Skip to main content

Advertisement

SpringerLink
Log in

The development of an Epoxy-amine/Thiol-ene photocurable system

  • Original Paper
  • Published:
Journal of Polymer Research Aims and scope Submit manuscript

Abstract

In this study is reported a new method to photocure epoxy resins rapid and quantitatively. It was combined the thiol-ene photopolymerization with the anionic polymerization of an epoxy resin. A tetrallylic tertiary diamine was used as the curing agent. The basic character of the diamine initiated the anionic polymerization of the epoxy resin and at the same time, the allylic groups of the curing agent reacted with a multifunctional thiol. It was found that increasing the concentration of the thiol-ene system in the epoxy formulation resulted in a higher photopolymerization rate and conversion of the epoxy groups. The moduli of the polymers with increasing concentrations of the thiol-ene system were higher than the modulus of a polymer cured with diethylenetriamine which is a conventional curing agent. A study with model compounds revealed that tertiary amine and multifunctional thiol, as well as the polythioethers formed in the thiol-ene reaction induced the anionic polymerization of the epoxy resin.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

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

Similar content being viewed by others

References

  1. Acosta Ortiz R, Garcia Valdéz AE, Berlanga Duarte ML, Guerrero Santos R, Ovando Flores LR, Soucek MD (2008) Development and Study of a Coupling Agent for Photocurable Hybrid Thiol-Ene/cationic Formulations. Macromol Chem Phys 209:2157–2168

    Article  Google Scholar 

  2. Acosta Ortiz R, Puente Urbina BA, Cabello Valdez LV, Berlanga Duarte ML, Guerrero Santos R, García Valdez AE, Soucek MD (2007) The effect of introducing a cationic system into a Thiol-Ene Photopolymerizable Formulation. J Polym Sci A Polym Chem 45:4829–4843

    Article  Google Scholar 

  3. Acosta Ortiz R, Puente Urbina BA, Guerrero Santos R, Berlanga Duarte ML, Garcia Valdez AE, Soucek MD (2008) Development of hybrid polymeric materials based on Photocurable Thiol-Ene/cationic formulations. Macromol Mater Eng 293:731–739

    Article  Google Scholar 

  4. Ashcroft WR (1993) Curing Agents for epoxy resins. Blackie Academic & Professional, Bishonpbriggs

    Book  Google Scholar 

  5. Beyazkilic Z, Kahveci MU, Aydogan B, Kiskan B, Yagci Y (2012) Synthesis of polybenzoxazine precursors, using thiols: simultaneous thiol-ene and ring-opening reactions. J Polym Sci: Part A: Polym Chem 40:4029–4036

    Article  Google Scholar 

  6. Bor-sem C, Khan SA (1997) Real-time FTIR and in situ rheological studies on the UV curing kinetics of thiol-ene polymers Real-time FTIR and in situ rheological studies on the UV curing kinetics of thiol-ene polymers. Macromolecules 30:7322–7328

    Article  Google Scholar 

  7. Carioscia JA, Liu H, Stansbury JW, Bowman CN (2005) Thiol-ene oligomers as dental restorative materials. Dent Mater 21:1137–1143

    Article  CAS  Google Scholar 

  8. Carioscia JA, Stansbury JW, Bowman CN (2007) Evaluation and control of thiol-ene/thiol-epoxy hybrid networks. Polymer 48:1526–1532

    Article  CAS  Google Scholar 

  9. Cho JD, Hong JW (2004) UV-initiated free radical and cationic photopolymerizations of Acrylate/Epoxide and Acrylate/Vinyl Ether Hybrid systems with and without Photosensitizers. J Appl Polym Sci 93:1473–1483

    Article  CAS  Google Scholar 

  10. Cramer NB, Bowman CN (2001) Kinetics of Thiol-ene and Thiol-Acrylate Photopolymerizations with Real-Time Fourier Transform Infrared. J Polym Scie: Part A: Polym Chem 39:3311–3318

    Article  CAS  Google Scholar 

  11. Flores M, Tomuta AM, Fernández-Francos X, Ramis X, Sangermano M, Serra A (2013) A new two-stage curing system: Thiol-ene/epoxy homopolymerization using an allyl terminated hyperbranched polyester as reactive modifier. Polymer 54:5473–5481

    Article  CAS  Google Scholar 

  12. Henkel, Ag & Co Kgaa 2013 US patent application 20130146223, 13 junio

  13. Hodgkin, J.H.; Demerac, S. (1980) Ions in polymers, Cyclopolymerization of N, N-disubstituted diallyl amines, In Advances in Chemistry, ed. Adi Eisenberg, vol 187, chap14, p.211-233, ACS publications

