Preparation and Properties of UV-cured Self-healing Polyurethane Coatings Based on Diels-Alder Reaction

doi:10.7517/issn.1674-0475.180604

Abstract

Abstract: N,N'-4,4'-Diphenylmethane-bismaleimide (BMI) and furfuryl alcohol (FA) were used to synthesize the modified DA monomers with hydroxyl groups through Diels-Alder reaction, and then use the polycarbonates diols (PCDL)with different molecular weights, isophorone isocyanate (IPDI) and modified DA monomers as reaction monomers to obtain a polyurethane prepolymer. Then the UV cured self-healing polyurethane were prepared by reaction of the prepolymer and hydroxyethyl methacrylate (HEMA). Fourier transform infrared (FT-IR) and nuclear magnetic resonance (¹HNMR) spectra were used to characterize the structure and double bond conversion of the self-healing polyurethane. In addition, the UV cured self-healing polyurethane coatings were prepared by designing a series of coating formulations with the polyurethane. The self-healing properties and thermal properties of the coatings were tested by ultra-deep-depth microscope and thermal gravimetric analyzer (TGA). The results showed that the hardness of the coatings decreased as the molecular weight of PCDL increased, and the introduction of the DA monomer imparts self-healing properties to the coating while increasing the hardness of the coating.

Key words: self-healing, UV-cured, Diels-Alder, polyurethane, coatings

CAO Jiancheng, LU Fukang, LIU Jingcheng, LIU Ren, YUAN Yan. Preparation and Properties of UV-cured Self-healing Polyurethane Coatings Based on Diels-Alder Reaction[J]. Imaging Science and Photochemistry, 2018, 36(6): 489-497.

References

[1] Binder W H. Self-Healing Polymers:From Principles to Applications[M]. America:John Wiley & Sons, 2013. 90-109.
[2] Ghosh S K. Self-Healing Materials:Fundamentals, Design Strategies, and Applications[M]. America:John Wiley & Sons, 2009. 95-120.
[3] Patrick J F, Robb M J, Sottos N R, Moore J S, White S R. Polymers with autonomous life-cycle control[J]. Nature, 2016, 540(7633):363-370.
[4] Yamaguchi M, Ono S, Terano M. Self-repairing property of polymer network with dangling chains[J]. Materials Letters, 2007, 61(6):1396-1399.
[5] Cho S H, White S R, Braun P V. Self-healing polymer coatings[J]. Advanced Materials, 2009, 21(6):645-649.
[6] White S R, Sottos N R, Geubelle P H, Moore J S, Kessler M R, Sriram S R, Brow E N, Viswanathan S. Autonomic healing of polymer composites[J]. Nature, 2001, 409(6822):794-797.
[7] Toohey K S, Sottos N R, Lewis J A, Moore J S, White S R. Self-healing materials with microvascular networks[J]. Nature Materials, 2007, 6(8):581-585.
[8] Yuan C E, Rong M Z, Zhang M Q, Zhang Z P, Yuan Y C. Self-healing of polymers via synchronous covalent bond fission/radical recombination[J]. Chemistry of Materials, 2011, 23(22):5076-5081.
[9] Jia X Y, Mei J F, Lai J C, Li C H, You X Z. A self-healing PDMS polymer with solvatochromic properties[J]. Chemical Communications, 2015, 51(43):8928-8930.
[10] Burattini S, Colquhoun H M, Fox J D, Friedmann D, Greenland B W, Harris P J, Hayes W, Mackay M E, Rowan S J. A Self-repairing, supramolecular polymer system:heal ability as a consequence of donor-acceptor π-π stacking interactions[J]. Chemical Communications, 2009, (44):6717-6719.
[11] Kim Y H, Wool R P. A theory of healing at a polymer-polymer interface[J]. Macromolecules, 1983, 16(7):1115-1120.
[12] Chen Y, Kushner A M, Williams G A, Guan Z. Multiphase design of autonomic self-healing thermoplastic elastomers[J]. Nature Chemistry, 2012, 4(6):467-472.
[13] Liu R, Zhu G, Li Z, Liu X, Chen Z, Ariyasivam S. Cardanol-based oligomers with "hard core, flexible shell" structures:from synthesis to UV curing applications[J]. Green Chemistry, 2015, 17(6):3319-3325.
[14] Liu R, Yang X, Yuan Y, Liu J, Liu X. Synthesis and properties of UV-curable self-healing oligomer[J]. Progress in Organic Coatings, 2016, 101:122-129.
[15] Gao F, Cao J, Wang Q, Liu R, Zhang S, Liu J, Liu X. Properties of UV-cured self-healing coatings prepared with PCDL-based polyurethane containing multiple H-bonds[J]. Progress in Organic Coatings, 2017, 113:160-167.
[16] Liu Y L, Chen Y W. Thermally reversible cross-linked polyamides with high toughness and self-repairing ability from maleimide and furan functionalized aromatic polyamides[J]. Macromolecular Chemistry and Physics, 2007, 208(2):224-232.
[17] Vilela C, Cruciani L, Silvestre A J, Gandini A. A double click strategy applied to the reversible polymerization of furan/vegetable oil monomers[J]. Macromolecular Rapid Communications, 2011, 32(17):1319-1323.
[18] Huang Y, Pang L, Wang H, Zhong R, Zeng Z, Yang J. Synthesis and properties of UV-curable tung oil based resins via modification of Diels-Alder reaction, nonisocyanate polyurethane and acrylates[J]. Progress in Organic Coatings, 2013, 76(4):654-661.
[19] Jo Y Y, Lee A S, Baek K Y, Lee H, Hwang S S. Multi-crosslinkable self-healing polysilsesquioxanes for the smart recovery of anti-scratch properties[J]. Polymer, 2017, 124:78-87.