Tunable Structure and Properties of Segmented Thermoplastic Polyurethanes as a Function of Flexible Segment

Polymers - Tập 11 Số 12 - Trang 1910
M. C. Asensio1, V. Da Costa2, Andrés Nohales2, Otávio Bianchi3, Clara M. Gómez1
1Institute of Materials Science, University of Valencia, 46980 Paterna, Valencia, Spain
2R&D Department UBE CORPORATION EUROPE, S.A., 12100 Castellon, Spain
3Chemical Engineering Department, University of Caxias do Sul, Caxias do Sul 95070560, Brazil

Tóm tắt

Segmented thermoplastic polyurethanes (PUs) were synthetized using macrodiols with different functional groups (carbonate, ester, and /or ether) as a segment with a molar mass of 1000 and 2000 g/mol, and 4,4’-diphenylmethane diisocyanate (MDI) and 1,4-butanediol as a rigid segment. The polyurethanes obtained reveal a wide variation of microphase separation degree that is correlated with mechanical properties and retention of tensile properties under degradation by heat, oil, weather, and water. Different techniques such as differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), Fourier transform infrared (FTIR), and synchrotron small-angle X-ray scattering (SAXS) were used to determine rigid-flexible segments’ phase behaviour. Retention of tensile properties determines the stability of the samples under different external factors. This work reveals that pure polycarbonate-based macrodiols induce the highest degree of phase miscibility, better tensile properties, hardness shore A, and retention of tensile properties under external agents.

Từ khóa


Tài liệu tham khảo

Brains, P.F. (1969). Polyurethanes Technology, John Wiley and Sons.

Hepburn, C. (1991). Polyurethane Elastomers, Elsevier Applied Science. [2nd ed.].

Wirpsza, Z. (1993). Polyurethane: Chemistry, Technology and Applications, Ellis Horwood.

Chattopadhyay, 2007, Structural engineering of polyurethane coatings for high performance applications, Prog. Polym. Sci., 32, 352, 10.1016/j.progpolymsci.2006.05.003

2007, Synthesis methods, chemical structures and phase structures of linear polyurethanes. Properties and applications of linear polyurethanes in polyurethane elastomers, copolymers and ionomers, Prog. Mater. Sci., 52, 915, 10.1016/j.pmatsci.2006.11.001

Puska, A. (2018). Thermal and mechanical behavior of new transparent thermoplastic polyurethane elastomers derived from cycloaliphatic diisocyanate. Polymers, 16.

Smulders, 2009, Supramolecular Polymerization, Chem. Rev., 109, 5687, 10.1021/cr900181u

Strawhecker, 2013, Influence of microstructure on micro-/nano-mechanical measurements of select model transparent poly(urethane urea) elastomers, Polymer, 54, 901, 10.1016/j.polymer.2012.12.018

Lee, 2007, Preparation and properties of transparent thermoplastic segmented polyurethanes derived from different polyols, Polym. Eng. Sci., 47, 695, 10.1002/pen.20742

Hodan, 2017, The effect of pre-set extension on the degree of hydrolytic degradation in multicomponent polyurethane elastomers, Polym. Degrad. Stab., 142, 69, 10.1016/j.polymdegradstab.2017.05.033

Kojio, 2004, Effect of the composition ratio of copolymerized poly(carbonate) glycol on the microphase-separated structures and mechanical properties of polyurethane elastomers, J. Polym. Sci. Part B Polym. Phys., 42, 4448, 10.1002/polb.20303

Wiggins, 2004, Effect of soft-segment chemistry on polyurethane biostability during in vitro fatigue loading, J. Biomed. Mater. Res., 68, 668, 10.1002/jbm.a.20081

Khan, 2005, Analysis and evaluation of a biomedical polycarbonate urethane tested in a vitro study and an ovine arthroplasty model Part I: Materials selection and evaluation, Biomaterials, 26, 621, 10.1016/j.biomaterials.2004.02.065

Geary, 2008, Characterization of Biomate polycarbonate polyurethanes for orthopaedic applications, J. Mater. Sci. Mater. Med., 19, 3355, 10.1007/s10856-008-3472-8

Gopalakrishnan, 2011, Studies on ageing performance of some novel polyurethanes, J. Chem. Pharm. Res., 3, 848

Costa, 2012, Enhanced polyurethanes based on different polycarbonatediols, J. Elastomers Plast., 45, 217, 10.1177/0095244312452274

