Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Original Article
  • Published:

Effect of UV-curing conditions on the polymer structures: a comparison between coating and adhesive

Polymer Journal volume 52, pages 1153–1163 (2020)Cite this article

Subjects

Abstract

Radical photopolymerization of acrylate was carried out without a degassing process under conditions suitable for UV-curable coatings and UV-curable adhesives. We examined the differences in the resulting polymer structures obtained from the coating and adhesive by employing the same formulation. 2,2-Dimethoxy-2-phenylacetophenone was employed as a photoinitiator. The UV-curable coating yielded polymers terminated by either a hydroxyl group or a terminal carbonyl group as the main products. On the other hand, the UV-curable adhesive yielded a multitude of polymers that were terminated by disproportionation. In the latter case, some polymers underwent hydrogen abstraction from the polymer backbone, resulting in β-scission of the midchain radical to generate polymers with an α-substituted acryloyl group as the terminal group.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Fig. 1
Fig. 2
Scheme 1
Scheme 2
Scheme 3
Fig. 3
Scheme 4
Scheme 5
Scheme 6
Fig. 4

Similar content being viewed by others

References

  1. Hoyle CE. Photocurable coatings. In: Hoyle CE, Kinstle JF, editors. ACS Symposium Series 417: Radiation curing of polymeric materials. Washington, DC: American Chemical Society; 1990. p. 1–16.

  2. Vanderhoff JW. Ultraviolet light cured inks-a review. In: Labana SS, editor. ACS Symposium Series: Ultraviolet light induced reactions in polymers. Washington, DC: American Chemical Society; 1976. p. 162–87.

  3. Yagci Y, Jockusch S, Turro NJ. Photoinitiated polymerization: advance, challenges, and opportunities. Macromolecules. 2010;43:6245–60.

    Article  CAS  Google Scholar 

  4. O’Brien AK, Bowman CN. Impact of oxygen on photopolymerization kinetics and polymer structure. Macromolecules. 2006;39:2501–6.

    Article  CAS  Google Scholar 

  5. Krongauz VV, Chawla CP, Dupre J. Oxygen and radical photopolymerization in films. In: Belfield KD, Crivello JV, editors. ACS Symposium Series: Photoinitiated polymerization. Washington, DC: American Chemical Society; 2003; p. 165–75.

  6. Decker C, Moussa K. UV-radiation- and laser-induced polymerization of acrylic monomers. In: Hoyle CE, Kinstle JF, editors. ACS Symposium Series 417: Radiation curing of polymeric materials. Washington, DC: American Chemical Society: 1990; p. 439–56.

  7. Crivello JV, Reichmanis E. Photopolymer materials and processes for advanced technologies. Chem Mater. 2014;26:533–48.

    Article  CAS  Google Scholar 

  8. Huber HF Radiation cure of pressure-sensitive adhesives. In: Fouassier JP, Rabek JF, editors. Radiation curing in polymer science and technology-volume IV practical aspects and applications. London and New York: Elsevier Applied Science; 1993. p. 51–72.

  9. Ellerstein SM, Lee SA, Palit TK. Radiation-curable adhesives. In: Fouassier JP, Rabek JF, editors. Radiation curing in polymer science and technology-volume IV practical aspects and applications. London and New York: Elsevier Applied Science; 1993. p. 73–85.

  10. Khudyakov IV, Legg JC, Purvis MB, Overton BJ. Kinetics of photopolymerization of acrylates with functionality of 1-6. Ind Eng Chem Res. 1999;38:3353–9.

    Article  CAS  Google Scholar 

  11. Fouassier JP. An introduction to the basic principles in UV curing. In: Fouassier JP, Rabek JF, editors. Radiation curing in polymer science and technology-volume I fundamentals and methods. London and New York: Elsevier Applied Science; 1993. p. 49–113.

  12. Kurdikar DL, Peppas NA. Method of determination of initiator efficiency: application to UV polymerizations using 2,2-dimethoxy-2-phenylacetophenone. Macromolecules. 1994;27:733–8.

    Article  CAS  Google Scholar 

  13. Szablan Z, Junkers T, Koo SPS, Lovestead TM, Davis TP, Stenzel MH, et al. Mapping photolysis product radical reactivities via soft ionization mass spectrometry in acrylate, methacrylate, and itaconate systems. Macromolecules. 2007;40:6820–33.

    Article  CAS  Google Scholar 

  14. Willemse RXE, van Herk AM, Panchenko E, Junkers T, Buback M. PLP-ESR monitoring of midchain radicals in n-butyl acrylate polymerization. Macromolecules. 2005;38:5098–103.

    Article  CAS  Google Scholar 

  15. Nikitin AN, Hutchinson RA. The effect of intramolecular transfer to polymer on stationary free radical polymerization of alkyl acrylates. Macromolecules. 2005;38:1581–90.

    Article  CAS  Google Scholar 

  16. Junkers T, Koo SPS, Davis TP, Stenzel MH, Barner-Kowollik C. Mapping poly (butyl acrylate) product distributions by mass spectrometry in a wide temperature range: suppression of midchain radical side reactions. Macromolecules. 2007;40:8906–12.

