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Synthesis, UV-curing Behavior and Surface Properties of New Fluorine-containing Aromatic Oxetane Monomers

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Abstract

In this paper, we combined high-end cationic UV-curable material with fluorinated chain obtaining a series of new fluorine-containing aromatic oxetane monomers via a mild nucleophilic substitution reaction. The structures and properties of monomers were characterized using 1H-NMR, 19F-NMR, dynamic viscosity tests and differential scanning calorimetry (DSC). It was determined that all of the fluorinated monomers obtained had much lower viscosity and higher thermostability after the introduction of hexafluorobenzene. Then, UV-curable coatings were prepared using four fluorine-containing aromatic oxetane monomers (FOX1–4); the UV-curing kinetics, with three kinds of initiators, and properties of the cured films were evaluated using real-time Fourier transform infrared (FTIR) spectroscopy, water and diiodomethane contact angle tests, surface energy calculations and scanning electron microscopy (SEM). The FTIR spectroscopy results showed that the coatings possessed excellent conversion rate (> 99% with liquid initiator PAG-201 in 150 s), and as the fluorine content increased, the monomers exhibited decreased mobility with the increasing viscosity and worse solubility with fluorinated monomers, resulting in a lower conversion rate. Moreover, the coatings possessed favorable hydrophobic and oleophobic properties and low surface energies owing to the fluoride chains floating to the membrane-air interface, which was also confirmed by discrete concave structures in SEM images. These new kinds of monomers can replace traditional fluorinated cationic monomers applied to the fingerprint resistant, fouling resistant, scratch resistant and anti-aging coatings, adhesives or printing ink materials.

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References

  1. Sangermano, M.; Bongiovanni, R.; Malucelli, G.; Priola, A.; Thomas, R. R.; Medsker, R. E.; Kim, Y.; Kausch, C. M. Synthesis and cationic photopolymerization of a new fluorinated oxetane monomer. Polymer 2004, 45(7), 2133–2139

    Article  CAS  Google Scholar 

  2. Yang, J.; Huang, W. Y. Synthesis and characterization of a novel fluorine-containing hydrophobically associating polymer. Chinese J. Polym. Sci. 1999, 17(3), 281–288

    CAS  Google Scholar 

  3. Wan, S. C.; Huang, B. W.; Du, Z. P. Study on the synthesis of 3,3′-[1,4-butanediylbis(oxymethylene)]bis[(3-ethyl)oxetane] for the novel cationic curing monomer. Imag. Sci. Photochem. 2016, 181–189

    Google Scholar 

  4. Kurt, P.; Wynne, K. J. Co-polyoxetanes with alkylammonium and fluorous or PEG-like side chains: soft blocks for surface modifying polyurethanes. Macromolecules 2007, 40(26), 9537–9543

    Article  CAS  Google Scholar 

  5. Škola, O.; Jašúrek, B.; Veselý, D.; Němec, P. Mechanical properties of polymer layers fabricated via hybrid free radical-cationic polymerization of acrylate, epoxide, and oxetane binders. Prog. Org. Coat. 2016, 101, 279–287

    Article  Google Scholar 

  6. Nakano, Y.; Tsutsumi, H. Ion conduction and electrochemical performance of poly(oxetane)-based electrolytes with tri(cyanoethoxymethyl) moiety as a side chain. ECS Transactions 2014, 62(1), 255–263

    Article  CAS  Google Scholar 

  7. Zhan, F.; Cheng, X.; Shi, W. F. Synthesis and properties of oxetane-based polysiloxanes used for cationic UV curing coatings. Polym. Adv. Technol. 2012, 23(3), 645–651

    Article  CAS  Google Scholar 

  8. Bongiovanni, R.; Malucelli, G.; Sangermano, M.; Priola, A. Fluorinated networks through photopolymerisation processes: synthesis, characterisation and properties. J. Fluorine Chem. 2004, 125(2), 345–351

    Article  CAS  Google Scholar 

  9. Mou, H.; Chen, L.; Wang, C.; Wang Y. L.; Wang, X. L. Paint Coat. Ind. 2015, 2, 1–6

    Google Scholar 

  10. Tan, J. Q.; Liu, W. Q.; Wang, Z. F. Preparation and performance of waterborne UV-curable polyurethane containing long fluorinated side chains. J. Appl. Polym. Sci. 2017, DOI: 10.1002/app.44506

    Google Scholar 

  11. Liu, B.; Bao, Y.; Ling, H. F.; Zhu, W. S.; Gong, R. J.; Lin, J. Y.; Xie, L. H.; Yi, M. D.; Huang, W. Fluorinated p-n type copolyfluorene as polymer electret for stable nonvolatile organic transistor memory device. Chinese J. Polym. Sci. 2016, 34(10), 1183–1195

