Abstract
A novel environmentally friendly fluorinated diamine N-[2-[(2-aminoethyl) amino]ethyl]-perfluoro-2,5-dimethyl-3,6-dioxa-nonanamide(FDETA) was synthesized for the first time based on diethylenetriamine and ethyl perfluoro-2,5-dimethyl-3,6-dioxa-nonanoate (FEt). It was characterized by means of Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR) and mass spectroscopy (MS). Subsequently, fluorinated polyurethanes (FPUs) containing various amounts of FDETA were then synthesized using hexamethylene diisocyanate (HDI), poly(tetramethylene oxide glycol) (PTMG), FDETA and 1,4-butanediol (BDO) as the main starting materials. Results of proton 1H NMR and FTIR had verified successful incorporation of the FDETA chain extenders into FPU backbones. The surface properties of FPUs were detected by contact angle measurement, scanning electron microscope (SEM), and energy-dispersive X-ray spectroscopy (EDX). The thermal property of FPUs was also investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Results from EDX, SEM and contact angle studies indicated that fluorinated side chains in the hard segments had indeed migrated onto the surface. Results from DSC and TGA studies indicated that the thermal stability and the degree of phase separation were also improved.
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References
Chattopadhyay DK, Raju KVSN (2007) Structural engineering of polyurethane coatings for high performance applications. Prog Polym Sci 32:352–418. https://doi.org/10.1016/j.progpolymsci.2006.05.003
Ge Z, Zhang X, Dai J, Li W, Luo Y (2009) Synthesis, characterization and properties of a novel fluorinated polyurethane. Eur Polym J 45:530–536. https://doi.org/10.1016/j.eurpolymj.2008.11.008
Jiang M, Zhao X, Ding X, Zheng Z, Peng Y (2005) A novel approach to fluorinated polyurethane by macromonomer copolymerization. Eur Polym J 41:1798–1803. https://doi.org/10.1016/j.eurpolymj.2005.02.013
Kim YS, Lee JS, Ji Q, McGrath JE (2002) Surface properties of fluorinated oxetane polyol modified polyurethane block copolymers. Polymer 43:7161–7170. https://doi.org/10.1016/S0032-3861(02)00458-5
Li J, Zhang X, Liu Z, Li W, Dai J (2015) Studies on waterborne polyurethanes based on new medium length fluorinated diols. J Fluorine Chem 175:12–17. https://doi.org/10.1016/j.jfluchem.2015.02.015
Lindstrom AB, Strynar MJ, Libelo EL (2011) Polyfluorinated compounds: past, present, and future. Environ Sci Technol 45:7954–7961. https://doi.org/10.1021/es2011622
Lu YH, Xiao GY, Chi HJ, Dong Y, Hu ZZ (2013) Effects of tert-butyl substitutes of fluorinated diamine on the properties of polyimides. High Perform Polym 25:894–900. https://doi.org/10.1177/0954008313487930
Qin XM, Fang F, Yang XH, Wang XL, Zheng Z (2006) Synthesis and characterization of polyurethane urea based on fluorine-containing bisphenoxydiamine. J Appl Polym Sci 102:1863–1869. https://doi.org/10.1002/app.24138
Ratna D, Karger-Kocsis J (2008) Recent advances in shape memory polymers and composites: a review. J Mater Sci 43:254–269. https://doi.org/10.1007/s10853-007-2176-7
Shin M, Lee Y, Rahman M, Kim H (2013) Synthesis and properties of waterborne fluorinated polyurethane-acrylate using a solvent-/emulsifier-free method. Polymer 54:4873–4882. https://doi.org/10.1016/j.polymer.2013.07.005
Su SK, Gu JH, Lee HT, Wu CL, Hwang JJ, Suen MC (2017) Synthesis and properties of novel biodegradable polyurethanes containing fluorinated aliphatic side chains. J Polym Res 24:142–158. https://doi.org/10.1007/s10965-017-1301-9
Tan H, Xie XY, Li JH, Zhong YP, Fu Q (2004) Synthesis and surface mobility of segmented polyurethanes with fluorinated side chains attached to hard blocks. Polymer 45:1495–1502. https://doi.org/10.1016/j.polymer.2003.12.068
Tan JQ, Liu WQ, Wang ZF (2017) Preparation and performance of waterborne UV-curable polyurethane containing long fluorinated side chains. J Appl Polym Sci 134:44506. https://doi.org/10.1002/app.44506
