Skip to main content
SpringerLink
Log in

Preparation and properties of crosslinkable waterborne polyurethane and polyurethane-acrylic hybrid emulsions and their crosslinked polymers

  • ORIGINAL PAPER
  • Published:
Journal of Polymer Research Aims and scope Submit manuscript

Abstract

Stable emulsions of crosslinkable waterborne polyurethanes (CWPU) and waterborne polyurethane-acrylic (CWPU/AC) hybrid with various contents of trifunctional monomer (trimethylolpropane, TMP) and acrylic monomers were successfully prepared in this study. This study focused on the effects of crosslinkable TMP and acrylic monomer contents on the stability/average particle size/viscosity of CWPU and CWPU/AC hybrid emulsions, the mechanical/dynamic mechanical thermal properties, surface contact angle/tension and hardness/water swelling of CWPU and CWPU/AC hybrid film materials. The as-polymerized CWPU emulsion containing 0.06 mol (4.11 mol%) of TMP and CWPU/AC hybrid emulsion containing 60 wt% of acrylic monomer were found to be unstable, indicating that these contents were beyond the limit value of the self-emulsifying ability of dimethylol propionic acid (18.26 mol%). By XPS analysis, CWPU and CWPU/AC film samples were found to have silicone/fluorine enriched surface. The tensile strength/modulus/hardness of the film samples increased markedly with increasing crosslinkable TMP/acrylic monomer up to 0.04 mol/50 wt%, respectively. Meanwhile the elongation at break and water swelling % decreased significantly. The water/ethylene glycol contact angles increased/the surface tension decreased significantly with increasing crosslinkable TMP/acrylic monomer contents up to 0.04 mol/50 wt%. Thus, the optimum TMP/acrylic monomer contents were found to be about 0.04 mol/50 wt% to obtain high performance antifouling coating materials.

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
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  1. Lu YS, Richard CL (2007) New hybrid latexes from a soybean oil-based waterborne polyurethane and acrylics via emulsion polymerization. Biomacromolecules 8:3108–3114

    Article  CAS  Google Scholar 

  2. Modesti M, Lorenzetti A (2001) An experimental method for evaluating isocyanate conversion and trimer formation in polyisocyanate–polyurethane foams. Eur Polym J 37:949–954

    Article  CAS  Google Scholar 

  3. Lee SY, Lee JS, Kim BK (1997) Preparation and properties of water-borne polyurethanes. Polym Int 42:67–76

    Article  CAS  Google Scholar 

  4. Rahman MM, Kim HD (2006) Synthesis and characterization of waterborne polyurethane adhesives containing different amount of ionic groups (I). J Appl Polym Sci 102:5684–5691

    Article  CAS  Google Scholar 

  5. Shin MS, Lee YH, Rahman M, Kim HD (2013) Synthesis and properties of waterborne fluorinated polyurethane-acrylate using a solvent−/emulsifier-free method. Polymer 54:4873–4882

    Article  CAS  Google Scholar 

  6. Kim BG, Sohn EH, Cho K, Lee JC (2008) Semifluorinated side group poly(oxyethylene) derivatives having extremely low surface energy: synthesis, characterization, and surface properties. Eur Polym J 44:2912–2919

    Article  CAS  Google Scholar 

  7. Zhao Z, Li X, Li P, Wang C, Luo Q (2014) Study on properties of waterborne fluorinated polyurethane/acrylate hybrid emulsion and films. J Polym Res 21:460–468

    Article  Google Scholar 

  8. Xiao X, Wang Y (2009) Emulsion copolymerization of fluorinated acrylate in the presence of a polymerizable emulsifier, colloids. Surf A Physicochem Eng Asp 348:151–156

    Article  CAS  Google Scholar 

  9. Hirose M, Kadowaki F, Zhou J (1997) The structure and properties of core-shell type acrylic-polyurethane hybrid aqueous emulsions. Prog Org Coat 31:157–169

    Article  CAS  Google Scholar 

  10. Lee SW, Lee YH, Park H, Kim HD (2013) Effect of total acrylic/fluorinated acrylic monomer contents on the properties of waterborne polyurethane/acrylic hybrid emulsions. Macromol Res 21:709–718

    Article  CAS  Google Scholar 

  11. Park YG, Lee YH, Rahman MM, Park CC, Kim HD (2015) Preparation and properties of waterborne polyurethane/self-cross-linkable fluorinated acrylic copolymer hybrid emulsions using a solvent/emulsifier-free method. Colloid Polym Sci 293:1369–1382

