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Thermoplastic polyurethane (PU) elastomers have attracted significant attention because of their many important industrial applications. However, the creation of fire-retardant and anti-dripping PU elastomers has remained a grant challenge due to the lack of crosslinking and weak interchain interactions. Herein, we report a mechanically robust, biodegradable, fire-retardant, and anti-dripping biobased PU elastomer with excellent biodegradability using an abietic acid-based compound as hard segments and polycaprolactone diol (PCL) as soft segments, followed by physically crosslinking with cellulose nanocrystals (CNC) through dynamic hydrogen-bonding. The resultant elastomer shows the balanced mechanical and fire-retardant properties, e.g., a tensile strength and break strain of 9.1 MPa and 560%, a self-extinguishing ability (V-0 rating in UL-94 testing), and an anti-dripping behavior. Moreover, the as-developed PU can be completely degraded in 1.0 wt.% lipase solution at 37 °C in 60 days, arising from the catalytic and wicking effect of CNC on PU chains. This work provides an innovative and versatile strategy for constructing robust, fire-retardant, anti-dripping, and biodegradable PU elastomers, which hold great promise for practical applications in electronic and automobile sectors.
Wang, F. F.; Yang, Z. J.; Li, J.; Zhang, C.; Sun, P. C. Bioinspired polyurethane using multifunctional block modules with synergistic dynamic bonds. ACS Macro Lett. 2021, 10, 510–517.
Ying, W. B.; Wang, G. Y.; Kong, Z. Y.; Yao, C. K.; Wang, Y. B.; Hu, H.; Li, F. L.; Chen, C.; Tian, Y.; Zhang, J. W. et al. A biologically muscle-inspired polyurethane with super-tough, thermal reparable and self-healing capabilities for stretchable electronics. Adv. Funct. Mater. 2021, 31, 2009869.
Du, R. C.; Xu, Z. C.; Zhu, C.; Jiang, Y. W.; Yan, H. P.; Wu, H. C.; Vardoulis, O.; Cai, Y. F.; Zhu, X. Y.; Bao, Z. N. et al. A highly stretchable and self-healing supramolecular elastomer based on sliding crosslinks and hydrogen bonds. Adv. Funct. Mater. 2020, 30, 1907139.
Xu, W.; Zhang, R. Y.; Liu, W.; Zhu, J.; Dong, X.; Guo, H. X.; Hu, G. H. A multiscale investigation on the mechanism of shape recovery for IPDI to PPDI hard segment substitution in polyurethane. Macromolecules 2016, 49, 5931–5944.
Hu, J.; Mo, R. B.; Sheng, X. X.; Zhang, X. Y. A self-healing polyurethane elastomer with excellent mechanical properties based on phase-locked dynamic imine bonds. Polym. Chem. 2020, 11, 2585–2594.
Li, Z. Q.; Zhu, Y. L.; Niu, W. W.; Yang, X.; Jiang, Z. Y.; Lu, Z. Y.; Liu, X. K.; Sun, J. Q. Healable and recyclable elastomers with record-high mechanical robustness, unprecedented crack tolerance, and superhigh elastic restorability. Adv. Mater. 2021, 33, 2101498.
Yao, Y.; Liu, B.; Xu, Z. Y.; Yang, J. H.; Liu, W. G. An unparalleled H-bonding and ion-bonding crosslinked waterborne polyurethane with super toughness and unprecedented fracture energy. Mater. Horiz. 2021, 8, 2742–2749.
Wang, X. H.; Zhan, S. N.; Lu, Z. Y.; Li, J.; Yang, X.; Qiao, Y. N.; Men, Y.; Sun, J. Q. Healable, recyclable, and mechanically tough polyurethane elastomers with exceptional damage tolerance. Adv. Mater. 2020, 32, 2005759.
Chen, H.; Deng, C.; Zhao, Z. Y.; Huang, S. C.; Wei, Y. X.; Wang, Y. Z. Novel alkynyl-containing phosphonate ester oligomer with high charring capability as flame retardant additive for thermoplastic polyurethane. Compos. Part B: Eng. 2020, 199, 108315.
