Tuning Thermal, Morphological, and Physicochemical Properties of Thermoplastic Polyurethanes (TPUs) by the 1,4-Butanediol (BDO)/Dipropylene Glycol (DPG) Ratio.
Ernzen, Juliano R; Romoaldo, Carlos H; Gommes, Cédricet al.
[en] Thermoplastic polyurethanes (TPUs) are versatile polymers presenting a broad range of properties as a result of their countless combination of raw materials-in essence, isocyanates, polyols, and chain extenders. This study highlights the effect of two different chain extenders and their combination on the structure-property relationships of TPUs synthesized by reactive extrusion. The TPUs were obtained from 4,4-diphenylmethane diisocyanate (MDI), polyester diols, and the chain extenders 1,4-butanediol (BDO) and dipropylene glycol (DPG). The BDO/DPG ratios studied were 100/0, 75/25, 50/50, 25/75, and 0/100 wt.%. The TPUs were characterized by size exclusion chromatography (SEC), Fourier-transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS), UV-vis spectroscopy, and physical-mechanical properties. The results indicate that DPG promotes compatibility between rigid (HS) and flexible (SS) segments of TPUs. Consequently, increasing DPG content (>75 wt.%) reduced the organization of the rigid segments and the degree of phase separation, increasing the polydispersity of the interdomain distance and the transparency in the UV-visible spectrum of the TPUs. Furthermore, increasing DPG content also reduced the amount of hydrogen bonds present in the rigid phase, reducing or extinguishing its glass transition temperature (TgHS) and melting temperature (Tm), and increasing the glass transition temperature of the flexible phase (TgSS). Therefore, increasing DPG content leads to a deterioration in mechanical properties and hydrolysis resistance.
Disciplines :
Chemistry Materials science & engineering
Author, co-author :
Ernzen, Juliano R; Mantoflex Poliuretanos, Caxias do Sul 95045175, Brazil ; Chemical Engineering Department, University of Caxias do Sul, Caxias do Sul 95070560, Brazil
Romoaldo, Carlos H ; Chemical Engineering Department, University of Caxias do Sul, Caxias do Sul 95070560, Brazil
Gommes, Cédric ; Université de Liège - ULiège > Department of Chemical Engineering
Covas, José A ; Institute for Polymers and Composites (IPC), University of Minho, Campus de Azurém, 4800-058 Guimarães, Portugal
Marcos-Fernández, Angel ; Elastomers Group, Institute of Polymer Science and Technology (ICTP-CSIC), Juan de la Cierva, 3, 28006 Madrid, Spain
Fiorio, Rudinei ; Faculty of Science and Engineering, Maastricht University, 6200 MD Geleen, The Netherlands
Bianchi, Otávio ; Chemical Engineering Department, University of Caxias do Sul, Caxias do Sul 95070560, Brazil ; Department of Materials Engineering (DEMAT), Federal University of Rio Grande do Sul (UFRGS), Porto Alegre 90040040, Brazil
Language :
English
Title :
Tuning Thermal, Morphological, and Physicochemical Properties of Thermoplastic Polyurethanes (TPUs) by the 1,4-Butanediol (BDO)/Dipropylene Glycol (DPG) Ratio.
CNPq - National Council for Scientific and Technological Development [BR] MINECO - Spanish Government. Ministry of Economy, Industry and Competitiveness [ES]
Funding text :
The authors thank the Brazilian agency Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) for their financial support. OB thanks the National Council for Scientific and Technological Development (CNPq) fellows (grant number 308567/2018-8 and 305814/2021-4). AMF thanks the Spanish Ministerio de Economía e Innovación (project PID2020-119047RB-I00) for partial financial support. The authors also acknowledge the Brazilian Synchrotron Light Laboratory (LNLS) for the use of its facilities (SAXS1 beamline).This research was funded by Brazilian National Council for Scientific and Technological Development (CNPq) grant numbers 308567/2018-8 and 305814/2021-4. Spanish Ministerio de Economía e Innovación grant numbers PID2020-119047RB-I00 funded the APC.
