Abstract
Polyurethane (PU) elastomers with their broad range of strength and elasticity are ideal materials for additive manufacturing of shapes with gradients of mechanical properties. By adjusting the mixing ratio of different polyurethane reactants during 3D-printing it is possible to change the mechanical properties. However, to guarantee intra- and inter-layer adhesion, it is essential to know the reaction kinetics of the polyurethane reaction, and to be able to influence the reaction speed in a wide range. In this study, the effect of adding three different catalysts and two inhibitors to the reaction of polyurethane elastomers were studied by comparing the time of crossover points between storage and loss modulus G′ and G′′ from time sweep tests of small amplitude oscillatory shear at 30°C. The time of crossover points is reduced with the increasing amount of catalysts, but only the reaction time with one inhibitor is significantly delayed. The reaction time of 90% NCO group conversion calculated from the FTIR-spectrum also demonstrates the kinetics of samples with different catalysts. In addition, the relation between the conversion as determined from FTIR spectroscopy and the mechanical properties of the materials was established. Based on these results, it is possible to select optimized catalysts and inhibitors for polyurethane 3D-printing of materials with gradients of mechanical properties.
References
[1] Ligon S.C., Liska R., Stampfl J., Gurr M. and Mülhaupt R., Polymers for 3d printing and customized additive manufacturing, Chem Rev, 2017, 117, 10212-10290.10.1021/acs.chemrev.7b00074Search in Google Scholar PubMed PubMed Central
[2] Elsner P., 3D-Drucktechnologie–Grundlagen zur Herstellung polymerer Bauteile mit gradierten Werkstoffeigenschaften, Dissertation, Technische Universität Berlin, Berlin, Germany, 2009.Search in Google Scholar
[3] Müller M., Huynh Q-U., Uhlmann E. and Wagner M.H., Study of inkjet printing as additive manufacturing process for gradient polyurethane material, Production Engineering, 2013, 8, 25-32.10.1007/s11740-013-0504-0Search in Google Scholar
[4] Uhlmann E., Wagner M.H. and Gerlitzky G., Additives Fertigungsverfahren zur Herstellung von Bauteilen mit Eigenschaftsgradienten, ZWF Zeitschrift für wirtschaftlichen Fabrikbetrieb, 2018, 113, 290-294.10.3139/104.111918Search in Google Scholar
[5] Uhlmann E., Wagner M.H. and Gerlitzky G., Additive Fertigung mittels 3D-Gradientendruck, Ingenieurspiegel, 2018, August.Search in Google Scholar
[6] Feng X., Yusheng S. and Shuhuai H., Synthesis and performance of transparent casting polyurethane resin, Journal of Wuhan University of Technology-Mater. Sci. Ed., 2005, 20, 24-28.10.1007/BF02838480Search in Google Scholar
[7] Chen X-D., Zhou N-Q. and Zhang H., Preparation and properties of cast polyurethane elastomers with molecularly uniform hard segments based on 2,4-toluene diisocyanate and 3,5-dimethylthioltoluenediamine, Journal of Biomedical Science and Engineering, 2009, 02, 245-253.10.4236/jbise.2009.24038Search in Google Scholar
[8] Lligadas G., Ronda J.C., Galià M., Biermann U. and Metzger J.O., Synthesis and characterization of polyurethanes from epoxidized methyl oleate based polyether polyols as renewable resources, Journal of Polymer Science Part A: Polymer Chemistry, 2006, 44, 634-645.10.1002/pola.21201Search in Google Scholar
[9] Krol P., Synthesis methods, chemical structures and phase structures of linear polyurethanes. Properties and applications of linear polyurethanes in polyurethane elastomers, copolymers and ionomers, Progress in Materials Science, 2007, 52, 915-1015.10.1016/j.pmatsci.2006.11.001Search in Google Scholar
[10] Fiori S., Mariani A., Ricco L. and Russo S., First synthesis of a polyurethane by frontal polymerization, Macromolecules, 2003, 36, 2674-2679.10.1021/ma0211941Search in Google Scholar
[11] Pattanayak A. and Jana S.C., Synthesis of thermoplastic polyurethane nanocomposites of reactive nanoclay by bulk polymerization methods, Polymer, 2005, 46, 3275-3288.10.1016/j.polymer.2005.02.081Search in Google Scholar
[12] Niyogi S., Sarkar S. and Adhikari B., Catalytic activity of dbtdl in polyurethane formation, Indian Journal of Chemical Technology, 2002, 9, 330-333.Search in Google Scholar
[13] Yang Y. and Urban M.W., Self-repairable polyurethane networks by atmospheric carbon dioxide and water, Angew Chem Int Ed Engl, 2014, 53, 12142-12147.10.1002/anie.201407978Search in Google Scholar PubMed
