Synthesis and Characterization of Benzodioxinone-Bearing Methacrylate-Based Random Copolymer via Atom Transfer Radical Polymerization

Year 2021, Volume: 8 Issue: 2, 501 - 510, 31.05.2021

Cumali Çelik , Gokhan Acik

https://doi.org/10.18596/jotcsa.879021

Abstract

Methacrylate-benzodioxinone (BDMA) as a monomer was firstly synthesized and then copolymerized with methyl methacrylate and 2-hydroxyethyl methacrylate via atom transfer radical polymerization (ATRP) in the presence of CuCl/pentamethyldiethylene triamine (PMDETA) catalytic system using ethyl 2-bromopropionate (EtBrP) as an initiator. Successful formation of the block copolymer was also confirmed in detail by proton nuclear magnetic resonance spectroscopy (1H NMR), Fourier-transform infrared spectroscopy (FT-IR), and gel permeation chromatography (GPC) appropriately. Secondly, photochemical acylation of obtained copolymer through hydroxyl and benzodioxinone groups led to the release of benzophenone compound and ester-linkage on the polymer backbone. The formation of ester-linkage increases the glass transition temperature and the thermal stability of the obtained copolymer.

Keywords

Atom transfer radical polymerization, ketene chemistry, photochemical acylation, random copolymer