Oertel G.A. Polyurethane Handbook: Chemistry, Raw Materials, Processing, Application, Properties Hanser Publishers New York, NY, USA 1985
Ionescu M. Chemistry and Technology of Polyols for Polyurethanes iSmithers Rapra Publishing Shrewsbury, UK 2005
Lee D.K. Tsai H.B. Tsai R.S. Chen P.H. Preparation and properties of transparent thermoplastic segmented polyurethanes derived from different polyols Polym. Eng. Sci. 2007 47 695 701 10.1002/pen.20742
Gomez C.M. Gutierrez D. Asensio M. Costa V. Nohales A. Transparent thermoplastic polyurethanes based on aliphatic diisocyanates and polycarbonate diol J. Elastomers Plast. 2017 49 77 95 10.1177/0095244316639633
Sonnenschein M.F. Rondan N. Wendt B.L. Cox J.M. Synthesis of transparent thermoplastic polyurethane elastomers J. Polym. Sci. Part A Polym. Chem. 2004 42 271 278 10.1002/pola.11017
Chen R. Zhang X. Wang P. Xie K. Jian J. Zhang Y. Zhang J. Yuan Y. Na P. Yi M. Transparent thermoplastic polyurethane air filters for efficient electrostatic capture of particulate matter pollutants Nanotechnology 2018 30 015703 10.1088/1361-6528/aae611
Chen P.H. Yang Y.F. Lee D.K. Lin Y.F. Wang H.H. Tsai H.B. Tsai R.S. Synthesis and properties of transparent thermoplastic segmented polyurethanes Adv. Polym.Technol. J. Polym. Process. Inst. 2007 26 33 40 10.1002/adv.20086
Xiang C. Chen H. Wang W. Dai Q. Liu Z. Yang B. Zhou Y. Zhou Y. Transparency-tunable and moderate-temperature healable thermoplastic polyurethane elastomer based on bisphenol A chain-extender J. Appl. Polym. Sci. 2021 138 49794 49804 10.1002/app.49794
Zhang J. Tu W. Dai Z. Transparent polyester polyol-based polyurethane coatings: The effect of alcohols J. Coat. Technol. Res. 2013 10 887 895 10.1007/s11998-013-9527-x
Puszka A. Kultys A. New thermoplastic polyurethane elastomers based on aliphatic diisocyanate J. Therm. Anal. Calorim. 2017 128 407 416 10.1007/s10973-016-5923-7
Li W. Ryan A.J. Meier I.K. Effect of chain extenders on the morphology development in flexible polyurethane foam Macromolecules 2002 35 6306 6312 10.1021/ma020231l
Wang X. Zhang H. Yang B. Wang L. Sun H. A colorless, transparent and self-healing polyurethane elastomer modulated by dynamic disulfide and hydrogen bonds New J. Chem. 2020 44 5746 5754 10.1039/C9NJ06457E
Bai J. Ren W. Wang Y. Li X. Zhang C. Li Z. Xie Z. High-performance thermoplastic polyurethane elastomer/carbon dots bulk nanocomposites with strong luminescence High Perform. Polym. 2020 32 857 867 10.1177/0954008320907123
Tyl R.W. Myers C.B. Marr M.C. Thomas B.F. Keimowitz A.R. Brine D.R. Veselica M.M. Fail P.A. Chang T.Y. Seely J.C. et al. Three-Generation Reproductive Toxicity Study of Dietary Bisphenol A in CD Sprague-Dawley Rats Toxicol. Sci. 2002 68 121 146 10.1093/toxsci/68.1.121 12075117
Tarafdar A. Sirohi R. Balakumaran P.A. Reshmy R. Madhavan A. Sindhu R. Binod P. Kumar Y. Kumar D. Sim S.J. The hazardous threat of Bisphenol A: Toxicity, detection and remediation J. Hazard. Mater. 2022 423 127097 10.1016/j.jhazmat.2021.127097 34488101
Parmar P.K. Wadhawan J. Bansal A.K. Pharmaceutical nanocrystals: A promising approach for improved topical drug delivery Drug Discov. Today 2021 26 2329 2349 10.1016/j.drudis.2021.07.010
