2021 (4) 5

https://doi.org/10.15407/polymerj.43.04.287

KINETICS OF FORMATION AND PROPERTIES OF PHOTOCURED SIMULTANEOUS EPOXY-ACRYLATE IPNS WITH THE PREVAILING CONTENT OF AN EPOXY COMPONENT

N.V. Yarova,
Institute of macromolecular Chemistry NAS of Ukraine, 48, Kharkivske shose, Kyiv, 02160, Ukraine,

e-mail: ynv25@ukr.net

ORCID: 0000-0002-3347-8073

T.F. Samoilenko,
Institute of macromolecular Chemistry NAS of Ukraine, 48, Kharkivske shose, Kyiv, 02160, Ukraine,
ORCID: 0000-0002-3232-1621
L.M. Yashchenko,
Institute of macromolecular Chemistry NAS of Ukraine, 48, Kharkivske shose, Kyiv, 02160, Ukraine,
ORCID: 0000-0002-0736-8073

O.O. Brovko,
Institute of macromolecular Chemistry NAS of Ukraine, 48, Kharkivske shose, Kyiv, 02160, Ukraine,
ORCID: 0000-0003-0238-1137

Polym. J., 2021, 43, no. 4: 287-294.

Section: Structure and properties.

Language: Ukrainian.

Abstract:

The distinct features of UV induced polymerization of epoxy-acrylate blends leading to the formation of simultaneous interpenetrating polymer networks (IPNs) have been studied. Different ratios of components within a prevailing content of an epoxy one have been used for the synthesis. Such a content of epoxy monomer is required to create a barrier preventing oxygen diffusion into a curing sample. It allows retardation of the well-known oxygen-inhibition effect, which acrylate monomers are susceptible to. Hence, the conduction of their polymerization in open-air conditions is possible. The proceeding of the polymerization reactions of acrylate (TEGDM) via free radical mechanism and of epoxy (UP-650D) via cationic one have been monitored by FTIR-spectroscopy. Namely, the conversion degrees have been calculated for double bonds of TEGDM and for epoxy groups of UP-650D respectively. A mixture of triphenylsulfonium hexafluorophosphate salts, which is capable of generating both free radical and cationic reactive species, have been used as a single photoinitiator for the formulations being investigated. Almost complete conversion of acrylate double bonds was reached after 60 min of UV irradiation irrespective of epoxy content. On the contrary, conversion of epoxy groups of aliphatic epoxy, which is known to be rather unreactive towards cationic photopolymerization, when mixed may be either higher or lower compared to the neat epoxy network. Such results are attributed to dual influence of acrylate network on the formation of epoxy one. Firstly, cationic polymerization of epoxy component is sensitized by acrylate macroradicals in terms of free radical promoted cationic polymerization. On the other hand, the mobility of epoxy macrocations is restricted by the rapid build-up of acrylate network. At the weight ratio of UP-650D and TEGDM 70/30 the sensitizing effect of acrylate is revealed to be dominant, so the given composition may be considered as optimal. Regardless of low conversion of epoxy groups, the content of the estimated gel fraction is high, and the epoxy component is found not to be leached in the process of extraction in acetone. Furthermore, physicomechanical properties of obtained UV-cured IPNs have been investigated. The results of the measurements, namely, impact resistance by the Gardner test, crosshatch adhesion test to different substrates (including silicon), and accelerated weathering test in a climatic chamber, show that all the samples exhibit good operational properties essential for effective protecting coatings of outdoor exposure.

Key words: interpenetrating polymer networks, photopolymerization, oxygen inhibitory effect, free radical promoted cationic polymerization.

