A Well-defined Hierarchical Hydrogen Bonding Strategy to Polyureas with Simultaneously Improved Strength and Toughness

Ting Li; Tian-Ze Zheng; Zhao-Xia Guo; Jun Xu; Bao-Hua Guo

doi:10.1007/s10118-019-2275-3

Your Location：

Home >

Browse articles >

A Well-defined Hierarchical Hydrogen Bonding Strategy to Polyureas with Simultaneously Improved Strength and Toughness

ARTICLE | Updated：2021-02-18

- A Well-defined Hierarchical Hydrogen Bonding Strategy to Polyureas with Simultaneously Improved Strength and Toughness
- Chinese Journal of Polymer Science Vol. 37, Issue 12, Pages: 1257-1266(2019)
- Affiliations：
  
  Key Laboratory of Advanced Materials (Ministry of Education), Department of Chemical Engineering, Tsinghua University, Beijing 100084, China
- Author bio：
  
  jun-xu@mail.tsinghua.edu.cn (J.X.)
  bhguo@mail.tsinghua.edu.cn (B.H.G.)
- Funds：
- DOI：10.1007/s10118-019-2275-3
  CLC：
- Received：16 March 2019，
  
  Revised：2019-4-11，
  
  Accepted：15 April 2019，
  
  Online First：13 June 2019，
  
  Published：2019-12
- Accepted：
Scan QR Code
Li, T.; Zheng, T. Z.; Guo, Z. X.; Xu, J.; Guo, B. H. A well-defined hierarchical hydrogen bonding strategy to polyureas with simultaneously improved strength and toughness. Chinese J. Polym. Sci. 2019, 37, 1257–1266.

Ting Li, Tian-Ze Zheng, Zhao-Xia Guo, et al. A Well-defined Hierarchical Hydrogen Bonding Strategy to Polyureas with Simultaneously Improved Strength and Toughness[J]. Chinese Journal of Polymer Science, 2019, 37(12): 1257-1266.
Li, T.; Zheng, T. Z.; Guo, Z. X.; Xu, J.; Guo, B. H. A well-defined hierarchical hydrogen bonding strategy to polyureas with simultaneously improved strength and toughness. Chinese J. Polym. Sci. 2019, 37, 1257–1266. DOI： 10.1007/s10118-019-2275-3.

Ting Li, Tian-Ze Zheng, Zhao-Xia Guo, et al. A Well-defined Hierarchical Hydrogen Bonding Strategy to Polyureas with Simultaneously Improved Strength and Toughness[J]. Chinese Journal of Polymer Science, 2019, 37(12): 1257-1266. DOI： 10.1007/s10118-019-2275-3.

摘要

Abstract

A well-defined quadruple hydrogen bonding strategy involving dimerization of 2-ureido-4[1

]-pyrimidone (UPy) units is innovatively designed to prepare polyureas with high overall mechanical properties. Three polyureas containing different amounts of UPy units were synthesized by replacing a portion of isophorone diisocyanate (IPDI) with a UPy-derived diisocyanate. The formation of quadruple hydrogen bonds in hard segments

via

UPy dimers was confirmed by nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscopy (FTIR). The mechanical properties of the polyureas were evaluated by uniaxial tensile testing. Compared to the polyurea without UPy units

remarkable improvements in Young’s modulus

tensile strength

and toughness were simultaneously achieved when UPy units were incorporated. The mechanism behind the strong strengthening effect rooted in the stronger intermolecular forces among hard segments brought by the quadruple hydrogen bonds

which were stronger than the inherent bidentate and monodentate hydrogen bonds among urea groups

and the slower soft segmental dynamics reaveled by both increased

and relaxation time of the soft segments. The mechanism behind the strong toughening effect was ascribed to more effective energy dissipation brought by the quadruple hydrogen bonds that served as stronger sacrificial bonds upon deformation. This work may offer new insight into the design of polyurea elastomers with comprehensively improved mechanical properties.

关键词

Keywords

references

Roland, C. M.; Twigg, J. N.; Vu, Y.; Mott, P. H . High strain rate mechanical behavior of polyurea . Polymer , 2007 . 48 574 - 578 . DOI: 10.1016/j.polymer.2006.11.051 http://doi.org/10.1016/j.polymer.2006.11.051 .