Amin K.N.M. Amiralian N. Annamalai P.K. Edwards G. Chaleat C. Martin D.J. Scalable processing of thermoplastic polyurethane nanocomposites toughened with nanocellulose Chem. Eng. J. 2016 302 406 416 10.1016/j.cej.2016.05.067
Niemczyk A. Piegat A. Olalla Á.S. El Fray M. New approach to evaluate microphase separation in segmented polyurethanes containing carbonate macrodiol Eur. Polym. J. 2017 93 182 191 10.1016/j.eurpolymj.2017.05.046
Favero D. Marcon V. Figueroa C.A. Gómez C.M. Cros A. Garro N. Sanchis M.J. Carsí M. Bianchi O. Effect of chain extender on the morphology, thermal, viscoelastic, and dielectric behavior of soybean polyurethane J. Appl. Polym. Sci. 2021 138 50709 50725 10.1002/app.50709
Coleman M.M. Skrovanek D.J. Hu J. Painter P.C. Hydrogen bonding in polymer blends. 1. FTIR studies of urethane-ether blends Macromolecules 1988 21 59 65 10.1021/ma00179a014
Yilgör I. Yilgör E. Wilkes G.L. Critical parameters in designing segmented polyurethanes and their effect on morphology and properties: A comprehensive review Polymer 2015 58 A1 A36 10.1016/j.polymer.2014.12.014
Rogulska M. Polycarbonate-based thermoplastic polyurethane elastomers modified by DMPA Polym. Bull. 2019 76 4719 4733 10.1007/s00289-018-2632-3
Sung C.S.P. Schneider N. Infrared studies of hydrogen bonding in toluene diisocyanate based polyurethanes Macromolecules 1975 8 68 73 10.1021/ma60043a015
Meaurio E. Sanchez-Rexach E. Zuza E. Lejardi A. del Pilar Sanchez-Camargo A. Sarasua J.-R. Predicting miscibility in polymer blends using the Bagley plot: Blends with poly (ethylene oxide) Polymer 2017 113 295 309 10.1016/j.polymer.2017.01.041
Bianchi O. Ornaghi H.L. Jr. Martins J.N. Dal Castel C. Bresciani Canto L. A survey of the rheological properties, phase morphology, and crystallization behavior of PP-POSS materials with weak phase separation Polym. Eng. Sci. 2020 60 2272 2284 10.1002/pen.25469
Van Krevelen D.W. Te Nijenhuis K. Properties of Polymers: Their Correlation with Chemical Structure Their Numerical Estimation and Prediction from Additive Group Contributions Elsevier Amsterdam, The Netherlands 2009
Gallu R. Méchin F. Dalmas F. Gérard J.-F. Perrin R. Loup F. On the use of solubility parameters to investigate phase separation-morphology-mechanical behavior relationships of TPU Polymer 2020 207 122882 10.1016/j.polymer.2020.122882
Yılgör E. Yılgör I. Yurtsever E. Hydrogen bonding and polyurethane morphology. I. Quantum mechanical calculations of hydrogen bond energies and vibrational spectroscopy of model compounds Polymer 2002 43 6551 6559 10.1016/S0032-3861(02)00567-0
Garrett J. Runt J. Lin J. Microphase separation of segmented poly (urethane urea) block copolymers Macromolecules 2000 33 6353 6359 10.1021/ma000600i
Asensio M. Costa V. Nohales A. Bianchi O. Gómez C.M. Tunable structure and properties of segmented thermoplastic polyurethanes as a function of flexible segment Polymers 2019 11 1910 10.3390/polym11121910 31756912
