A Yield Study on Self-Initiated Photopolymerization of Acrylate Monomers Bearing Benzophenone Pendant Unit

Year 2020, Volume: 9 Issue: 1, 1 - 8, 30.05.2020

Uğur Soykan , Bahattin Öztoprak

Abstract

The objective of this study was to determine the photo-initiator potentials of the acrylate monomers, p-benzophenoneoxycarbonylphenyl acrylate (U1) and p-benzophenone oxycarbonyl phenyl metacrylate (U2), having self-initiated photo-polymerization characteristic thanks to benzophenone groups presenting in their molecular structures. The effect of the co-inititiator types (triethylamine, N-methyldiethanolamine and 4,N,N-trimethylanaline), the solvents used in the photo reactions (DMSO, EtOAc, acetone) and co-initiator concentration on the percent conversion of both monomers were investigated in details. The characterization of the obtained polymer products were done by FTIR, 1H-NMR and DSC techniques. Among co-initiators, the results revealed that the maximum percent conversion, 21.32% was obtained from the photo-reaction carried out with TEA with the use of U1 monomer. Moreover, the obtained findings showed that the degree of monomer conversion increased with the increasing of the solvent polarity strength (DMSO˃EtOAc˃acetone). Correspondingly, the maxima, 25.54% and 19.28% were recorded with DMSO for both U1 and U2 monomers, respectively. Moreover, the percent conversion increased almost linearly with the increasing of the co-initiator concentration in the reaction medium. The maximum values were found to be 31.27 and 26.10% for U1 and U2 at 13.5x10-2 M triethylamine concentration, respectively. This was caused probably from the increment in the rate of polymerization reaction due to the formation of the relatively higher amount radicals during the photo-reaction.

Keywords

: photo-polymerization, percent conversion, p-benzophenoneoxycarbonylphenyl acrylate, , p-benzophenone oxycarbonyl phenyl metacrylate, benzophenone group

Supporting Institution

Department of Chemistry at Bolu Abant Izzet Baysal University

Project Number

This study was not carried out with any project but, supported by Bolu Abant İzzet Baysal University, Department of Chemistry.

Thanks

This work was supported by Department of Chemistry at Bolu Abant Izzet Baysal University. The author thanks to Prof. Dr. Izzet Morkan for providing the photo reactor so that the photo polymerization reactions are carried out. Furthermore, the author is also grateful to Innovative Food Technologies Development Application and Research Center for DSC measurements and Scientific, Industrial and Technological Application and Research Center for 1H-NMR measurements.

