; Dhedan, R.M; Mahmood, W.A.; Musa, A. Copolymers of Castor and Corn
Oils with Lauryl Methacrylate as Green Lubricating Additives. Egyptian Journal of Chemistry
, 64, 1-2.