Sarva, S . Stress-strain behavior of a polyurea and a polyurethane from low to high strain rates . Polymer , 2007 . 48 2208 - 2213 . DOI: 10.1016/j.polymer.2007.02.058 http://doi.org/10.1016/j.polymer.2007.02.058 .

Yi, J . Large deformation rate-dependent stress-strain behavior of polyurea and polyurethanes . Polymer , 2006 . 47 319 - 329 . DOI: 10.1016/j.polymer.2005.10.107 http://doi.org/10.1016/j.polymer.2005.10.107 .

Choi, T.; Fragiadakis, D.; Roland, C. M.; Runt, J . Microstructure and segmental dynamics of polyurea under uniaxial deformation . Macromolecules , 2012 . 45 3581 - 3589 . DOI: 10.1021/ma300128d http://doi.org/10.1021/ma300128d .

Li, T.; Xie, Z.; Xu, J.; Weng, Y.; Guo, B. H . Design of a self-healing cross-linked polyurea with dynamic cross-links based on disulfide bonds and hydrogen bonding . Eur. Polym. J. , 2018 . 107 249 - 257 . DOI: 10.1016/j.eurpolymj.2018.08.005 http://doi.org/10.1016/j.eurpolymj.2018.08.005 .

Rinaldi, R. G.; Boyce, M. C.; Weigand, S. J.; Londono, D. J.; Guise, M. W . Microstructure evolution during tensile loading histories of a polyurea . J. Polym. Sci., Part B: Polym. Phys. , 2011 . 49 1660 - 1671 . DOI: 10.1002/polb.v49.23 http://doi.org/10.1002/polb.v49.23 .

Castagna, A. M.; Pangon, A.; Dillon, G. P.; Runt, J . Effect of thermal history on the microstructure of a poly(tetramethylene oxide)-based polyurea . Macromolecules , 2013 . 46 6520 - 6527 . DOI: 10.1021/ma400856w http://doi.org/10.1021/ma400856w .

Chao, L.; Ma, C.; Xie, Q.; Zhang, G . Self-repairing silicone coating for marine anti-biofouling . J. Mater. Chem. A , 2017 . 5 15855 - 15861 . DOI: 10.1039/C7TA05241C http://doi.org/10.1039/C7TA05241C .

Engels, H. W.; Pirkl, H. G.; Albers, R.; Albach, R. W.; Krause, J.; Hoffmann, A.; Casselmann, H.; Dormish, J . Polyurethanes: Versatile materials and sustainable problem solvers for today’s challenges . Angew. Chem. Int. Ed. , 2013 . 52 9422 - 9441 . DOI: 10.1002/anie.v52.36 http://doi.org/10.1002/anie.v52.36 .

Fragiadakis, D.; Gamache, R.; Bogoslovov, R. B.; Roland, C. M . Segmental dynamics of polyurea: Effect of stoichiometry . Polymer , 2010 . 51 178 - 184 . DOI: 10.1016/j.polymer.2009.11.028 http://doi.org/10.1016/j.polymer.2009.11.028 .

Xuan, L.; Kuang, W.; Guo, B . Preparation of rubber/graphene oxide composites with in situ interfacial design . Polymer , 2015 . 56 553 - 562 . DOI: 10.1016/j.polymer.2014.11.048 http://doi.org/10.1016/j.polymer.2014.11.048 .

Qiao, H.; Wang, R.; Yao, H.; Zhou, X.; Lei, W.; Hu, X.; Zhang, L . Preparation of graphene oxide/bio-based elastomer nanocomposites through polymer design and interface tailoring . Polym. Chem. , 2015 . 6 6140 - 6151 . DOI: 10.1039/C5PY00720H http://doi.org/10.1039/C5PY00720H .

Qian, X.; Song, L.; Yu, B.; Yang, W.; Wang, B.; Hu, Y.; Yuen, R. K . One-pot surface functionalization and reduction of graphene oxide with long-chain molecules: Preparation and its enhancement on the thermal and mechanical properties of polyurea . Chem. Eng. J. , 2014 . 236 233 - 241 . DOI: 10.1016/j.cej.2013.09.061 http://doi.org/10.1016/j.cej.2013.09.061 .