Chen, H.; Deng, C.; Zhao, Z. Y.; Wan, L.; Yang, A. H.; Wang, Y. Z. Novel piperazine-containing oligomer as flame retardant and crystallization induction additive for thermoplastics polyurethane. Chem. Eng. J. 2020, 400, 125941.
Xing, W. Y.; Xi, J. C.; Qi, L. Y.; Hai, Z. B.; Cai, W.; Zhang, W. J.; Wang, B. Y.; Chen, L.; Hu, Y. Construction of a flame retardant polyurethane elastomer with degradability, high mechanical strength and shape memory. Compos. Part A: Appl. Sci. Manuf. 2023, 169, 107512.
Wang, H.; Liu, Q.; Zhao, X.; Jin, Z. Synthesis of reactive DOPO-based flame retardant and its application in polyurethane elastomers. Polym. Degrad. Stab. 2021, 183, 109440.
Pan, G. F.; Wang, Z.; Kong, D. Q.; Sun, T. W.; Zhai, H.; Tian, T.; Wang, Y. F.; Xing, R. G.; Zhang, B. W. Transparent, flame-retarded, self-healable, mechanically strong polyurethane elastomers: Enabled by the synthesis of phosphorus/nitrogen-containing oxime chain-extender. J. Appl. Polym. Sci. 2022, 139, 51598.
Kang, K. S.; Phan, A.; Olikagu, C.; Lee, T.; Loy, D. A.; Kwon, M.; Paik, H. J.; Hong, S. J.; Bang, J.; Parker, W. O. Jr. et al. Segmented polyurethanes and thermoplastic elastomers from elemental sulfur with enhanced thermomechanical properties and flame retardancy. Angew. Chem., Int. Ed. 2021, 60, 22900–22907.
Xue, Y. J.; Lin, J. Y.; Wan, T.; Luo, Y. L.; Ma, Z. W.; Zhou, Y. H.; Tuten, B. T.; Zhang, M.; Tao, X. Y.; Song, P. A. Stretchable, ultratough, and intrinsically self-extinguishing elastomers with desirable recyclability. Adv. Sci. 2023, 10, 2207268.
Xue, Y. J.; Ma, Z. W.; Xu, X. D.; Shen, M. X.; Huang, G. B.; Bourbigot, S.; Liu, X. Q.; Song, P. A. Mechanically robust and flame-retardant polylactide composites based on molecularly-engineered polyphosphoramides. Compos. Part A: Appl. Sci. Manuf. 2021, 144, 106317.
Xue, Y. J.; Zhang, T. C.; Tian, L. F.; Feng, J. B.; Song, F.; Pan, Z.; Zhang, M.; Zhou, Y. H.; Song, P. A. A molecularly engineered bioderived polyphosphonate containing Schiff base towards fire-retardant PLA with enhanced crystallinity and mechanical properties. Chem. Eng. J. 2023, 472, 144986.
Xue, Y. J.; Feng, J. B.; Huo, S. Q.; Song, P. A.; Yu, B.; Liu, L.; Wang, H. Polyphosphoramide-intercalated MXene for simultaneously enhancing thermal stability, flame retardancy and mechanical properties of polylactide. Chem. Eng. J. 2020, 397, 125336.
Xue, Y. J.; Feng, J. B.; Ma, Z. W.; Liu, L. N.; Zhang, Y.; Dai, J. F.; Xu, Z. G.; Bourbigot, S.; Wang, H.; Song, P. A. Advances and challenges in eco-benign fire-retardant polylactide. Mater. Today Phys. 2021, 21, 100568.
Wang, H. F.; Wang, J.; Guo, H. M.; Chen, X. G.; Yu, X. Y.; Ma, Y. H.; Ji, P. G.; Naito, K.; Zhang, Z. J.; Zhang, Q. X. A novel high temperature vinylpyridine-based phthalonitrile polymer with a low melting point and good mechanical properties. Polym. Chem. 2018, 9, 976–983.
Gu, J. W.; Dang, J.; Wu, Y. L.; Xie, C.; Han, Y. Flame-retardant, thermal, mechanical and dielectric properties of structural non-halogenated epoxy resin composites. Polym. Plast. Technol. Eng. 2012, 51, 1198–1203.
