Abstract
In this study, a novel photo- and pH-sensitive cationic waterborne polyurethane containing side chain aromatic azo groups (Azo-CWPU) was synthesized by step-growth addition polymerization from polyether polylol, isophorone diisocyanate, N-methyl diethanolamine and a new aromatic azo-containing monomer, 2,2′-(4-((4-ethylphenyl)diazenyl)phenylazanediyl)diethanol (EDPD). Azo-CWPU showed a significant hypsochromic contrast to the azo monomer and rapid changes in UV–Vis absorption spectra at different irradiation times. Azo-CWPU dispersion displays bright yellow, orange and red color with the change of pH values. Regarding the orange dispersion, we assume that there is a mixture of the azoic form and the hydrazone form. Compared to cationic waterborne polyurethane dispersion without aromatic azo groups (CWPU), Azo-CWPU dispersion with smaller hydrodynamics radius and more narrow distribution shows good thermodynamic properties of polyurethane.
Similar content being viewed by others
References
Delaire JA, Nakatani K (2000) Linear and nonlinear optical properties of photochromic molecules and materials. Chem Rev 100(5):1817–1845
Li Z, Wang J, Liu X, Liu S, Ou J, Yang S (2011) Electrostatic layer-by-layer self-assembly multilayer films based on graphene and manganese dioxide sheets as novel electrode materials for supercapacitors. J Mater Chem 21:3397–3403
Coady DJ, Khramov DM, Norris BC, Tennyson AG, Bielawski CW (2009) Adapting N-heterocyclic carbene/azide coupling chemistry for polymer synthesis: enabling access to aromatic polytriazenes. Angew Chem Int Ed 48(28):5187–5190
Natansohn A, Rochon P (2002) Photoinduced motions in azo-containing polymers. Chem Rev 102(11):4139–4175
Ikeda T, Tsutsumi O (1995) Optical switching and image storage by means of azobenzene liquid-crystal films. Science 268:1873–1875
Wang G, Wang X (2002) A novel hyperbranched polyester functionalized with azo chromophore: synthesis and photoresponsive properties. Polym Bull 49(1):1–8
Ikeda T, Mamiya J, Yu Y (2007) Photomechanics of liquid-crystalline elastomers and other polymers. Angew Chem Int Ed 46(4):506–528
Zhu Z, Li Q, Zeng Q, Li Z, Li Z, Qin J, Ye C (2008) New azobenzene-containing polyurethanes: post-functional strategy and second-order nonlinear optical properties. Dyes Pigm 78(3):199–206
Liu L, Nakatani K, Pansu R, Vachon J, Tauc P, Ishow E (2007) Fluorescence patterning through photoinduced migration of squaraine-functionalized azo derivatives. Adv Mater 19(3):433–436
Li N, Xu Q, Lu J, Xia X, Wang L (2007) Atom transfer radical polymerization and third-order nonlinear optical properties of new azobenzene-containing side-chain polymers. Macromol Chem Phys 208(4):399–404
Dautzenberg H, Jaeger W, Kotz J, Philipp B, Seidel Ch, Stscherbina D (1994) Polyelectrolytes: formation, characterization and application. Hanser Publ, Munich
Hara M (1993) Polyelectrolytes: science and technology. Marcel Dekker Inc, New York
Lee S-H, Balasubramanian S, Kim D, Viswanathan N, Bian S, Kumar J, Tripathy S (2000) Azo polymer multilayer films by electrostatic self-assembly and layer-by-layer post azo functionalization. Macromolecules 33(17):6534–6540
Roberts MJ, Lindsay GA (1998) Thermally stable nonlinear optical films by alternating polyelectrolyte deposition on hydrophobic substrates. J Am Chem Soc 120(43):11202–11203
Dante S, Advincula R, Frank CW, Stroeve P (1999) Photoisomerization of polyionic layer-by-layer films containing azobenzene. Langmuir 15(1):193–201
Chattopadhyay DK, Raju KVSN (2007) Structural engineering of polyurethane coatings for high performance applications. Prog Polym Sci 32(3):352–418
Wang Y, Qiu F, Xu B, Xu J, Jiang Y, Yang D, Li P (2013) Preparation, mechanical properties and surface morphologies of waterborne fluorinated polyurethane-acrylate. Prog Org Coat 76(5):876–883
Buruiana EC, Buruiana T (2001) Polyurethane cationomers with azobenzene side groups in the flexible component. synthesis, characterization, and properties. Polym J 33:723–731
Buruiana EC, Buruiana T (2001) New quinone polyetherurethane cationomers. synthesis of some ionenes based on hydroquinone diamine. Polym J 33:42–48
Buruiana EC, Buruiana T, Strat G, Strat M (2002) Synthesis and optical properties of new polyurethane cationomers with anchored stilbene chromophores. J Polym Sci, Part A: Polym Chem 40(11):1918–1928
Buruiana EC, Buruiana T (2001) Synthesis of polyetherurethane cationomers with anthraquinone structure. Eur Polym J 37(12):2505–2511
Samal SK, Dash M, Van Vlierberghe S, Kaplan DL, Chiellini E, van Blitterswijk C, Moroni L, Dubruel P (2012) Cationic polymers and their therapeutic potential. Chem Soc Rev 41:7147–7194
De Smedt SC, Demeester J, Hennink WE (2000) Cationic polymer based gene delivery systems. Pharm Res 17(2):113–126
Król P, Król B, Stagraczyński R, Skrzypiec K (2013) Waterborne cationomer polyurethane coatings with improved hydrophobic properties. J Appl Polym Sci 127(4):2508–2519
Krol P, Krol B (2012) Surface free energy of polyurethane coatings with improved hydrophobicity. Colloid Polym Sci 290(10):879–893
ASTM D2572-97 (2010) Standard test method for isocyanate groups in urethane materials or prepolymers. ASTM International, West Conshohocken, PA. http://www.astm.org
Su W, Zhao H, Wang Z, Li Y, Zhang Q (2007) Sphere to disk transformation of micro-particle composed of azobenzene-containing amphiphilic diblock copolymers under irradiation at 436 nm. Eur Polym J 43(2):657–662
Sekkat Z, Knoll W (2002) Photoreactive organic thin films. Academic Press, San Diego
Dirksen A, de Cola L (2003) Photo-induced processes in dendrimers. C R Chim 6:873–882
Christie RM (2001) Colour chemistry. The Royal Society of Chemistry, London
Kim YB, Kim HK, Yoo JK, Hong JW (2002) UV-curable polyurethane dispersion for cationic electrodeposition coating. Surf Coat Tech 157(1):40–46
Acknowledgments
Financial supports from the National High Technology Research and Development Program of China (No. 2014AAQ00294) and the National Natural Science Foundation of China (No. 51073144) are acknowledged. We thank Dr Feng Jiang for his artwork support and discussions.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Li, J., Zhang, X., Gooch, J. et al. Photo- and pH-sensitive azo-containing cationic waterborne polyurethane. Polym. Bull. 72, 881–895 (2015). https://doi.org/10.1007/s00289-015-1312-9
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00289-015-1312-9