    Article  CAS  Google Scholar 

  12. Wang L, Shen Y, Lai X, Li Z, Liu M (2011) Synthesis and properties of crosslinked waterborne polyurethane. J Polym Res 18:469–476

    Article  CAS  Google Scholar 

  13. Lai X, Shen Y, Wang L (2011) Preparation and properties of self-crosslinkable polyurethane/silane hybrid emulsion. J Polym Res 18:2425–2433

    Article  CAS  Google Scholar 

  14. Yue S, Zhang Z, Xiao C (2015) Effect of 3-aminopropyltriethoxysilane on solvent resistance, thermal and mechanical properties of two-component waterborne polyurethane. Int J Polym Anal Ch 20:285–297

    Article  CAS  Google Scholar 

  15. Lopez A, Degrandi-Contraires E, Canetta E, Creton C, Keddie JL, Asua JM (2011) Waterborne Polyurethane − Acrylic hybrid nanoparticles by Miniemulsion polymerization: applications in pressure-sensitive adhesives. Langmuir 27:3878–3888

    Article  CAS  Google Scholar 

  16. Mequanint K, Sanderson R (2003) Self-assembling metal coatings from phosphated and siloxane-modified polyurethane dispersions: an analysis of the coating–air interface. J Appl Polym Sci 8:893–899

    Article  Google Scholar 

  17. Lee JR, Jin FL, Park SJ, Park JM (2004) Study of new fluorine-containing epoxy resin for low dielectric constant. Surf Coat Technol 180:650–654

    Article  Google Scholar 

  18. Cui X, Zhong S, Wang H (2007) Synthesis and characterization of emulsifier-free core–shell fluorine-containing polyacrylate latex. Colloids Surf A Physicochem Eng Asp 303:173–178

    Article  CAS  Google Scholar 

  19. Saidi S, Guittard F, Guimon C, Géribaldi S (2006) Synthesis and characterization of copolymers based on styrene and partially fluorinated acrylates. Eur Polym J 42:702–710

    Article  CAS  Google Scholar 

  20. Rahman MM, Lee I, Chun HH, Kim HD, Park H (2014) Properties of waterborne polyurethane-fluorinated marine coatings: the effect of different types of diisocyanates and tetrafluorobutanediol chain extender content. J Appl Polym Sci 131:39905

    Google Scholar 

  21. Kong X, Liu G, Curtis JM (2011) Characterization of canola oil based polyurethane wood adhesives. Int J Adhes Adhes 31:559–564

    Article  CAS  Google Scholar 

  22. Chattopadhyay DK, Webster DC (2009) Thermal stability and flame retardancy of polyurethanes. Prog Polym Sci 34:1068–1133

    Article  CAS  Google Scholar 

  23. Rahman MM, Kim HD, Lee WK (2009) Properties of waterborne polyurethane adhesives: effect of chain extender and polyol content. J Adhes Sci Technol 23:177–193

    Article  CAS  Google Scholar 

  24. Levine F, Scala JL, Kosik W (2010) Properties of clear polyurethane films modified with a fluoropolymer emulsion. Prog Org Coat 69:63–72

    Article  CAS  Google Scholar 

  25. Kaelble D, Moacanin J (1977) A surface energy analysis of bioadhesion. Polymer 18:475–482

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIP) through GCRC-SOP (No. 2011-0030013).

Author information

Authors and Affiliations

  1. Department of Organic Material Science and Engineering, College of Engineering, Pusan National University, 2, Busandaehak-ro 63, Geumjeong-Gu Busan, 46241, South Korea

    Kim HyeLin, Lee YoungHee & Kim HanDo

  2. Industrial Materials Fusion Technology Center, Korea institute of Footwear and Leather Technology, Busan, 47154, South Korea

    Kim JungSoo

  3. Division of Energy & Bio Engineering, Dongseo University, Busan, 47011, South Korea

    Park ChaCheol

  4. Global Core Research Center for Ships and Offshore Plants, Pusan National University, Busan, 46241, South Korea

    Park Hyun

  5. Department of Naval Architecture and Ocean Engineering, Pusan National University, Busan, 46241, South Korea

    Chun HoHwan

Authors
  1. Kim HyeLin
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Lee YoungHee
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Kim JungSoo
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Park ChaCheol
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Park Hyun
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Chun HoHwan
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Kim HanDo
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Kim HanDo.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

HyeLin, K., YoungHee, L., JungSoo, K. et al. Preparation and properties of crosslinkable waterborne polyurethane and polyurethane-acrylic hybrid emulsions and their crosslinked polymers. J Polym Res 23, 240 (2016). https://doi.org/10.1007/s10965-016-1134-y

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s10965-016-1134-y

Keywords

Search

Navigation