Jiao, Y. Z.; Rong, Z. H.; Gao, C. H.; Wu, Y. M.; Liu, Y. T. Tannic acid crosslinked self-healing and reprocessable silicone elastomers with improved antibacterial and flame retardant properties. Macromol. Rapid Commun. 2023, 44, 2200681.
Wang, Z. H.; Liu, B. W.; Zeng, F. R.; Lin, X. C.; Zhang, J. Y.; Wang, X. L.; Wang, Y. Z.; Zhao, H. B. Fully recyclable multifunctional adhesive with high durability, transparency, flame retardancy, and harsh-environment resistance. Sci. Adv. 2022, 8, eadd8527.
Grimme, S. Do special noncovalent π–π stacking interactions really exist. Angew. Chem., Int. Ed. 2008, 47, 3430–3434.
Wang, L.; Peng, Y. W.; Xu, Y. L.; Zhang, J. J.; Liu, C. G.; Tang, X. J.; Lu, Y.; Sun, H. W. Earthworms’ degradable bioplastic diet of polylactic acid: Easy to break down and slow to excrete. Environ. Sci. Technol. 2022, 56, 5020–5028.
Martin, R. T.; Camargo, L. P.; Miller, S. A. Marine-degradable polylactic acid. Green Chem. 2014, 16, 1768–1773.
Mi, H. Y.; Jing, X.; Napiwocki, B. N.; Hagerty, B. S.; Chen, G. J.; Turng, L. S. Biocompatible, degradable thermoplastic polyurethane based on polycaprolactone- block-polytetrahydrofuran- block-polycaprolactone copolymers for soft tissue engineering. J. Mater. Chem. B 2017, 5, 4137–4151.
Al Hosni, A. S.; Pittman, J. K.; Robson, G. D. Microbial degradation of four biodegradable polymers in soil and compost demonstrating polycaprolactone as an ideal compostable plastic. Waste Manage. 2019, 97, 105–114.
Wang, H.; Wei, D. F.; Zheng, A. N.; Xiao, H. N. Soil burial biodegradation of antimicrobial biodegradable PBAT films. Polym. Degrad. Stab. 2015, 116, 14–22.
Liu, B.; Guan, T. H.; Wu, G.; Fu, Y.; Weng, Y. X. Biodegradation behavior of degradable mulch with poly (butylene adipate-co-terephthalate) (PBAT) and poly (butylene succinate) (PBS) in simulation marine environment. Polymers 2022, 14, 1515.
Sun, M.; Yang, Y. K.; Huang, M. L.; Fu, S. K.; Hao, Y. Y.; Hu, S. Y.; Lai, D. L.; Zhao, L. Adsorption behaviors and mechanisms of antibiotic norfloxacin on degradable and nondegradable microplastics. Sci. Total Environ. 2022, 807, 151042.
Qi, J. F.; Wu, J.; Chen, J. Y.; Wang, H. P. An investigation of the thermal and (bio)degradability of PBS copolyesters based on isosorbide. Polym. Degrad. Stab. 2019, 160, 229–241.
Xun, X. C.; Zhao, X.; Li, Q.; Zhao, B.; Ouyang, T.; Zhang, Z.; Kang, Z.; Liao, Q. L.; Zhang, Y. Tough and degradable self-healing elastomer from synergistic soft-hard segments design for biomechano-robust artificial skin. ACS Nano 2021, 15, 20656–20665.
Sun, P. H.; Wang, S. H.; Huang, Z.; Zhang, L.; Dong, F. H.; Xu, X.; Liu, H. Water-resistant, strong, degradable and recyclable rosin-grafted cellulose composite paper. Green Chem. 2022, 24, 7519–7530.
Huo, S. Q.; Sai, T.; Ran, S. Y.; Guo, Z. H.; Fang, Z. P.; Song, P. A.; Wang, H. A hyperbranched P/N/B-containing oligomer as multifunctional flame retardant for epoxy resins. Compos. Part B: Eng. 2022, 234, 109701.
Zhang, H. Y.; Van Hertrooij, A.; Schnitzer, T.; Chen, Y. J.; Majumdar, S.; Van Benthem, R. A. T. M.; Sijbesma, R. P.; Heuts, J. P. A. Benzene tetraamide: A covalent supramolecular dual motif in dynamic covalent polymer networks. Macromolecules 2023, 56, 6452–6460.