Qian, X.; Song, L.; Tai, Q.; Hu, Y.; Yuen, R. K . Graphite oxide/polyurea and graphene/polyurea nanocomposites: A comparative investigation on properties reinforcements and mechanism . Compos. Sci. Technol. , 2013 . 74 228 - 234 . DOI: 10.1016/j.compscitech.2012.11.018 http://doi.org/10.1016/j.compscitech.2012.11.018 .

Wu, C.; Zhang, M. Q.; Rong, M. Z.; Friedrich, K . Silica nanoparticles filled polypropylene: Effects of particle surface treatment, matrix ductility and particle species on mechanical performance of the composites . Compos. Sci. Technol. , 2005 . 65 635 - 645 . DOI: 10.1016/j.compscitech.2004.09.004 http://doi.org/10.1016/j.compscitech.2004.09.004 .

Sánchez-Ferrer, A.; Rogez, D.; Martinoty, P . Synthesis and characterization of new polyurea elastomers by sol/gel chemistry . Macromol. Chem. Phys. , 2010 . 211 1712 - 1721 . DOI: 10.1002/macp.201000117 http://doi.org/10.1002/macp.201000117 .

Bras, W.; Derbyshire, G. E.; Bogg, D.; Cooke, J.; Elwell, M. J.; Komanschek, B. U.; Naylor, S.; Ryan, A. J . Simultaneous studies of reaciton-kinetics and structure development in polymer processing . Science , 1995 . 267 996 - 999 . DOI: 10.1126/science.267.5200.996 http://doi.org/10.1126/science.267.5200.996 .

Elwell, M. J.; Ryan, A. J.; Grünbauer, H. J. M.; Lieshout, H. C. V . In situ studies of structure development during the reactive processing of model flexible polyurethane foam systems using FTIR spectroscopy, synchrotron SAXS, and rheology . Macromolecules , 1996 . 212 2960 - 2968 . .

Sami, S.; Yildirim, E.; Yurtsever, M.; Yurtsever, E.; Yilgor, E.; Yilgor, I.; Wilkes, G. L . Understanding the influence of hydrogen bonding and diisocyanate symmetry on the morphology and properties of segmented polyurethanes and polyureas: Computational and experimental study . Polymer , 2014 . 55 4563 - 4576 . DOI: 10.1016/j.polymer.2014.07.028 http://doi.org/10.1016/j.polymer.2014.07.028 .

Das, S.; Cox, D. F.; Wilkes, G. L.; Klinedinst, D. B.; Yilgor, I.; Yilgor, E.; Beyer, F. L . Effect of symmetry and H-bond strength of hard segments on the structure-property relationships of segmented, nonchain extended polyurethanes and polyureas . J. Polym. Sci., Part B: Polym. Phys. , 2007 . 46 853 - 875 . .

Das, S.; Yilgor, I.; Yilgor, E.; Wilkes, G. L . Probing the urea hard domain connectivity in segmented, non-chain extended polyureas using hydrogen-bond screening agents . Polymer , 2008 . 49 174 - 179 . DOI: 10.1016/j.polymer.2007.10.046 http://doi.org/10.1016/j.polymer.2007.10.046 .

Aneja, A.; Wilkes, G. L . Exploring macro-and microlevel connectivity of the urea phase in slabstock flexible polyurethane foam formulations using lithium chloride as a probe . Polymer , 2002 . 43 5551 - 5561 . DOI: 10.1016/S0032-3861(02)00355-5 http://doi.org/10.1016/S0032-3861(02)00355-5 .

Mattia, J.; Painter, P . A comparison of hydrogen bonding and order in a polyurethane and poly(urethane-urea) and their blends with poly(ethylene glycol) . Macromolecules , 2007 . 40 1546 - 1554 . DOI: 10.1021/ma0626362 http://doi.org/10.1021/ma0626362 .

Appel, W. P. J.; Portale, G.; Wisse, E.; Dankers, P. Y. W.; Meijer, E. W . Aggregation of ureido-pyrimidinone supramolecular thermoplastic elastomers into nanofibers: A kinetic analysis . Macromolecules , 2011 . 44 6776 - 6784 . DOI: 10.1021/ma201303s http://doi.org/10.1021/ma201303s .