    Article  CAS  Google Scholar 

  12. Li, W.; Feng, P.; Zou, Y. Q.; Hai, B. Synthesis and cationic photopolymerization of fluorine-containing vinyl ether monomers for the hydrophobic films. J. Appl. Polym. Sci. 2014, DOI: 10.1002/app.41019

    Google Scholar 

  13. Li, W.; Zou, Y. Q. Synthesis, UV-curing behavior and surface properties of fluorine-containing vinyl ether polymers. Chinese J. Polym. Sci. 2014, 32(8), 1032–1039

    Article  Google Scholar 

  14. Canak, T. C.; Hamuryudan, E.; Serhatli, I. E. Synthesis and characterization of perfluorinatedacrylatemethyl methacrylate copolymers. J. Appl. Polym. Sci. 2013, 128(3), 1450–1461

    CAS  Google Scholar 

  15. Lin, Y.; Liao, K.; Huang, C.; Chou, N.; Wang, S.; Chu, S.; Hsieh, K. Superhydrophobic films of UV-curable fluorinated epoxy acrylate resins. Polym. Int. 2010, 59(9), 1205–1211

    Article  CAS  Google Scholar 

  16. Wang, J.; Huang, J. Q.; Huang Y. G.; Qing, F. L. Synthesis and characterization of novel oxetane monomers containing short perfluorocarbon side chains. Chinese J. Org. Chem. 2009, 1969–1974

    Google Scholar 

  17. Xie, K.; Hou, A.; Shi, Y. Synthesis of fluorine-containing acrylate copolymer and application as resinson dyed polyester microfiber fabric. J. Appl. Polym. Sci. 2008, 108(3), 1778–1782

    Article  CAS  Google Scholar 

  18. Kurt, P.; Chakravorty, A.; Zeng, X. M.; Wynne, K. J. Strongly amphiphilic wetting behavior for polyurethanes with polyoxetane soft blocks having ―CF2H terminated side chains. Polymer 2014, 55(9), 2170–2178

    Article  CAS  Google Scholar 

  19. Deng, C.; Xie, W. F.; Huang, B. W. Study on the properties of oxetane/acrylate UV-cured hybrid system. Imag. Sci. Photochem. 2014, 289–299

    Google Scholar 

  20. Yang, S.; Jin, J.; Kwak, S.; Bae, B. Photocurable transparent cycloaliphatic epoxy hybrid materials crosslinked by oxetane. J. Appl. Polym. Sci. 2012, 126(S2), E380–E386

    Article  CAS  Google Scholar 

  21. Zhan, F.; Zhang, Y.; Shi, W. F. Synthesis of perfluorinated oxetane and surface properties of its cationic UV cured coating as a reactive additive. Chem. Res. Chinese U. 2012, 28(3), 550–558

    CAS  Google Scholar 

  22. Ertekin, A.; Kim, Y.; Kausch, C. M.; Thomas, R. R. Adsorption properties of oligo(fluorooxetane)-b-poly(ethylene oxide)-boligo( fluorooxetane) triblock copolymers at the air-water interface: comparison of hydroxyl and acetate end groups. J. Colloid Interf. Sci. 2009, 336(1), 40–45

    Article  CAS  Google Scholar 

  23. Song, B. J.; Park, J. K.; Kim, H. K. Novel photocurable multifunctional acrylate monomers containing perfluorinated aromatic units and their copolymers for photonic applications. J. Polym. Sci., Part A: Polym. Chem. 2004, 42(24), 6375–6383

    Article  CAS  Google Scholar 

  24. Liu, H. T.; Mo, J. H.; Liu, H. C. HuaZhong U. Sci. Technol., Nat. Sci. Ed. 2008, 36, 129–132

    Google Scholar 

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Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (No. 21574014).

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  1. College of Chemistry, Beijing Normal University, Beijing, 100875, China

    Shu-Qing Fang, Yu-Lian Pang & Ying-Quan Zou

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  1. Shu-Qing Fang
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  2. Yu-Lian Pang
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Correspondence to Ying-Quan Zou.

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Fang, SQ., Pang, YL. & Zou, YQ. Synthesis, UV-curing Behavior and Surface Properties of New Fluorine-containing Aromatic Oxetane Monomers. Chin J Polym Sci 36, 521–527 (2018). https://doi.org/10.1007/s10118-018-2048-4

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  • DOI: https://doi.org/10.1007/s10118-018-2048-4

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