References

• 1. Klok HA, Lecommandoux S. Supramolecular materials via block copolymer self-assembly. Advanced Materials. 2001; 13(16): 1217-29.
• 2. Grayson SM, Frechet JM. Convergent dendrons and dendrimers: from synthesis to applications. Chemical Reviews. 2001; 101(12): 3819-68.
• 3. Cho I. New ring-opening polymerizations for copolymers having controlled microstructures. Progress in Polymer Science. 2000; 25(8): 1043-87.
• 4. Song A, Parker KA, Sampson NS. Synthesis of copolymers by alternating ROMP (AROMP). Journal of the American Chemical Society. 2009; 131(10): 3444-5.
• 5. Wang JS, Matyjaszewski K. "Living"/Controlled Radical Polymerization. Transition-Metal-Catalyzed Atom Transfer Radical Polymerization in the Presence of a Conventional Radical Initiator. Macromolecules. 1995; 28(22): 7572-3.
• 6. Kato M, Kamigaito M, Sawamoto M, Higashimuro T. Polymerization of methyl methacrylate with the carbon tetrachloride/dichlorotris-(triphenylphosphine) ruthenium (II)/methylaluminum bis (2, 6-di-tert-butylphenoxide) initiating system: possibility of living radical polymerization. Macromolecules. 1995; 28(5): 1721-3.
• 7. Rizzardo E, Chiefari J, Mayadunne R, Moad G, Thang S. Tailored polymer architectures by reversible addition-frasmentation chain transfer. Macromolecular Symposia. 2001; 174(1): 209-12.
• 8. Barner-Kowollik C, Davis PT, Heuts PAJ, Stenzel HM, Vana P, Whittaker M. RAFTing down under: Tales of missing radicals, fancy architectures, and mysterious holes. Journal of Polymer Science Part A: Polymer Chemistry. 2003; 41(3): 365-75.
• 9. Matyjaszewski K, Xia J. Atom transfer radical polymerization. Chemical Reviews. 2001; 101(9): 2921-90.
• 10. Kamigaito M, Ando T, Sawamoto M. Metal-catalyzed living radical polymerization. Chemical Reviews, 2001; 101(12): 3689-746.
• 11. Wang JS, Matyjaszewski K. Controlled/"living" radical polymerization. Atom transfer radical polymerization in the presence of transition-metal complexes. Journal of the American Chemical Society. 1995; 117(20): 5614-5.
• 12. Percec V, Barboiu B. "Living" Radical Polymerization of Styrene Initiated by Arenesulfonyl Chlorides and CuI (bpy) nCl. Macromolecules. 1995; 28(23): 7970-2.
• 13. Georges MK, Veregin RPN, Kazmaier PM, Hemer GK. Narrow molecular weight resins by a free-radical polymerization process. Macromolecules. 1993; 26(11): 2987-8.
• 14. Hawker CJ, Bosman AW, Harth E. New polymer synthesis by nitroxide mediated living radical polymerizations. Chemical Reviews. 2001; 101(12): 3661-88.
• 15. Patten TE, Xia J, Abernathy T, Matyjaszewski K. Polymers with very low polydispersities from atom transfer radical polymerization. Science. 1996; 272(5263): 866-8.
• 16. Wang JS, Matyjaszewski K. Controlled/"living" radical polymerization. Halogen atom transfer radical polymerization promoted by a Cu (I)/Cu (II) redox process. Macromolecules. 1995; 28(23): 7901-10.
• 17. Matyjaszewski K. New (co) polymers by atom transfer radical polymerization. Macromolecular Symposia. 1999; 143(1): 257-68.
• 18. Matyjaszewski K. General concepts and history of living radical polymerization. Handbook of Radical Polymerization. 2002; 361-406.
• 19. Patten TE, Matyjaszewski K. Copper (I)-catalyzed atom transfer radical polymerization. Accounts of Chemical Research. 1999; 32(10): 895-903.
• 20. Tasdelen MA, Yagci Y. Benzodioxinone Photochemistry in Macromolecular Science: Progress, Challenges, and Opportunities. ACS Macro Letters. 2017; 6(12): 1392-7.
• 21. Kumbaraci V, Talinli N, Yagci Y. Photoinduced synthesis of oligoesters. Macromolecules. 2006; 39(18): 6031-5.
• 22. Tasdelen MA, Kumbaraci V, Talinli N, Yagci Y. Photochemically masked benzophenone: Photoinitiated free radical polymerization by using benzodioxinone. Polymer. 2006; 47(22): 7611-4.
• 23. Kumbaraci V, Aydogan B, Talinli N, Yagci Y. Naphthodioxinone-1, 3-benzodioxole as photochemically masked one-component type II photoinitiator for free radical polymerization. Journal of Polymer Science Part A: Polymer Chemistry. 2012; 50(13): 2612-8.
• 24. Tasdelen MA, Kumbaraci V, Jockusch S, Turro NJ, Talinli N, Yagci Y. Photoacid generation by stepwise two-photon absorption: photoinitiated cationic polymerization of cyclohexene oxide by using benzodioxinone in the presence of iodonium salt. Macromolecules, 2008. 41(2): 295-7.
• 25. Leibfarth FA, Kang M, Ham M, Kim J, Campos LM, Gupto N, Moon B, Hawker CJ. A facile route to ketene-functionalized polymers for general materials applications. Nature Chemistry. 2010; 2(3): 207-12.
• 26. Leibfarth FA, Schneider Y, Lynd NA, Schultz A, Moon B, Kramer EJ, Bazan GC, Hawker CJ. Ketene functionalized polyethylene: Control of cross-link density and material properties. Journal of the American Chemical Society. 2010; 132(42): 14706-9.
• 27. Wolffs M, Kade MJ, Hawker CJ. An energy efficient and facile synthesis of high molecular weight polyesters using ketenes. Chemical Communications. 2011; 47(38): 10572-4.
• 28. Arslan M, Motallebzadeh A, Kiskan B, Demirel AL, Kumbaraci V, Yagci Y. Combining benzoxazine and ketene chemistries for self-healing of high performance thermoset surfaces. Polymer Chemistry. 2018; 9(15): 2031-9.
• 29. Alkan Goksu Y, Kumbaraci V, Yagci Y. Modular photoinduced grafting onto approach by ketene chemistry. Journal of Polymer Science Part A: Polymer Chemistry. 2019; 57(3): 274-80.
• 30. Aydogan C, Ciftci M, Kumbaraci V, Talinli N, Yagci Y. Hyperbranced Polymers by Photoinduced Self-Condensing Vinyl Polymerization Using Bisbenzodioxinone. Macromolecular Chemistry and Physics. 2017; 218(10): 1700045.
• 31. Cross SE, Anderson C, Roberts MS. Topical penetration of commercial salicylate esters and salts using human isolated skin and clinical microdialysis studies. British Journal of Clinical Pharmacology. 1998; 46(1): 29-35.
• 32. Durmaz YY, Kumbaraci V, Demirel AL, Talinli N, Yagci Y. Graft Copolymers by the Combination of ATRP and Photochemical Acylation Process by Using Benzodioxinones. Macromolecules. 2009; 42(11): 3743-3749.
• 33. Soltani O, De Brabander JK. Synthesis of functionalized salicylate esters and amides by photochemical acylation. Angewandte Chemie International Edition. 2005; 44(11): 1696-9.
• 34. Tasdelen MA, Taskin OS, Celik C. Orthogonal Synthesis of Block Copolymer via Photoinduced CuAAC and Ketene Chemistries. Macromolecular Rapid Communications. 2016; 37(6): 521-6.
• 35. Kumbaraci V, Talinli N, Yagci Y. Photoinduced crosslinking of polymers containing pendant hydroxyl groups by using bisbenzodioxinones. Macromolecular Rapid Communications. 2007; 28(1): 72-7.
• 36. Patel M, Braden M, Davy K. Polymerization shrinkage of methacrylate esters. Biomaterials. 1987; 8(1): 53-6.
• 37. Levi G, Karel M. Volumetric shrinkage (collapse) in freeze-dried carbohydrates above their glass transition temperature. Food Research International. 1995; 28(2): 145-51.
• 38. Dewaele M, Asmussen E, Peutzfedt A, Munksgaard EC, Benetti AR, Finne G, Leloup G, Devaux J. Influence of curing protocol on selected properties of light-curing polymers: degree of conversion, volume contraction, elastic modulus, and glass transition temperature. Dental Materials. 2009; 25(12): 1576-84.
• 39. Caykara T, Özyürek C, Kantoğlu Ö. Investigation of thermal behavior of poly (2-hydroxyethyl methacrylate-co-itaconic acid) networks. Journal of Applied Polymer Science. 2007; 103(3): 1602-7.
• 40. Acevedo B, Martinez F, Olea A. Synthesis, thermal behavior, and aggregation in aqueous solution of poly (methyl methacrylate)-b-poly (2-hydroxyethyl methacrylate). Journal of the Chilean Chemical Society. 2013; 58(4): 2038-42.
• 41. Marcilla A, Beltran M. Kinetic study of the thermal decomposition of polystyrene and polyethylene-vinyl acetate graft copolymers by thermogravimetric analysis. Polymer Degradation and Stability. 1995; 50(1): 117-24.
• 42. Maurin MB, Dittert LW, Hussain AA. Thermogravimetric analysis of ethylene-vinyl acetate copolymers with Fourier transform infrared analysis of the pyrolysis products. Thermochimica Acta. 1991; 186(1): 97-102.