  14. Hoyle CE, Bowman CN (2010) Thiol-Ene Click Chemistry Angew. Chem, Inter Ed 49(9):1540–1573

    Article  CAS  Google Scholar 

  15. Hoyle CE, Lee TY, Roper TT-e (2004) Chemistry of the past with prommise for the future. J Polym Sci: Part A: Polym Chem 42:5301–5338

    Article  CAS  Google Scholar 

  16. Jacobine, A.F. (1993); In Radiation curing in polymer scienceand technology, III, polymerization mechanism, Fouassier, J.D. Rabek, J.F. eds. Elsevier Applied Polymer Science, London,, Vol.3

  17. Kim SK, Baguenard C, Guymon CA (2013) Influence of Photopolymerization Characteristics onThermo-Mechanical Properties of Nanocomposites Utilizing Polymerizable Organoclays in Thiol-Acrylate Systems. Macromol Symp 329:173–192

    Article  CAS  Google Scholar 

  18. Lee TY, Roper TM, Jonsson ES, Guymon CA, Hoyle CE (2004) Thiol-Ene Photopolymerization of vinyl acrylate/Multifunctional Thiol mixtures. Macromolecules 37:3606–3613

    Article  CAS  Google Scholar 

  19. Lee TY, Smith Z, Reddy SK, Cramer NB, Bowman CN (2007) Thiol-Allyl Ether-Methacrylate ternary systems. Polymerization mechanism, Macromolecules 40:1466–1472

    Article  CAS  Google Scholar 

  20. Liow SS, Lipik VT, Widjaja LK, Abadie MJM (2012) Synthesis, characterization and photopolymerization of vinyl ether and acrylate functionalized hybrid oligo-caprolactone. J Polym Res 19:9748–9756

    Article  Google Scholar 

  21. Lowe A (2010) Thiol-Ene Click reactions and recent applications in polymer and material synthesis. Polym Chem 1:17–36

    Article  CAS  Google Scholar 

  22. Rozenberg BA (1986) Advances in Polymer Sciences 75:113–165

    Article  Google Scholar 

  23. Tanaka, Y.M., (1973) Epoxide-curig reactions, In: Epoxy resins, chemistry and technology, ed. C.T., May, New York, Marcel Dekker

  24. Van Assche G, Swier S, Van Mele B (2002) Modeling and experimental verification of the kinetics of reacting polymer systems. Thermochim Acta 388:327–314

    Article  Google Scholar 

  25. Xiao M, He Y, Nie J (2008) Novel Bisphenol A epoxide-acrylate hybrid oligomer and its photopolymerization. Designed Monomer and Polymers 11(4):383–394

    Article  CAS  Google Scholar 

  26. Ying C, Jessop JLP (2006) Decreased Oxygen Inhibition in photopolymerized Acrylate/Epoxide Hybrid polymer coatings as demostrated by Raman Spectroscopy. Polymer 47(19):6560–6566

    Article  Google Scholar 

Download references

Acknowledgments

The authors thank the Mexican National Council of Science and Technology (CONACYT) for funding this project 151489. We also gratefully acknowledged the assistance in analysis of samples by Guadalupe Mendez, Jose Luis Saucedo, Sergio Zertuche and Rodrigo Cedillo,

Author information

Authors and Affiliations

  1. Centro de Investigación en Química Aplicada, Blvd. Enrique Reyna #140, C.P. 25294, Saltillo, Coahuila, Mexico

    Ricardo Acosta Ortiz, Aida Esmeralda García Valdez, Ana Gabriela Navarro Tovar, Adrián Alejandro Hilario de la Cruz, Luis Fernando González Sánchez, Justo Horacio García Trejo & Jorge Félix Espinoza Muñoz

  2. Politecnico di Torino, Cso. Duca degli Abruzzi 24, Torino, 10129, Italy

    Marco Sangermano

Authors
  1. Ricardo Acosta Ortiz
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Aida Esmeralda García Valdez
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Ana Gabriela Navarro Tovar
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Adrián Alejandro Hilario de la Cruz
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Luis Fernando González Sánchez
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Justo Horacio García Trejo
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Jorge Félix Espinoza Muñoz
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Marco Sangermano
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Ricardo Acosta Ortiz.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Acosta Ortiz, R., García Valdez, A.E., Navarro Tovar, A.G. et al. The development of an Epoxy-amine/Thiol-ene photocurable system. J Polym Res 21, 504 (2014). https://doi.org/10.1007/s10965-014-0504-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s10965-014-0504-6

Keywords

Search

Navigation