Cheng, C. C.; Yen, Y. C.; Chang, F. C . Self-supporting polymer from a POSS derivative . Macromol. Rapid Commun. , 2011 . 32 927 - 932 . DOI: 10.1002/marc.v32.12 http://doi.org/10.1002/marc.v32.12 .

Söntjens, S. H. M.; Renken, R. A. E.; Gemert, G. M. L. V.; Engels, T. A. P.; Bosman, A. W.; Janssen, H. M.; Govaert, L. E.; Baaijens, F. P. T . Thermoplastic elastomers based on strong and well-defined hydrogen-bonding interactions . Macromolecules , 2008 . 41 5703 - 5708 . DOI: 10.1021/ma800744c http://doi.org/10.1021/ma800744c .

Gooch, A.; Nedolisa, C.; Houton, K. A.; Lindsay, C. I.; Saiani, A.; Wilson, A. J . Tunable self-assembled elastomers using triply hydrogen-bonded arrays . Macromolecules , 2012 . 45 4723 - 4729 . DOI: 10.1021/ma3001109 http://doi.org/10.1021/ma3001109 .

Dankers, P. Y. W.; Zhang, Z.; Wisse, E.; Grijpma, D. W.; Sijbesma, R. P.; Feijen, J.; Meijer, E. W . Oligo(trimethylene carbonate)-based supramolecular biomaterials . Macromolecules , 2006 . 39 8763 - 8771 . DOI: 10.1021/ma061078o http://doi.org/10.1021/ma061078o .

Hirschberg, J. H. K. K.; Beijer, F. H.; Aert, H. A. V.; Magusin, P. C. M. M.; Sijbesma, R. P.; Meijer, E. W . Supramolecular polymers from linear telechelic siloxanes with quadruple-hydrogen-bonded units . Macromolecules , 1999 . 32 2696 - 2705 . DOI: 10.1021/ma981950w http://doi.org/10.1021/ma981950w .

Yan, X.; Liu, Z.; Zhang, Q.; Lopez, J.; Wang, H.; Wu, H. C.; Niu, S.; Yan, H.; Wang, S.; Lei, T . Quadruple H-bonding crosslinked supramolecular polymeric materials as substrates for stretchable, anti-tearing, and self-healable thin film electrodes . J. Am. Chem. Soc. , 2018 . 140 5280 - 5289 . DOI: 10.1021/jacs.8b01682 http://doi.org/10.1021/jacs.8b01682 .

Song, Y.; Liu, Y.; Qi, T.; Li, G. L . Towards dynamic but supertough healable polymers through biomimetic hierarchical hydrogen-bonding interactions . Angew. Chem. Int. Ed. , 2018 . 57 13838 - 13842 . DOI: 10.1002/anie.201807622 http://doi.org/10.1002/anie.201807622 .

Luo, M. C.; Jian, Z.; Xuan, F.; Huang, G.; Wu, J . Toughening diene elastomers by strong hydrogen bond interactions . Polymer , 2016 . 106 21 - 28 . DOI: 10.1016/j.polymer.2016.10.056 http://doi.org/10.1016/j.polymer.2016.10.056 .

Jie, L.; Tang, Z.; Jing, H.; Guo, B.; Huang, G . Promoted strain-induced-crystallization in synthetic cis -1,4-polyisoprene via constructing sacrificial bonds . Polymer , 2016 . 97 580 - 588 . DOI: 10.1016/j.polymer.2016.06.001 http://doi.org/10.1016/j.polymer.2016.06.001 .

Havriliak, S.; Negami, S . A complex plane representation of dielectric and mechanical relaxation processes in some polymers . Polymer , 1967 . 8 161 - 210 . DOI: 10.1016/0032-3861(67)90021-3 http://doi.org/10.1016/0032-3861(67)90021-3 .

Sontjens, S. H. M.; Sijbesma, R. P.; van Genderen, M. H. P.; Meijer, E. W . Stability and lifetime of quadruply hydrogen bonded 2-ureido-4[1 H ]-pyrimidinone dimers . J. Am. Chem. Soc. , 2000 . 122 7487 - 7493 . DOI: 10.1021/ja000435m http://doi.org/10.1021/ja000435m .