REFERENCES

1. Babkin O. E. Polymer coatings UV-curing. SPb .: ed. SPbGUKiT (Rus), 2012: 47.
2. Cai Y., Jessop J. L. P Decreased oxygen inhibition in photopolymerized acrylate/epoxide hybrid polymer coatings as demonstrated by Raman spectroscopy. Polymer, 2006, no. 47: 6560–6566. https://doi.org/10.1016/j.polymer.2006.07.031.
3. Sharma A., Agarwal D., Singh J. Study of curing kinetics and thermal degradation of UV curable epoxy acrylate resin. E-Journal of Chemistry, 2008, 5, no. 4: 904–913. https://doi.org/10.1155/2008/697371.
4. De Brito M., Allonas X., Croutxe-Barghorna C., Palmieria M., Dietlin C., Agarwal S., Lellinger D., Alig I. Kinetic study of photoinduced quasi-simultaneous interpenetrating polymer networks. Progress in Organic Coatings, 2012, 73, Issues 2–3: 186–193. https://doi.org/10.1016/j.porgcoat.2011.10.014.
5. Decker C. Light-induced crosslinking polymerization. Polymer International, 2002, no. 51: 1141–1150. https://doi.org/10.1002/pi.821.
6. Decker C., Viet T. N. T. , Decker D. , Weber-Koehl E. UV-radiation curing of acrylate/epoxide systems. Polymer, 2001, no. 42: 5531–5541. https://doi.org/10.1016/S0032-3861(01)00065-9.
7. Sangermano М., Carbonaro W., Malucelli G., Priola A. UV-cured interpenetrating acrylic-epoxy polymer networks: Preparation and characterization. Macromol Mater Eng. 2008; 293(6):515–520. https://doi.org/10.1002/mame.200800020.
8. Decker C., Moussa K. UV-curable acrylic resins for production of glass laminates. Journal of Applied Polymer Science, 1995, 55: 359–369. https://doi.org/10.1002/app.1995.070550218.
9. Studer K., Decker C., Beck E., Schwalm R. Overcoming oxygen inhibition in UV-curing of acrylate coatings by carbon dioxide inerting. Part I. Progress in Organic Coatings, 2003, no. 48: 92–100. https://doi.org/10.1016/S0300-9440(03)00120-6.
10. Fouassier J. P., Lalevéе J. Photochemical production of interpenetrating polymer networks; simultaneous initiation of radical and cationic polymerization reactions. Polymers, 2014, no. 6: 2588–2610. https://doi.org/10.3390/polym6102588.
11. Samoilenko T. F. , Brovko О. О., Yarova N.V. UV Curable Epoxy-Acrylate Formulations. Polym. J. (Ukr.), 2014, 36, no. 1: 66–77.
12. Samoilenko T.F. , Yarova N.V., Menzheres G.Y., Brovko О.О. The kinetics of UV initiated formation of epoxy-acrylate interpenetrating polymer networks in different curing conditions. Ukrainian Chemistry Journal (Ukr), 2014, 80, no. 6: 110–116.
13. Samoilenko T., Yarova N., Menzheres H., Brovko O. The sensitization of aliphatic epoxy photopolymerization in epoxy-acrylate interpenetrating polymer networks. Fr Ukr. J. Chem., 2014, 2, no. 1: 5–9. https://doi.org/10.17721/fujcV2I1P5-9.
14. GOST 4765-73 Paints and varnishes. Method for Determination of Impact Strength. Moscow: Publishing house of standards: 7 p.
15. GOST 15140-78 Paints and varnishes. Methods for determining adhesion. Moscow: Publishing house of standards: 10 p.
16. Sperling L. H. Interpenetrating polуmer networks and related materials. Moscow: Mir, 1984: 328.
17. Brovko О.О., Goncharova L.A., Shtompel V.I., Sergeeva L.M., Kochetov O.O., Bondarenko P. O. Epoxy-acrylate interpenetrating polуmer networks: synthesis, microphases structure and properties. Polym. J. (Ukr.), 2005, 27, no. 1: 45–50.
18. Crivello J. V., J. H. W. Lam. Triarylsulfonium salts as photoinitiators of free radical and cationic polymerization. Journal of Polymer Science: Polymer Letters Edition, 1979, no. 17: 759–764. https://doi.org/10.1002/pol.1979.130171203.
19. Bulut U., Crivello J. V. Investigation of the reactivity of epoxide monomers in photoinitiated cationic polymerization. Macromolecules, 2005, 38, no. 9: 3584–3595. https://doi.org/10.1021/ma050106k.
