Preparation and characterization of dimer fatty acid epoxy-acrylate resin hybrid emulsion for photocurable coatings

  • Shengyuan Liang
  • Kai XuEmail author
  • Hongbo Liu
  • Xuefeng Gui
  • Tian Zhang
Original Contribution


UV-curable epoxy acrylate oligomer was synthesized via one-pot and two-step method by the ring-opening reaction of bisphenol-A epoxy resin (DGEBA) with dimer acid (DA) and acrylic acid (AA) in this paper. The molecular chain was firstly extended with DA. Then, AA, as a blocking agent, played the role in introducing unsaturated bonds to the chain. The water-based dispersion of epoxy acrylate was fabricated by subsequent phase-inversion emulsification in the presence of methacryloxypropyl silsesquioxane (MASQ). Compared with the traditional UV-curable epoxy acrylate, emulsions contain much less volatile organic compounds (VOC), which are more widely used in the coating industry. Because of the introduction of unsaturated bonds, MASQ participated in free-radical polymerization when incurred by UV, resulting in a better compatibility with epoxy acrylate. The cured samples were characterized with dynamic thermomechanical analysis (DMA), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and contact angle measurement (CA). The results indicated that the thermal property, flexibility, and water resistance all improved with the increasing proportion of DA, which may contribute to the long hydrophobic chain. Besides, the organic-inorganic and cage-like structure of MASQ also contributed to the enhancement of thermal property, water resistance, glass transition temperature, and storage modulus. With the above favorable properties and performances, the dimer fatty acid epoxy-acrylate resins will demonstrate promising applications in waterborne coatings.

Graphical abstract



Photo-curing Waterborne coatings Epoxy acrylate Dimer fatty acids 


Funding information

The National Nature Science Foundation of China (no. 21174162) and the Province Natural Science Fund of Guangdong (no. 2016A030313162) provided financial support. This work was also supported by Guangzhou Science and Technology Plan projects (no. 201505051006333) and Shenzhen Basic Research Project (no. JCYJ20170818114324998).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

396_2019_4534_MOESM1_ESM.docx (707 kb)
ESM 1 (DOCX 707 kb)