Eceiza A. Martin M. De La Caba K. Kortaberria G. Gabilondo N. Corcuera M. Mondragon I. Thermoplastic polyurethane elastomers based on polycarbonate diols with different soft segment molecular weight and chemical structure: Mechanical and thermal properties Polym. Eng. Sci. 2008 48 297 306 10.1002/pen.20905
Hesketh T. Van Bogart J. Cooper S.L. Differential scanning calorimetry analysis of morphological changes in segmented elastomers Polym. Eng. Sci. 1980 20 190 197 10.1002/pen.760200304
Finnigan B. Halley P. Jack K. McDowell A. Truss R. Casey P. Knott R. Martin D. Effect of the average soft-segment length on the morphology and properties of segmented polyurethane nanocomposites J. Appl. Polym. Sci. 2006 102 128 139 10.1002/app.23347
Musselman S. Santosusso T. Barnes J. Sperling L. Domain structure and interphase dimensions in poly (urethaneurea) elastomers using DSC and SAXS J. Polym. Sci. Part B Polym. Phys. 1999 37 2586 2600 10.1002/(SICI)1099-0488(19990915)37:18<2586::AID-POLB4>3.0.CO;2-A
Camberlin Y. Pascault J.P. Quantitative DSC evaluation of phase segregation rate in linear segmented polyurethanes and polyurethaneureas J. Polym.Sci. Polym. Chem. Ed. 1983 21 415 423 10.1002/pol.1983.170210211
Behera P.K. Usha K. Guchhait P. Jehnichen D. Das A. Voit B. Singha N.K. A novel ionomeric polyurethane elastomer based on ionic liquid as crosslinker RSC Adv. 2016 6 99404 99413 10.1039/C6RA21650A
Aurilia M. Piscitelli F. Sorrentino L. Lavorgna M. Iannace S. Detailed analysis of dynamic mechanical properties of TPU nanocomposite: The role of the interfaces Eur. Polym. J. 2011 47 925 936 10.1016/j.eurpolymj.2011.01.005
Ernzen J.R. Bondan F. Luvison C. Henrique Wanke C. De Nardi Martins J. Fiorio R. Bianchi O. Structure and properties relationship of melt reacted polyamide 6/malenized soybean oil J. Appl. Polym. Sci. 2016 133 43050 43060 10.1002/app.43050
Paradinha M.M. Gonzalez Dias F.T. Wanke C.H. de Lima Novello J.C. Tondo E.C. De Nardi Martins J. Bianchi O. Preparation and characterization of the ethylene-vinyl acetate copolymer partially hydrolyzed assisted by microwave radiation J. Appl. Polym. Sci. 2017 134 44558 44567 10.1002/app.44558
Koberstein J. Morra B. Stein R. The determination of diffuse-boundary thicknesses of polymers by small-angle X-ray scattering J. Appl. Crystallogr. 1980 13 34 45 10.1107/S0021889880011478
D’Hollander S. Gommes C.J. Mens R. Adriaensens P. Goderis B. Du Prez F. Modeling the morphology and mechanical behavior of shape memory polyurethanes based on solid-state NMR and synchrotron SAXS/WAXD J. Mater. Chem. 2010 20 3475 3486 10.1039/b923734h
Zhang J. Tu W. Dai Z. Synthesis and characterization of transparent and high impact resistance polyurethane coatings based on polyester polyols and isocyanate trimers Prog. Org. Coat. 2012 75 579 583 10.1016/j.porgcoat.2012.05.005
Xie F. Zhang T. Bryant P. Kurusingal V. Colwell J.M. Laycock B. Degradation and stabilization of polyurethane elastomers Prog. Polym. Sci. 2019 90 211 268 10.1016/j.progpolymsci.2018.12.003
Chen S.-Y. Zhuang R.-Q. Chuang F.-S. Rwei S.-P. Synthetic scheme to increase the abrasion resistance of waterborne polyurethane–urea by controlling micro-phase separation J. Appl. Polym. Sci. 2021 138 50561 10.1002/app.50561