    Article  CAS  Google Scholar 

  17. Sanai Y, Kagami S, Kubota K. Cross-linking photopolymerization of monoacrylate initiated by benzophenone. J Polym Sci Part A. 2018;56:1545–53.

    Article  CAS  Google Scholar 

  18. Nonaka H, Ouchi M, Kamigaito M, Sawamoto M. MALDI-TOF-MS analysis of rutherium(II)-mediated living radical polymerizations of methyl methacrylate, methyl acrylate, and styrene. Macromolecules. 2001;34:2083–8.

    Article  CAS  Google Scholar 

  19. Farcet C, Belleney J, Charleux B, Pirri R. Structural characterization of nitroxide-terminated poly(n-butyl acrylate) prepared in bulk and miniemulsion polymerizations. Macromolecules. 2002;35:4912–8.

    Article  CAS  Google Scholar 

  20. Matyjaszewski K, Nakagawa Y, Jasieczec CB. Polymerization of n-butyl acrylate by atom transfer radical polymerization. Remarkable effect of ethylene carbonate and other solvents. Macromolecules. 1998;31:1535–41.

    Article  CAS  Google Scholar 

  21. Ligon SC, Husár B, Wutzel H, Holman R, Liska R. Strategies to reduce oxygen inhibition in photoinduced polymerization. Chem Rev. 2014;114:557–89.

    Article  CAS  Google Scholar 

  22. Pynaert R, Buguet J, Croutxé-Barghorn C, Moireau P, Allonas X. Effect of reactive oxygen species on the kinetics of free radical photopolymerization. Polym Chem. 2013;4:2475–9.

    Article  CAS  Google Scholar 

  23. Sanai Y, Kagami S, Kubota K. Initiation and termination pathways in the photopolymerization of acrylate using methyl phenylglyoxylate as an initiator. Polym J. 2020;52:375–85.

    Article  CAS  Google Scholar 

  24. Klems JP, Lippa KA, McGivern WS. Quantitative evidence for organic peroxy radical photochemistry at 254 nm. J Phys Chem A. 2015;119:344–51.

    Article  CAS  Google Scholar 

  25. Buback M, Günzeler F, Russell GT, Vana P. Determination of the mode of termination in radical polymerization. Macromolecules 2009;42:652–62.

    Article  CAS  Google Scholar 

  26. Harada T, Zetterlund PB, Yamada B. Preparation of macromonomers by copolymerization of methyl acrylate dimer involving β Fragmentation. J Polym Sci Part A. 2004;42:597–607.

    Article  CAS  Google Scholar 

  27. Pitts MR, Harrison JR, Moody CJ. Indium metal as a reducing agent in organic synthesis. J Chem Soc Perkin Trans 1. 2001;1:955–77.

    Article  CAS  Google Scholar 

  28. Gregg BT, Golden KC, Quinn JF. Indium(III)trifluoromethanesulfonate as a mild, efficient catalyst for the formation of acetals and ketals in the presence of acid sensitive functional groups. Tetrahedron. 2008;64:3287–95.

    Article  CAS  Google Scholar 

  29. Sakai N, Moritaka K, Konakahara T. A novel approach to the practical synthesis of sulfides: an InBr3-Et3SiH catalytic system promoted the direct reductive sulfidation of acetals with disulfides. Eur J Org Chem. 2009;24:4123–7.

    Article  CAS  Google Scholar 

  30. Iwasaki T, Maegawa Y, Hayashi Y, Ohshima T, Mashima K. Transesterification of various methyl esters under mild conditions catalyzed by tetranuclear zinc cluster. J Org Chem. 2008;73:5147–50.

    Article  CAS  Google Scholar 

  31. Werner T, Barrett GM. Simple method for the preparation of esters from Grignard reagents and alkyl 1-imidazolecarboxylates. J Org Chem. 2006;71:4302–4.

    Article  CAS  Google Scholar 

  32. Ghebreyessus KY, Angelici RJ. Isomerizing-hydroboration of the monounsaturated fatty acid ester methyl oleate. Organometallics. 2006;25:3040–4.

    Article  CAS  Google Scholar 

  33. Hirano T, Yamada B. Macromonomer formation by sterically hindered radical polymerization of methyl acrylate trimer at high temperature. Polymer. 2003;44:347–54.

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors thank Chisato Shimaoka (Base Technology Center, Toagosei Co., Ltd) for helping with the SEC measurements.

Author information

Authors and Affiliations

  1. Productive Technology Department, Nagoya Plant, Toagosei Co. Ltd, 8, Showa-cho, Minato-ku, Nagoya, 455-0026, Japan

    Yasuyuki Sanai

  2. Base Technology Center, Toagosei Co. Ltd, 8, Showa-cho, Minato-ku, Nagoya, 455-0026, Japan

    Kouzou Kubota

Authors
  1. Yasuyuki Sanai
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Kouzou Kubota
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Yasuyuki Sanai.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Sanai, Y., Kubota, K. Effect of UV-curing conditions on the polymer structures: a comparison between coating and adhesive. Polym J 52, 1153–1163 (2020). https://doi.org/10.1038/s41428-020-0347-4

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41428-020-0347-4

This article is cited by

Search

Advanced search

Quick links