  1. 1.
    Endruweit A, Johnson MS, Long AC (2006) Curing of composite components by ultraviolet radiation: a review. Polym Compos 27(2):119–128. Google Scholar
  2. 2.
    Javadi A, Mehr HS, Sobani M, Soucek MD (2016) Cure-on-command technology: a review of the current state of the art. Prog Org Coat 100:2–31. Google Scholar
  3. 3.
    Lligadas G, Ronda JC, Galià M, Cádiz V (2013) Renewable polymeric materials from vegetable oils: a perspective. Mater Today 16(9):337–343. Google Scholar
  4. 4.
    Dehghan A, Zohuriaan-Mehr MJ, Salimi A (2017) Rapid preparation of epoxy acrylate-clay nanocomposite: simultaneous acrylation/nanoclay dispersion under ultrasonication. Prog Org Coat 108:44–50. Google Scholar
  5. 5.
    Chambhare SU, Lokhande GP, Jagtap RN (2017) Design and UV-curable behaviour of boron based reactive diluent for epoxy acrylate oligomer used for flame retardant wood coating. Des Monomers Polym 20(1):125–135. Google Scholar
  6. 6.
    Darani MK, Bastani S, Ghahari M, Kardar P, Mohajerani E (2017) NIR induced photopolymerization of acrylate-based composite containing upconversion particles as an internal miniaturized UV sources. Prog Org Coat 104:97–103. Google Scholar
  7. 7.
    Rwei SP, Chen YM, Chiang WY, Ting YT (2017) A study of the curing and flammability properties of bisphenol a epoxy Diacrylate resin utilizing a novel flame retardant monomer, bis[di-acryloyloxyethyl]-p-tert-butyl-phenyl phosphate. Materials 10(2):202. Google Scholar
  8. 8.
    Jeong WW, Kim JW, Suh KD (1998) Ultraviolet-curable epoxy acrylate dispersions: effect of urethane acrylate anionomers on stabilizing and film properties. Colloid Polym Sci 276(11):976–983. Google Scholar
  9. 9.
    Najafi F, Shirkavand Hadavand B, Pournamdar A (2017) Trimethoxysilane-assisted UV-curable urethane acrylate as clear coating: from synthesis to properties. Colloid Polym Sci 295(9):1717–1728. Google Scholar
  10. 10.
    Zhang P, Xin J, Zhang J (2013) Effects of catalyst type and reaction parameters on one-step Acrylation of soybean oil. ACS Sustain Chem Eng 2(2):181–187. Google Scholar
  11. 11.
    Llevot A (2016) Sustainable synthetic approaches for the preparation of plant oil-based thermosets. J Am Oil Chem Soc 94(2):169–186. Google Scholar
  12. 12.
    Zhang C, Yan M, Cochran EW, Kessler MR (2015) Biorenewable polymers based on acrylated epoxidized soybean oil and methacrylated vanillin. Mater Today Commun 5:18–22. Google Scholar
  13. 13.
    Sharmin E, Zafar F, Akram D, Alam M, Ahmad S (2015) Recent advances in vegetable oils based environment friendly coatings: a review. Ind Crop Prod 76:215–229. Google Scholar
  14. 14.
    Thames SF, Yu H (1999) Cationic UV-cured coatings of epoxide-containing vegetable oils. Surf Coat Technol 115(2–3):208–214. Google Scholar
  15. 15.
    Lomege J, Lapinte V, Negrell C, Robin JJ, Caillol S (2019) Fatty acid-based radically Polymerizable monomers: from novel poly(meth)acrylates to cutting-edge properties. Biomacromolecules 20(1):4–26. Google Scholar
  16. 16.
    Fertier L, Koleilat H, Stemmelen M, Giani O, Joly-Duhamel C, Lapinte V, Robin J-J (2013) The use of renewable feedstock in UV-curable materials – a new age for polymers and green chemistry. Prog Polym Sci 38(6):932–962. Google Scholar
  17. 17.
    Liu R, Zhu J, Luo J, Liu X (2014) Synthesis and application of novel UV-curable hyperbranched methacrylates from renewable natural tannic acid. Prog Org Coat 77(1):30–37. Google Scholar
  18. 18.
    Keramatinia M, Najafi F, Saeb MR (2017) Synthesis and viscoelastic properties of acrylated hyperbranched polyamidoamine UV-curable coatings with variable microstructures. Prog Org Coat 113:151–159. Google Scholar
  19. 19.
    Ligon-Auer SC, Schwentenwein M, Gorsche C, Stampfl J, Liska R (2016) Toughening of photo-curable polymer networks: a review. Polym Chem 7(2):257–286. Google Scholar
  20. 20.
    Li H, Zhang Z, Ma X, Hu M, Wang X, Fan P (2007) Synthesis and characterization of epoxy resin modified with nano-SiO2 and γ-glycidoxypropyltrimethoxy silane. Surf Coat Technol 201(9–11):5269–5272. Google Scholar
  21. 21.
    Trujillo-Lemon M, Ge J, Lu H, Tanaka J, Stansbury JW (2006) Dimethacrylate derivatives of dimer acid. J Polym Sci Part A Polym Chem 44(12):3921–3929. Google Scholar
  22. 22.
    Li S, Yang X, Huang K, Li M, Xia J (2014) Design, preparation and properties of novel renewable UV-curable copolymers based on cardanol and dimer fatty acids. Prog Org Coat 77(2):388–394. Google Scholar
  23. 23.
    Liu X, Xu K, Liu H, Cai H, Su J, Fu Z, Guo Y, Chen M (2011) Preparation and properties of waterborne polyurethanes with natural dimer fatty acids based polyester polyol as soft segment. Prog Org Coat 72(4):612–620. Google Scholar
  24. 24.
    Jiang L, Xu Q, Hu C (2006) Preparation and characterization of waterborne Polyurethaneurea composed of dimer fatty acid polyester polyol. J Nanomater 2006:1–10. Google Scholar
  25. 25.