Tewes F, Krafft MP, Boury F (2011) Dynamical and rheological properties of fluorinated surfactant films adsorbed at the pressurized CO2-H2O Interface. Langmuir 27:8144–8152. https://doi.org/10.1021/la201009z
Tien YI, Wei KH (2001) Hydrogen bonding and mechanical properties in segmented montmorillonite/polyurethane nanocomposites of different hard segment ratios. Polymer 42:3213–3321. https://doi.org/10.1016/S0032-3861(00)00729-1
Tsujii K, Yamamoto T, Onda T, Shibuichi S (1997) Super oil-repellent surfaces. Angew Chem Int Ed 36:1011–1012. https://doi.org/10.1002/anie.199710111
Wang LF (2005) Effect of soft segment length on the thermal behaviors of fluorinated polyurethanes. Eur Polymer J 41:293–301. https://doi.org/10.1016/j.eurpolymj.2004.09.017
Wang CB, Cooper SL (1983) Morphology and properties of segmented polyether polyurethaneureas. Macromolecules 16(5):775–786. https://doi.org/10.1021/ma00239a014
Wang LF, Wei YH (2005) Effect of soft segment length on properties of fluorinated polyurethanes. Colloids Surf B 41:249–255. https://doi.org/10.1016/j.colsurfb.2004.12.014
Wang Y, Qiu F, Xu B, Xu J, Jiang Y, Yang D (2013) Preparation, mechanical properties and surface morphologies of waterborne fluorinated polyurethane-acrylate. Prog Org Coat 76:876–883. https://doi.org/10.1016/j.porgcoat.2013.02.003
Wang X, Hu JJ, Li Y, Zhang JR, Ding YY (2015) The surface properties and corrosion resistance of fluorinated polyurethane coatings. J Fluorine Chem 176:14–19. https://doi.org/10.1016/j.jfluchem.2015.04.002
Xu W, Lu B, Hu Y, Song L, Nie S (2012) Synthesis and characterization of novel fluorinated polyurethane elastomers based on 2,2-bis[4-(4-amino-2- trifluoromehyloxyphenyl)phenyl]propane. Polym Adv Technol 23:877–883. https://doi.org/10.1002/pat.1983
Yang CP, Chen YC (2005) Organosoluble and light-colored fluorinated polyimides based on 1,1-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]-1- phenylethane and various aromatic dianhydrides. J Appl Polym Sci 96:2399–2412. https://doi.org/10.1002/app.21702
Yoon SC, Ratner BD (1986) Surface structure of segmented poly(ether urethanes) and poly(ether urethane ureas) with various perfluoro chain extenders. An X-ray photoelectron spectroscopic investigation. Macromolecules 19:1068–1079. https://doi.org/10.1021/ma00158a023.
Yoon SC, Ratner BD (1988a) Surface and bulk structure of segmented poly(ether urethanes) with perfluoro chain extenders. 2. FTIR, DSC, and x-ray photoelectron spectroscopic studies. Macromolecules 21:2392–2400. https://doi.org/10.1021/ma00186a016.
Yoon SC, Ratner BD (1988b) Surface and bulk structure of segmented poly(ether urethanes) with perfluoro chain extenders. 3. Effects of annealing, casting solvent, and casting conditions. Macromolecules 21:2401–2404. https://doi.org/10.1021/ma00186a017.
Zhao X, Ding J, Ye L (2014) Structure and solvent-resistant property of fluorinated polyurethane elastomer. J Fluorine Chem 159:38–47. https://doi.org/10.1016/j.jfluchem.2013.12.012
Zhao M, Li H, Wen L, Yu Z, Zhang S, Han Z (2016) Synthesis and characterization of fluorine-containing polyurethane-acrylate core-shell emulsion. J Appl Polym Sci 133:43357. https://doi.org/10.1002/app.43357
Zhou GG, Chen JG, Wang MX, Zhang M, Guo JL, Shen SK (2015) Insight into the role of intermolecular interactions on the enhanced solubility of fluorinated epoxide oligomers in supercritical CO2. Green Chem 17:4489–4498. https://doi.org/10.1039/C5GC01069A
Zhu MJ, Qing FL, Meng WD (2008) Novel waterborne polyurethanes containing short fluoroalkyl chains: synthesis and applications on cotton fabrics. J Appl Polym Sci 109:1911–1915. https://doi.org/10.1002/app.27929
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Shi, X., Shi, HX., Wu, HK. et al. A novel fluorinated diamine as an extender for polyurethanes. Chem. Pap. 72, 1525–1534 (2018). https://doi.org/10.1007/s11696-018-0403-0
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DOI: https://doi.org/10.1007/s11696-018-0403-0