Costa, 2015, Structure–property relationships of polycarbonate diol-based polyurethanes as a function of soft segment content and molar mass, J. Appl. Polym. Sci., 132, 41704, 10.1002/app.41704

Martins, 2015, Effects of POSS addition on Non-isothermal crystallization and morphology of PVDF, J. Polym. Res., 22, 224, 10.1007/s10965-015-0871-7

Albrecht, 1996, Observation of the Early Stages of Crystallization in Polyethylene by Time-Dependent SAXS:  Transition from Individual Crystals to Stacks of Lamellae, Macromolecules, 29, 783, 10.1021/ma9503524

Denchev, 2000, On the origin of the multiple melting behavior in poly(ethylene naphthalene-2,6-dicarboxylate): Microstructural study as revealed by differential scanning calorimetry and X-ray scattering, J. Polym. Sci. Part B Polym. Phys., 38, 1167, 10.1002/(SICI)1099-0488(20000501)38:9<1167::AID-POLB8>3.0.CO;2-8

Sun, 2006, Temperature-resolved SAXS studies of morphological changes in melt-crystallized poly(hexamethylene terephthalate) and its melting upon heating, Polymer, 47, 8032, 10.1016/j.polymer.2006.09.003

Carli, 2013, Morphological and structural characterization of PHBV/organoclay nanocomposites by small angle X-ray scattering, Mater. Sci. Eng. C., 33, 932, 10.1016/j.msec.2012.11.023

Musselman, 1999, Domain structure and interphase dimensions in poly(urethaneurea) elastomers using DSC and SAXS, J. Polym. Sci. Part B Polym. Phys., 37, 2586, 10.1002/(SICI)1099-0488(19990915)37:18<2586::AID-POLB4>3.0.CO;2-A

Koberstein, 1992, Compression-molded polyurethane block copolymers. 2.Evaluation of microphase compositions, Macromolecules, 25, 6205, 10.1021/ma00049a018

Koberstein, 1983, Small-angle x-ray scattering measurements of diffuse phase-boundary thicknesses in segmented polyurethane elastomers, J. Polym. Sci., 21, 2181

Eceiza, 2008, Thermoplastic polyurethane elastomers based on polycarbonate diols withdifferent soft segment molecular weight and chemical structure: mechanical and thermal properties, Polym. Eng. Sci., 48, 297, 10.1002/pen.20905

Chen, 2007, Synthesis and properties of transparent thermoplastic segmented polyurethanes, Adv. Polym. Technol., 26, 33, 10.1002/adv.20086

Small, 1953, Some factors affecting the solubility of polymers, J. Appl. Chem., 3, 71, 10.1002/jctb.5010030205

Wang, 1983, Morphology and properties of segmented polyether polyurethaneureas, Macromolecules, 16, 775, 10.1021/ma00239a014

Chang, 1982, Morphological study of the structure developed during the polymerization of a series of segmented polyurethanes, Polymer, 23, 1060, 10.1016/0032-3861(82)90409-8

Leung, 1986, DSC annealing study of microphase separation and multiple endothermic behavior in polyether-based polyurethane block copolymers, Macromolecules, 19, 706, 10.1021/ma00157a038

Hu, 1994, The effect of thermal annealing on the thermal properties and molecular weight of a segmented polyurethane copolymer, Polym. Sci. Polym. Phys., 32, 437, 10.1002/polb.1994.090320304

Chen, 1997, Glass transition behaviors of a polyurethane hard segment based on 4,4’-diisocyanatodiphenylmethane and 1,4-butanediol and the calculation of microdomain composition, Macromolecules, 30, 5068, 10.1021/ma9618639

Korley, 2006, Effect of the degree of soft and hard segment ordering on the morphology and mechanical behaviour of semicrystalline segmented polyurethanes, Polymer, 47, 3073, 10.1016/j.polymer.2006.02.093

Tanaka, 2002, Mechanical properties of thermoplastic polyurethanes containing aliphatic polycarbonate soft segments with different chemical structures, Polym. Eng. Sci., 42, 1333, 10.1002/pen.11035

Alves, 2009, Surface modification and characterization of thermoplastic polyurethane, Eur. Polym. J., 45, 1412, 10.1016/j.eurpolymj.2009.02.011

Lin, 2007, Effect of soft segment length on properties of hydrophilic/hydrophobic polyurethanes, Polym. Int., 56, 1415, 10.1002/pi.2291

