Kinetic Study of the Free Radical Copolymerization of Methyl Methacrylate with 2-Perfluorooctyl Ethyl Methacrylate by Quantum Computational Approach

Year 2021, Volume: 8 Issue: 4, 1263 - 1274, 30.11.2021

Ramazan Katırcı , Salih Özbay

https://doi.org/10.18596/jotcsa.945056

Cited By: 3

Abstract

Fluorinated copolymers with perfluoroalkyl side chains have widespread use in applications requiring superior technology due to their unique surface properties. Kinetic analysis of copolymerization of fluorinated acrylates with conventional acrylates is necessary to synthesize such copolymers efficiently. However, kinetic investigation of such reactions are limited in the literature due to the experimental difficulties. In this study, the kinetic of copolymerization of methyl methacrylate with 2-perfluorooctyl ethyl methacrylate in toluene medium using AIBN initiator was investigated using quantum chemistry postulates as an alternative to experimental methods. Reaction rate constants (kp) for propagation were determined using transition state theory. A terminal effect models were used to examine four different addition reactions involving monomeric and dimeric radicals and monomers for both self- and cross-propagation. Reactant and product conformations were optimized with a DFT method using PBE0 function. The Evans-Polanyi relationship was used to calculate the rate of self- and cross-propagation of monomers. The results showed that the reactivity ratio of 2-perfluorooctyl ethyl methacrylate was found to be higher than that of methyl methacrylate. In addition, it was observed that the reaction conditions caused the random polymer structure due to the different rate constants in self and cross propagation.

Keywords

2-Perfluorooctyl ethyl methacrylate, methyl methacrylate, free radical polymerization, kinetic, DFT