    Xing Y, Xu K, Peng J, Lin W, Gao S, Ren Y, Chen M (2016) Polymerizable molecular Silsesquioxane-cages armored hybrid microcapsules with in situ Shell functionalization. Chem Eur J 22(6):2114–2126. Google Scholar
  26. 26.
    Xing Y, Peng J, Xu K, Gao S, Gui X, Liang S, Sun L, Chen M (2017) A soluble star-shaped silsesquioxane-cored polymer-towards novel stabilization of pH-dependent high internal phase emulsions. Phys Chem Chem Phys 19(34):23024–23033. Google Scholar
  27. 27.
    Peng J, Xu K, Cai H, Wu J, Lin W, Yu Z, Chen M (2014) Can an intact and crystalline octakis(methacryloxypropyl) silsesquioxane be prepared by hydrolysis-condensation of a trimethoxysilane precursor? RSC Adv 4(14).
  28. 28.
    Shu F, Wang M, Pang J, Yu P (2018) A free-standing superhydrophobic film for highly efficient removal of water from turbine oil. Front Chem Sci Eng 13:393–399. Google Scholar
  29. 29.
    Yang Z, Xu Y, Zhao D, Xu M (2000) Preparation of waterborne dispersions of epoxy resin by the phase-inversion emulsification technique. 1. Experimental study on the phase-inversion process. Colloid Polym Sci 278(12):1164–1171. Google Scholar
  30. 30.
    Yuan C, Cui M, Feng L, Wang J, Peng Y (2016) Efficient removal of cu(II) using amino-functionalized superparamagnetic nanoparticles prepared via SI-ATRP. J Appl Polym Sci 133(1):42859. Google Scholar
  31. 31.
    Park J, Wang Z, Kim D, Lee J (2010) Effects of water on the esterification of free fatty acids by acid catalysts. Renew Energy 35(3):614–618. Google Scholar
  32. 32.
    Fatihanim MN, Suhaila M, Nor AI, Razali I (2008) Antioxidative properties of Pandanus amaryllifolius leaf extracts in accelerated oxidation and deep frying studies. Food Chem 110(2):319–327. Google Scholar
  33. 33.
    Grieths C (1952) Animal and vegetable oils, fats and waxes. Ind Lubr Tribol 4(8):19–24. Google Scholar
  34. 34.
    Chen W, Wang Y, Kuo S, Huang C, Tung P, Chang F (2004) Thermal and dielectric properties and curing kinetics of nanomaterials formed from poss-epoxy and meta-phenylenediamine. Polymer 45(20):6897–6908. Google Scholar
  35. 35.
    Choi J, Yee A, Laine R (2004) Toughening of cubic Silsesquioxane epoxy nanocomposites using Core-Shell rubber particles: a three-component hybrid system. Macromolecules 37(9):3267–3276. Google Scholar
  36. 36.
    Abad M, Barral L, Fasce D, Williams R (2003) Epoxy networks containing large mass fractions of a Monofunctional polyhedral oligomeric Silsesquioxane (POSS). Macromolecules 36(9):3128–3135. Google Scholar
  37. 37.
    Li D, Yee A, Chen I, Chang S, Takahashi K (1994) Fracture behaviour of unmodified and rubber-modified epoxies under hydrostatic pressure. J Mater Sci 29(8):2205–2215. Google Scholar
  38. 38.
    Fu Z, Sun Y (1989) Epoxy resin toughened by thermoplastics. Chin J Polym Sci 7(4):367–378Google Scholar
  39. 39.
    Zhang Z, Liang G, Wang J, Ren P (2007) Epoxy/POSS organic–inorganic hybrids: viscoelastic, mechanical properties and micromorphologies. Polym Compos 28(2):175–179. Google Scholar
  40. 40.
    Liu Y, Zheng S (2006) Inorganic-organic nanocomposites of polybenzoxazine with octa(propylglycidyl ether) polyhedral oligomeric silsesquioxane. J Polym Sci Part A Polym Chem 44(3):1168–1181. Google Scholar
  41. 41.
    Kinloch A, Maxwell D, Young R (1985) The fracture of hybrid-particulate composites. J Mater Sci 20:4169–4184Google Scholar
  42. 42.
    Wu S, Hayakawa T, Kikuchi R, Grunzinger S, Kakimoto M (2007) Synthesis and characterization of Semiaromatic polyimides containing POSS in Main chain derived from double-Decker-shaped Silsesquioxane. Macromolecules 40(16):5698–5705. Google Scholar
  43. 43.
    Choi J, Yee A, Zhu Q, Laine R (2001) Organic/inorganic hybrid composites from cubic Silsesquioxanes. J Am Chem Soc 123(46):11420–11430. Google Scholar
  44. 44.
    Chen G, Si L, Lu P, Li Q (2012) Epoxy hybrid composites cured with octaaminophenyl polyhedral oligomeric silsesquioxane. J Appl Polym Sci 125(5):3929–3935. Google Scholar
  45. 45.
    Ghanbari H, Cousins BG, Seifalian AM (2011) A nanocage for nanomedicine: polyhedral oligomeric silsesquioxane (POSS). Macromol Rapid Commun 32(14):1032–1046. Google Scholar
  46. 46.
    Wu Z, Zhang S, Li H, Liang Y, Qi Z, Xu Y, Tang Y, Gong C (2015) Linear sulfonated polyimides containing polyhedral oligomeric silsesquioxane (POSS) in main chain for proton exchange membranes. J Power Sources 290:42–52. Google Scholar
  47. 47.
    Evans P, Haase J, Seman A, Kiguchi M (2015) The search for durable exterior clear coatings for wood. Coatings 5(4):830–864. Google Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Shengyuan Liang
    • 1
    • 2
  • Kai Xu
    • 1
    • 2
    Email author
  • Hongbo Liu
    • 3
  • Xuefeng Gui
    • 1
    • 2
  • Tian Zhang
    • 1
  1. 1.Guangzhou Institute of ChemistryChinese Academy of SciencesGuangzhouPeople’s Republic of China
  2. 2.The University of the Chinese Academy of SciencesBeijingPeople’s Republic of China
  3. 3.School of Applied Chemistry and Biological TechnologyShenzhen PolytechnicShenzhenPeople’s Republic of China

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