[14] Skrobot J., Zair L., Ostrowski M. and El Fray M., New injectable elastomeric biomaterials for hernia repair and their biocompatibility, Biomaterials, 2016, 75, 182-192.10.1016/j.biomaterials.2015.10.037Search in Google Scholar PubMed
[15] Mathew S., Baudis S., Neffe A.T., Behl M., Wischke C. and Lendlein A., Effect of diisocyanate linkers on the degradation characteristics of copolyester urethanes as potential drug carrier matrices, Eur J Pharm Biopharm, 2015, 95, 18-26.10.1016/j.ejpb.2015.03.025Search in Google Scholar PubMed
[16] Yeganeh H. and Mehdizadeh M.R., Synthesis and properties of isocyanate curable millable polyurethane elastomers based on castor oil as a renewable resource polyol, European Polymer Journal, 2004, 40, 1233-1238.10.1016/j.eurpolymj.2003.12.013Search in Google Scholar
[17] Krol B., Krol P., Pikus S., Chmielarz P. and Skrzypiec K., Synthesis and characterisation of coating polyurethane cationomers containing fluorine built-in hard urethane segments, Colloid Polym Sci, 2010, 288, 1255-1269.10.1007/s00396-010-2244-4Search in Google Scholar PubMed PubMed Central
[18] Braun D., Cherdron H., Rehahn M., Ritter H. and Voit B., Polymer synthesis: Theory and practice: Fundamentals, methods, experiments, Springer Science & Business Media, 2012.10.1007/978-3-642-28980-4Search in Google Scholar
[19] Sardon H., Pascual A., Mecerreyes D., Taton D., Cramail H. and Hedrick J.L., Synthesis of polyurethanes using organocatalysis: A perspective, Macromolecules, 2015, 48, 3153-3165.10.1021/acs.macromol.5b00384Search in Google Scholar
[20] Chambon F. and Winter H.H., Stopping of crosslinking reaction in a pdms polymer at the gel point, Polymer Bulletin, 1985,13, 499-503.10.1007/BF00263470Search in Google Scholar
[21] Winter H.H. and Chambon F., Analysis of linear viscoelasticity of a crosslinking polymer at the gel point, Journal of Rheology, 1986, 30, 367-382.10.1122/1.549853Search in Google Scholar
[22] Chambon F., Petrovic Z.S., MacKnight W.J. and Winter H.H., Rheology of model polyurethanes at the gel point, Macromolecules, 1986, 19, 2146-2149.10.1021/ma00162a007Search in Google Scholar
[23] Chambon F. and Winter H.H., Linear viscoelasticity at the gel point of a crosslinking pdms with imbalanced stoichiometry, Journal of Rheology, 1987, 31, 683-697.10.1122/1.549955Search in Google Scholar
[24] Winter H., Can the gel point of a cross-linking polymer be detected by the G′–G′′ crossover?, Polymer Engineering & Science, 1987, 27, 1698-1702.10.1002/pen.760272209Search in Google Scholar
[25] Winter H.H., Morganelli P. and Chambon F., Stoichiometry effects on rheology of model polyurethanes at the gel point, Macromolecules, 1988, 21, 532-535.10.1021/ma00180a048Search in Google Scholar
[26] Hu X., Fan J. and Yue C.Y., Rheological study of crosslinking and gelation in bismaleimide/cyanate ester interpenetrating polymer network, Journal of Applied Polymer Science, 2001, 80, 2437-2445.10.1002/app.1350Search in Google Scholar
[27] Ketata N., Sanglar C., Waton H., Alamercery S., Delolme F., Paisse O., Rafln G. and Grenier-Loustalot M-F., Synthesis, mechanisms and kinetics of formation of bi-component polyurethanes, Polymers and Polymer Composites, 2004, 12, 645-665.10.1177/096739110401200801Search in Google Scholar
[28] Kröber P., Delaney J.T., Perelaer J. and Schubert U.S., Reactive inkjet printing of polyurethanes, Journal of Materials Chemistry, 2009, 19, 5234.10.1039/b823135dSearch in Google Scholar
[29] Trovati G., Sanches E.A., Neto S.C., Mascarenhas Y.P. and Chierice G.O., Characterization of polyurethane resins by ftir, tga, and xrd, Journal of Applied Polymer Science, 2010, 115, 263-268.10.1002/app.31096Search in Google Scholar
[30] Gogoi R., Sarwar Alam M. and Khandal R.K., Effect of reaction time on the synthesis and properties of isocyanate terminated polyurethane prepolymer, Int. J. Eng. Res. Technol, 2014, 3, 1404-1411.10.14419/ijbas.v3i2.2416Search in Google Scholar
[31] Song X. and Yunjun L., Effect of hyperbranched polyesters on htpb polyurethane curing kinetic, Materials Research, 2014, 17, 78-82.10.1590/S1516-14392013005000193Search in Google Scholar
[32] Elwell M.J., Ryan A.J., Grünbauer H.J. and Van Lieshout H.C., An ftir study of reaction kinetics and structure development in model flexible polyurethane foam systems, Polymer, 1996, 37, 1353-1361.10.1016/0032-3861(96)81132-3Search in Google Scholar
© 2019 Peng Wang et al., published by De Gruyter
This work is licensed under the Creative Commons Attribution 4.0 Public License.