References

• 1. Ciardelli F, Aglietto M, Montagnini di Mirabello L, Passaglia E, Giancristoforo S, Castelvetro V, et al. New fluorinated acrylic polymers for improving weatherability of building stone materials. Progress in Organic Coatings. 1997;32(1–4):43–50.
• 2. Anton D. Surface‐fluorinated coatings.". Advanced Materials. 1998;10:1197–205.
• 3. Imae T. Fluorinated polymers. Current Opinion in Colloid & Interface Science. 2003;8(3):307–14.
• 4. Huang P-Y, Chao Y-C, Liao Y-T. Preparation of fluoroacrylate nanocopolymer by miniemulsion polymerization used in textile finishing. Journal of Applied Polymer Science. 2004;94(4):1466–72.
• 5. Bruno A. Controlled Radical (Co)polymerization of Fluoromonomers. Macromolecules. 2010;43(24):10163–84.
• 6. Lee S, Park J-S, Lee TR. The Wettability of Fluoropolymer Surfaces: Influence of Surface Dipoles. Langmuir. 2008;24(9):4817–26.
• 7. Chang K-C, Chen H, Huang C-K, Huang S-I. Preparation of super-hydrophobic film with fluorinated-copolymer. Journal of Applied Polymer Science. 2007;104(3):1646–53.
• 8. Ozbay S, Erbil HY. Superhydrophobic and oleophobic surfaces obtained by graft copolymerization of perfluoroalkyl ethyl acrylate onto SBR rubber. Colloids and Surfaces A: Physicochemical and Engineering Aspects. 2015;481:537–46.
• 9. Tuteja A, Choi W, Ma M, Mabry JM, Mazzella SA, Rutledge GC, et al. Designing superoleophobic surfaces. Science. 2007;318(5856):1618–22.
• 10. Steele A, Bayer I, Loth E. Inherently Superoleophobic Nanocomposite Coatings by Spray Atomization. Nano Letters. 2009;9(1):501–5.
• 11. Xiong D, Liu G, Hong L, Duncan EJS. Superamphiphobic Diblock Copolymer Coatings. Chemistry of Materials. 2011;23(19):4357–66.
• 12. Lee SG, Ham DS, Lee DY, Bong H, Cho K. Transparent Superhydrophobic/Translucent Superamphiphobic Coatings Based on Silica–Fluoropolymer Hybrid Nanoparticles. Langmuir. 2013;29(48):15051–7.
• 13. Ozbay S, Cengiz U, Erbil HY. Solvent-Free Synthesis of a Superamphiphobic Surface by Green Chemistry. ACS Applied Polymer Materials. 2019;1(8):2033–43.
• 14. Katano Y, Tomono H, Nakajima T. Surface Property of Polymer Films with Fluoroalkyl Side Chains. Macromolecules. 1994;27(8):2342–4.
• 15. Park IJ, Lee S-B, Choi CK. Surface Properties of the Fluorine-Containing Graft Copolymer of Poly((perfluoroalkyl)ethyl methacrylate)- g -poly(methyl methacrylate). Macromolecules. 1998;31(21):7555–8.
• 16. Stone M, Nevell TG, Tsibouklis J. Surface energy characteristics of poly(perfluoroacrylate) film structures. Materials Letters. 1998;37(1–2):102–5.
• 17. Tsibouklis J, Graham P, Eaton PJ, Smith JR, Nevell TG, Smart JD, et al. Poly(perfluoroalkyl methacrylate) Film Structures: Surface Organization Phenomena, Surface Energy Determinations, and Force of Adhesion Measurements. Macromolecules. 2000;33(22):8460–5.
• 18. Park IJ, Lee S-B, Choi CK. Synthesis of fluorine-containing graft copolymers of poly(perfluoroalkylethyl methacrylate)-g-poly(methyl methacrylate) by the macromonomer technique and emulsion copolymerization method. Polymer. 1997;38(10):2523–7.
• 19. Van De Grampel RD, Van Geldrop J, Laven J, Van Der Linde R. P[CF3(CF2)5CH2MA-co-MMA] and P[CF3(CF2)5CH2MA-co-BA] copolymers: Reactivity ratios and surface properties. Journal of Applied Polymer Science. 2001;79(1):159–65.
• 20. Van de Grampel RD, Ming W, Gildenpfennig A, Van Gennip WJH, Laven J, Niemantsverdriet JW, et al. The Outermost Atomic Layer of Thin Films of Fluorinated Polymethacrylates. Langmuir. 2004;20(15):6344–51.
• 21. Nishino T, Urushihara Y, Meguro M, Nakamae K. Surface properties and structures of diblock and random copolymers with perfluoroalkyl side chains. Journal of Colloid and Interface Science. 2004;279(2):364–9.
• 22. Choi D, Yeom EH, Park M, Kim JK, Kim BC. Preparation and properties of methyl methacrylate and fluoroacrylate copolymers for plastic optical fiber cladding. Journal of Applied Polymer Science. 2004;93(5):2082–9.
• 23. Hartmann P, Collet A, Viguier M. Acrylic Copolymers with Perfluoroalkylated Biphenyl Side Groups: Correlation Structure−Surface Properties. Macromolecules. 2006;39(20):6975–82.