Beijer, F. H.; Sijbesma, R. P.; Kooijman, H.; Spek, A. L.; Meijer, E. W . Strong dimerization of ureidopyrimidones via quadruple hydrogen bonding . J. Am. Chem. Soc. , 1998 . 120 6761 - 6769 . DOI: 10.1021/ja974112a http://doi.org/10.1021/ja974112a .

Wei, M.; Zhan, M.; Yu, D.; Xie, H.; He, M.; Yang, K.; Wang, Y . Novel poly(tetramethylene ether)glycol and poly( ε -caprolactone) based dynamic network via quadruple hydrogen bonding with triple-shape effect and self-healing capacity . ACS Appl. Mater. Interfaces , 2015 . 7 2585 - 2596 . DOI: 10.1021/am507575z http://doi.org/10.1021/am507575z .

Lai, Y.; Kuang, X.; Zhu, P.; Huang, M.; Dong, X.; Wang, D . Colorless, transparent, robust, and fast scratch-self-healing elastomers via a phase-locked dynamic bonds design . Adv. Mater. , 2018 . 30 1802556 DOI: 10.1002/adma.v30.38 http://doi.org/10.1002/adma.v30.38 .

Teo, L. S.; Chen, C. Y.; Kuo, J. F . Fourier transform infrared spectroscopy study on effects of temperature on hydrogen bonding in amine-containing polyurethanes and poly(urethane-urea)s . Macromolecules , 1997 . 30 1793 - 1799 . DOI: 10.1021/ma961035f http://doi.org/10.1021/ma961035f .

Srichatrapimuk, V. W.; Cooper, S. L . Infrared thermal analysis of polyurethane block polymers . J. Polym. Sci., Part B: Polym. Phys. , 1978 . 15 267 - 311 . .

Prisacariu, C. Polyurethane elastomers : from morphology to mechanical aspects . Springer Science & amp; Business Media, 2011 .

Neal, J. A.; Mozhdehi, D.; Guan, Z . Enhancing mechanical performance of a covalent self-healing material by sacrificial noncovalent bonds . J. Am. Chem. Soc. , 2015 . 137 4846 - 4850 . DOI: 10.1021/jacs.5b01601 http://doi.org/10.1021/jacs.5b01601 .

Cordier, P.; Tournilhac, F.; Soulié-Ziakovic, C.; Leibler, L . Self-healing and thermoreversible rubber from supramolecular assembly . Nature , 2008 . 451 977 DOI: 10.1038/nature06669 http://doi.org/10.1038/nature06669 .

Liu, X. Y.; Ming, Z.; Shi, F. K.; Hao, X.; Xie, X. M . Multi-bond network hydrogels with robust mechanical and self-healable properties . Chinese J. Polym. Sci. , 2017 . 35 1253 - 1267 . DOI: 10.1007/s10118-017-1971-0 http://doi.org/10.1007/s10118-017-1971-0 .

Luo, M. C.; Zhang, X. K.; Zeng, J.; Gao, X. X.; Huang, G. S . Enhanced relaxation behavior below glass transition temperature in diene elastomer with heterogeneous physical network . Polymer , 2016 . 91 81 - 88 . DOI: 10.1016/j.polymer.2016.03.083 http://doi.org/10.1016/j.polymer.2016.03.083 .

Views

1782

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

Improvements of Hydrophobicity and Toughness of Epoxy Coatings Modified with Hydroxyl-terminated Fluororubber

Effects of Different Nucleating Agents, Annealing and Pre-stretching Process on the Crystallinity and Mechanical Properties of Poly(butylene carbonate)

Multifunctional Polyurethane with High Strength, Toughness, and Self-healing Capacity via Tannic Acid-modified Cellulose Nanocrystals

Green Fabrication of High-strength Silk Fibroin Hydrogels via Thermal Oscillation in All-aqueous Media

Advancing the Thin-film Mechanics of Conjugated Polymers: Characterization, Modulation, and Innovation

Related Author

Yu-Tong Zhou

You-Fan Wu

Qian-Qian Yang

Hai-Bao Zhang

Ting Zhang

Hao-Yan Guo

Zhen-Jun Wang

Gang Li

Related Institution

School of Materials Science and Engineering, Chang’an University

Shaanxi Union Research Center of University and Enterprise for Advanced Transportation Infrastructure Materials

College of Water Conservancy & Architectural Engineering, Shihezi University

Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences

University of Chinese Academy of Sciences

⁰