Harris, 1990, Polyurethane elastomers based on molecular weight advanced poly(ethylene ether carbonate) diols. I. Comparison to commercial diols, J. Appl. Polym. Sci., 41, 487, 10.1002/app.1990.070410304

Son, 1999, Thermal and phase behavior of polyurethane based on chain extender 2,2-bis-[4-(2-hydroxyethoxy) phenyl]propane, Polym. J., 31, 563, 10.1295/polymj.31.563

Barikani, 1996, Thermoplastic polyurethane elastomers: Synthesis and study of effective structural parameters, Iran. Polym. J., 5, 231

Kim, 1999, Preparation and properties of segmented thermoplastic polyurethane elastomers with two different soft segments, J. Appl. Polym. Sci., 73, 345, 10.1002/(SICI)1097-4628(19990718)73:3<345::AID-APP5>3.0.CO;2-T

Zhang, 2008, Synthesis, characterization and mechanical properties of polyester-based aliphatic polyurethane elastomers containing hyperbranched polyester segments, Eur. Polym. J., 44, 3708, 10.1016/j.eurpolymj.2008.08.019

Pan, 2009, Alternative block polyurethanes based on poly(3-hydroxybutyrate-co-4-hydroxybutyrate) and poly(ethylene glycol), Biomaterials, 30, 2975, 10.1016/j.biomaterials.2009.02.005

Velayutham, 2009, Synthesis and characterization of polyurethane coatings derived from polyols synthesized with glycerol, phthalic anhydride and oleic acid, Prog. Org. Coat., 66, 367, 10.1016/j.porgcoat.2009.08.013

Zhao, 2005, Synthesis and characterization of biodegradable poly(3-hydroxybutyrate) and poly(ethylene glycol) multiblock copolymers, Polymer, 46, 10561, 10.1016/j.polymer.2005.08.014

Spirkova, 2011, Novel polycarbonate-based polyurethane elastomers: Composition–property relationship, Eur. Polym. J., 47, 959, 10.1016/j.eurpolymj.2011.01.001

Rueda, 2008, Microdomain composition and properties differences of biodegradable polyurethanes based on MDI and HDI, Polym. Eng. Sci., 48, 519, 10.1002/pen.20983

Sung, 1975, Infrared studies of hydrogen bonding in toluene diisocyanate based polyurethanes, Macromolecules, 8, 68, 10.1021/ma60043a015

Javni, 2015, Thermoplastic polyurethanes with controlled morphology based on methylenediphenyldiisocyanate/isosorbide/butanediol hard segments, Polym. Int., 64, 1607, 10.1002/pi.4960

Choi, 2011, Segmented polyurethanes derived from novel siloxane–carbonate soft segments for biomedical applications, J. Polym. Sci. Part B Polym. Phys., 49, 865, 10.1002/polb.22260

Leung, 1985, Small-angle scattering analysis of hard-microdomain structure and microphase mixing in polyurethane elastomers, J. Polym. Sci. Polym. Phys. Ed., 23, 1883, 10.1002/pol.1985.180230912

Martin, 1996, Effect of soft-segment CH2/O ratio on morphology and properties of a series of polyurethane elastomers, J. Appl. Polym. Sci., 60, 557, 10.1002/(SICI)1097-4628(19960425)60:4<557::AID-APP9>3.0.CO;2-N

Kultys, 2012, New thermoplastic segmented polyurethanes with hard segments derived from 4,4′-diphenylmethane diisocyanate and methylenebis(1,4-phenylenemethylenethio) dialcanols, J. Appl. Polym. Sci., 123, 331, 10.1002/app.34102

Gunatillake, 1992, Polyurethane elastomers based on novel polyether macrodiols and MDI: Synthesis, mechanical properties and resistance to hydrolysis and oxidation, J. Appl. Polym. Sci., 46, 319, 10.1002/app.1992.070460213

Harris, 1992, Polyurethane elastomers based on molecular weight advanced poly(ethylene ether carbonate) polyols. IV. Effects of poly(propylene glycol) modified diols, J. Appl. Polym. Sci., 46, 1843, 10.1002/app.1992.070461016

Bajsic, 2003, Thermal degradation of polyurethane elastomers: Determination of kinetic parameters, J. Elast. Plast., 35, 311, 10.1177/009524403034393

Clemitson, I.R. (2008). Castable Polyurethane Elastomers, CRC Press Taylor & Francis Group.