References

• Akat, H., Gacal, B., Balta, D. K., Arsu, N.,Yagci, Y., 2010. Poly(ethylene glycol)-Thioxanthone Prepared by Diels-Alder Click Chemistry as One-Component Polymeric Photoinitiator for Aqueous Free-Radical Polymerization. Journal of Polymer Science Part a-Polymer Chemistry, 48(10), 2109-2114.
• Akat, H., Ozkan, M., Saltan, F., 2012. Investigation of Aliphatic Polyesters as Hydrogen Donor in Photoinitiated Free Radical Polymerization. Asian Journal of Chemistry, 24(10), 4558-4562.
• Allen, N. S., Catalina, F., Mateo, J. L., Sastre, R., Green, P. N., Green, W. A., 1988. Photochemistry of Novel Water-Soluble Para-Substituted Benzophenone Photoinitiators- a Photocalorimetric and Photoreduction Study. Journal of Photochemistry and Photobiology a-Chemistry, 44(2), 171-177.
• Aydin, M., Temel, G., Balta, D. K., Arsu, N., 2015. "Mono" and "Bifunctional" Aromatic Esterificated Benzophenone Photoinitiators for Free Radical Polymerization. Polymer Bulletin, 72(2), 309-322.
• Cramer, N. B., Bowman, C. N., 2001. Kinetics of Thiol-Ene and Thiol-Acrylate Photopolymerizations with Real-Time Fourier Transform Infrared. Journal of Polymer Science Part a-Polymer Chemistry, 39(19), 3311-3319.
• Czerwinski, W. K., 1991a. Solvent Effects on Free-Radical Polymerization .1. Solvent Effect on Initiation of Methyl-Methacrylate and N-Vinyl-2-Pyrrolidone. Makromolekulare Chemie-Macromolecular Chemistry and Physics, 192(6), 1285-1296. Czerwinski, W. K., 1991b. Solvent Effects on Free-Radical Polymerization .2. IR and NMR Spectroscopic Analysis of Monomer Mixtures of Methyl-Methacrylate and N-Vinyl-2-Pyrrolidone in Bulk and in Model Solvents. Makromolekulare Chemie-Macromolecular Chemistry and Physics, 192(6), 1297-1305.
• Fouassier, J. P., Erddalane, A., Morletsavary, F., Sumiyoshi, I., Harada, M., Kawabata, M., 1994. Photoinitiation Processes of Radical Polymerization in the Presence of a 3-Component System Based on Ketone Amine-Bromo Compound. Macromolecules, 27(12), 3349-3356.
• Hoyle, C. E., Lee, T. Y., Roper, T., 2004. Thiol-enes: Chemistry of the Past with Promise for the Future. Journal of Polymer Science Part a-Polymer Chemistry, 42(21), 5301-5338.
• Kabatc, J., Ortyl, J., Kostrzewska, K., 2017. New Kinetic and Kechanistic Aspects of Photosensitization of Idonium Salts in Photopolymerization of Acrylates. Rsc Advances, 7(66), 41619-41629.
• Kayaman, N., Onen, A., Yagci, Y., Schnabel, W., 1994. Photosensitized Free-Radical Polymerization Using Pyridinium Salts. Polymer Bulletin, 32(5-6), 589-596.
• Ozturk Sen, B., 2018. Preparation and Characterization of Some Side Chain Liquid Crystalline Polymer Graft Copolymers of High Density Polyethylene and Isotactic Polypropylene. Ph.D. Thesis, Graduate School of Natural and Applied Sciences, Department of Chemistry, p.195, Bolu –Turkey (in Inglish).
• Popielarz, R., Vogt, O., 2008. Effect of Coinitiator Type on Initiation Efficiency of Two-Component Photoinitiator Systems Based on Eosin. Journal of Polymer Science Part a-Polymer Chemistry, 46(11), 3519-3532.
• Sainath, A. V. S., Rao, A. K., Reddy, A. V. R., 2000. Synthesis, Characterization and Liquid Crystalline Properties of Polyacrylates and Polymethacrylates Containing Aryl Ester Pendant Unit. Journal of Applied Polymer Science, 75(4), 465-474.
• Schneider, L. F. J., Cavalcante, L. M., Consani, S., Ferracane, J. L., 2009. Effect of Co-Initiator Ratio on the Polymer Properties of Experimental Resin Composites Formulated with Camphorquinone and Phenyl-Propanedione. Dental Materials, 25(3), 369-375.
• Soykan, U., Cetin, S., 2015. Reinforcement of High Density Polyethylene with a Side Chain LCP by Graft Copolymerization-Thermal, Mechanical and Morphological Properties. Journal of Polymer Research, 22(11).
• Soykan, U., 2013. Graft Copolymerization of p-Benzophenoneoxycarbonylphenyl Acrylate onto High Density Polyethylene. Master Thesis, Bolu Abant Izzet Baysal University, Graduate School of Natural and Applied Sciences, Department of Chemistry, p.99, Bolu –Turkey (in Inglish).
• Tar, H., Esen, D. S., Aydin, M., Ley, C., Arsu, N., Allonas, X., 2013. Panchromatic Type II Photoinitiator for Free Radical Polymerization Based on Thioxanthone Derivative. Macromolecules, 46(9), 3266-3272.
• Tehfe, M. A., Dumur, F., Graff, B., Morlet-Savary, F., Gigmes, D., Fouassier, J. P., Lalevee, J., 2013. Design of New Type I and Type II Photoinitiators Possessing Highly Coupled Pyrene-Ketone Moieties. Polymer Chemistry, 4(7), 2313-2324.
• Temel, G., Karaca, N., Arsu, N., 2010. Synthesis of Main Chain Polymeric Benzophenone Photoinitiator via Thiol-ene Click Chemistry and Its Use in Free Radical Polymerization. Journal of Polymer Science Part a-Polymer Chemistry, 48(23), 5306-5312.
• Valdebenito, A., Encinas, M. V., 2010. Effect of Solvent on the Free Radical Polymerization of N,N-dimethylacrylamide. Polymer International, 59(9), 1246-1251.
• Wrzyszczynski, A., Bartoszewicz, J., Hug, G. L., Marciniak, B., Paczkowski, J., 2003. Photochemical Studies of a Photodissociative Initiator Based on a Benzophenone Derivative Possessing a Thioether Moiety. Journal of Photochemistry and Photobiology a-Chemistry, 155(1-3), 253-259.
• Yagci, Y., Jockusch, S., Turro, N. J., 2010. Photoinitiated Polymerization: Advances, Challenges, and Opportunities. Macromolecules, 43(15), 6245-6260.