• 24. Ye X, Zuo B, Deng M, Hei Y, Ni H, Lu X, et al. Surface segregation of fluorinated moieties on poly(methyl methacrylate-ran-2-perfluorooctylethyl methacrylate) films during film formation: Entropic or enthalpic influences. Journal of Colloid and Interface Science. 2010;349(1):205–14.
• 25. Ozbay S, Erbil HY. Solution copolymerization of perfluoroalkyl ethyl methacrylate with methyl methacrylate and butyl acrylate: Synthesis and surface properties. Colloids and Surfaces A: Physicochemical and Engineering Aspects. 2014;452:9–17.
• 26. DeSimone AJM, Guan Z, Elsbernd CS. Synthesis of Fluoropolymers in Supercritical Carbon Dioxide. Science. 1992;257(5072):945–7.
• 27. Cengiz U, Gengec NA, Ugur Kaya N, Yildirim Erbil H, Sezai Sarac A. Mechanical and thermal properties of perfluoroalkyl ethyl methacrylate–methyl methacrylate statistical copolymers synthesized in supercritical carbon dioxide. Journal of Fluorine Chemistry. 2011;132(5):348–55.
• 28. Cengiz U, Gengec NA, Erbil HY. Surface characterization of flat and rough films of perfluoromethacrylate-methylmethacrylate statistical copolymers synthesized in CO2-expanded monomers. Colloid and Polymer Science. 2013;291(3):641–52.
• 29. Ding L, Olesik S V. Dispersion Polymerization of MMA in Supercritical CO 2 in the Presence of Copolymers of Perfluorooctylethylene Methacrylate and Poly(propylene glycol) Methacrylate. Macromolecules. 2003;36(13):4779–85.
• 30. Valtola L, Hietala S, Tenhu H, Denifl P, Wilen C-E. Association behavior and properties of copolymers of perfluorooctyl ethyl methacrylate and eicosanyl methacrylate. Polymers for Advanced Technologies. 2009;20(3):225–34.
• 31. Fukuda T, Kubo K, Ma Y-D. Kinetics of free radical copolymerization. Progress in Polymer Science. 1992;17(5):875–916.
• 32. Yu X, Levine SE, Broadbelt LJ. Kinetic Study of the Copolymerization of Methyl Methacrylate and Methyl Acrylate Using Quantum Chemistry. Macromolecules. 2008;41(21):8242–51.
• 33. Asua JM, Beuermann S, Buback M, Castignolles P, Charleux B, Gilbert RG, et al. Critically Evaluated Rate Coefficients for Free-Radical Polymerization, 5,. Macromolecular Chemistry and Physics. 2004;205(16):2151–60.
• 34. Dossi M, Storti G, Moscatelli D. A quantum chemistry study of the free-radical copolymerization propagation kinetics of styrene and 2-hydroxyethyl acrylate. Polymer Engineering & Science. 2011;51(10):2109–14.
• 35. Neese F. The ORCA program system. WIREs Computational Molecular Science. 2012;2(1):73–8.
• 36. Neese F. Software update: the ORCA program system, version 4.0. WIREs Computational Molecular Science. 2018;8:e1327.
• 37. Treutler O, Ahlrichs R. Efficient molecular numerical integration schemes. The Journal of Chemical Physics. 1995;102(1):346–54.
• 38. Liu S, Srinivasan S, Tao J, Grady MC, Soroush M, Rappe AM. Modeling Spin-Forbidden Monomer Self-Initiation Reactions in Spontaneous Free-Radical Polymerization of Acrylates and Methacrylates. The Journal of Physical Chemistry A. 2014;118(40):9310–8.
• 39. Verma P, Perera A, Bartlett RJ. Increasing the applicability of DFT I: Non-variational correlation corrections from Hartree–Fock DFT for predicting transition states. Chemical Physics Letters. 2012;524:10–5.
• 40. Maeda S, Harabuchi Y, Ono Y, Taketsugu T, Morokuma K. Intrinsic reaction coordinate: Calculation, bifurcation, and automated search. International Journal of Quantum Chemistry. 2015;115(5):258–69.
• 41. Wubbels GG. Use of the Bell–Evans–Polanyi Principle to predict regioselectivity of nucleophilic aromatic photosubstitution reactions. Tetrahedron Letters. 2014;55(36):5066–9.
• 42. Mayo FR, Lewis FM. Copolymerization. I. A Basis for Comparing the Behavior of Monomers in Copolymerization; The Copolymerization of Styrene and Methyl Methacrylate. Journal of the American Chemical Society. 1944;66(9):1594–601.
• 43. Odian G. Principles of Polymerization [Internet]. Hoboken, NJ, USA: John Wiley & Sons, Inc.; 2004.