20. Menzheres G.Ya., Dyadusha A.G., Vatulev V.N., Chaiko A.K., Magdinets V.V. Photochemically initiated cationic polymerization of epoxy resins. Journal of Applied Chemistry. (Rus.), 1989, no. 10: 2348–2352.
21. Nakanisi K. Infrared spectra and structure of organic compounds. Moscow: Mir (Rus.), 1965: 216.
22. Bellami L. Infrared spectra of complex compounds. Translated from English by V. M. Akimov. Moscow: Foreign literature edition (Rus.), 1963: 592.
23. Pliiev T. N., Karpov O. N. Infrared spectra and structure of epoxies. Minsk: Viniti, (Rus.), 1989: 158.
24. Decker C., Bendaikha T. Interpenetrating Polymer Networks. II. Sunlight-Induced Polymerization of Multifunctional Acrylates. Journal of Applied Polymer Science, 1998, 11, no. 70: 2269–2282. https://doi.org/10.1002/(SICI)1097-4628(19981212)70:11<2269::AID-APP21>3.0.CO;2-D.
25. Lipatov Yu. S. Peculiarities of self-organization in the production of interpenetrating polymer networks. Journal of Macromolecular Science, Part C. Polymer Reviews, 1990, 30, no. 2: 209–232. https://doi.org/10.1080/07366579008050909.
26. Lipatov Yu. S., Alekseeva T. T. Phase-separated interpenetrating polymer networks. Springer-Verlag, Berlin, Heidelberg, 2007: 234.
27. Lipatov Yu. S. The kinetic peculiarities of interpenetrating polymer networks formation. Polymer, 1992, 33, no. 2: 361–364. https://doi.org/10.1016/0032-3861(92)90994-8.
28. Samoilenko T. F., Yarova N.V., Ostapiuk S.M., Tkalich M.H., Demchyna O.I., Yevcyuk I.I., Brovko O.O. Formation and properties of UV-cured diane epoxy resins and epoxy-acrylate interpenetrating polymer networks on their base. Polym. J. (Ukr.), 2016, 38, no. 1: 40–46.
29. Vabrik R., Czajlik I., Tury G., Rusznak I., Ille A., Vig A. A study of epoxy resin–acrylated polyurethane semi-interpenetrating polymer networks. Journal of Applied Polymer Science, 1998, no. 68: 111–119. https://doi.org/10.1002/(SICI)1097-4628(19980404)68:1<111::AID-APP12>3.0.CO;2-3.
30. Lin M.-Sh., Liu Ch.-Ch. Semi-IPNs formed from poly(ethylene glycol monomethyl ether acrylate) and an epoxy thermoset. Polymer International, 1999, 48, no. 12: 137–142. https://doi.org/10.1002/(SICI)1097-0126(199902)48:2<137::AID-PI122>3.0.CO;2-H.
31. Nowers J. R., B. Narasimhan The effect of interpenetrating polymer network formation on polymerization kinetics in an epoxy-acrylate system. Polymer, 2006, no. 47: 1108–1118. https://doi.org/10.1016/j.polymer.2005.12.030.
32. Suthar B., Xiao H. X., Klempner D., Frisch K. C. A review of kinetic studies on the formation of interpenetrating polymer networks. Polymers for Advanced Technologies, 1996. 7: 221–233. https://doi.org/10.1002/(SICI)1099-1581(199604)7:4<221::AID-PAT529>3.0.CO;2-A.
33. Tehfe M.-A., Lalevée J., Gigmes D. Green chemistry: sunlight-induced cationic polymerization of renewable epoxy monomers under air. Macromolecules, 43, no. 3: 1364–1370. https://doi.org/10.1021/ma9025702.
34. Hua Y., J. V. Crivello. Synergistic interaction of epoxides and N-vinylcarbazole during photoinitiated cationic polymerization. Journal of Polymer Science: Part A: Polymer Chemistry, 2000, 38, no. 19: 3697–3709. https://doi.org/10.1002/1099-0518(20001001)38:19<3697::AID-POLA240>3.0.CO;2-B.
35. Lalevée J., Tehfe M.-A., Zein-Fakih A. N-vinylcarbazole: an additive for free radical promoted cationic polymerization upon visible light. ACS MacroLetters, 2012, 1, no. 7: 802–806. https://doi.org/10.1021/mz3002325.
36. Aydogan B., Gacal B., Yildirim A. Wavelength tunability in photoinitiated cationic polymerization. Photochemistry and UV Curing: New Trends. Editor J. P. Fouassier, Kerala, India: Research Signpost, 2006: 187–202.
37. Samoilenko T, Yarova N, Brovko O. Features of phase morphology of photocured epoxy-acrylate interpenetrating polymer networks. The proceedings of VIІІ open Ukrainian conference on macromolecular compounds for young scientists. Kyiv, 2016: 9–11.