Xu, X. D.; Li, L. J.; Seraji, S. M.; Liu, L.; Jiang, Z.; Xu, Z. G.; Li, X.; Zhao, S.; Wang, H.; Song, P. A. Bioinspired, strong, and tough nanostructured poly(vinyl alcohol)/inositol composites: How hydrogen-bond cross-linking works. Macromolecules 2021, 54, 9510–9521.
Yao, Z.; Wu, D. F.; Chen, C.; Zhang, M. Creep behavior of polyurethane nanocomposites with carbon nanotubes. Compos. Part A: Appl. Sci. Manuf. 2013, 50, 65–72.
Huo, S. Q.; Wang, J.; Yang, S.; Li, C.; Wang, X. L.; Cai, H. P. Synthesis of a DOPO-containing imidazole curing agent and its application in reactive flame retarded epoxy resin. Polym. Degrad. Stab. 2019, 159, 79–89.
Huang, Z.; Wang, S. B.; Ren, C. Y.; Liu, H.; Xu, X.; Song, Z. Q. Preparation and application of rosin modified siloxane-based flame retardant. Chem. Ind. For. Prod. 2022, 42, 71–79.
Yao, M. H.; Liu, L. H.; Ma, C. C.; Zhang, H.; Zhang, Y.; Song, R. Y.; Fang, Z. P.; Song, P. A. A lysine-derived flame retardant for improved flame retardancy, crystallinity, and aqueous-phase degradation of polylactide. Chem. Eng. J. 2023, 462, 142189
Yanagisawa, Y.; Nan, Y. L.; Okuro, K.; Aida, T. Mechanically robust, readily repairable polymers via tailored noncovalent cross-linking. Science 2018, 359, 72–76.
Liu, Z.; Fan, X. L.; Zhang, J. L.; Chen, L. X.; Tang, Y. S.; Kong, J.; Gu, J. W. PBO fibers/fluorine-containing liquid crystal compound modified cyanate ester wave-transparent laminated composites with excellent mechanical and flame retardance properties. J. Mater. Sci. Technol. 2023, 152, 16–29.
Zhong, X.; Yang, X. T.; Ruan, K. P.; Zhang, J. L.; Zhang, H. T.; Gu, J. W. Discotic liquid crystal epoxy resins integrating intrinsic high thermal conductivity and intrinsic flame retardancy. Macromol. Rapid Commun. 2022, 43, 2100580.
Luo, Y.; Miao, Y. P.; Wang, H. M.; Dong, K.; Hou, L.; Xu, Y. Y.; Chen, W. C.; Zhang, Y.; Zhang, Y. Y.; Fan, W. Laser-induced Janus graphene/poly(p-phenylene benzobisoxazole) fabrics with intrinsic flame retardancy as flexible sensors and breathable electrodes for fire-fighting field. Nano Res. 2023, 16, 7600–7608.
Yao, K. J.; Wang, J. F.; Zhang, W. J.; Lee, J. S.; Wang, C. P.; Chu, F. X.; He, X. M.; Tang, C. B. Degradable rosin-ester-caprolactone graft copolymers. Biomacromolecules 2011, 12, 2171–2177.
Meabe, L.; Sardon, H.; Mecerreyes, D. Hydrolytically degradable poly(ethylene glycol) based polycarbonates by organocatalyzed condensation. Eur. Polym. J. 2017, 95, 737–745.
Liu, Q. Y.; Zhou, L.; Fan, D.; Guan, M. Z.; Ma, Q. Z.; Li, S.; Ouyang, X. P.; Qiu, X. Q.; Fan, W. Adsorption-enhanced glucan oligomer production from cellulose hydrolysis over hyper-cross-linked polymer in molten salt hydrate. ACS Appl. Mater. Interfaces 2021, 13, 52082–52091.
Schusser, S.; Menzel, S.; Bäcker, M.; Leinhos, M.; Poghossian, A.; Wagner, P.; Schöning, M. J. Degradation of thin poly(lactic acid) films: Characterization by capacitance-voltage, atomic force microscopy, scanning electron microscopy and contact-angle measurements. Electrochim. Acta 2013, 113, 779–784.
Wang, L.; Ma, Z. L.; Zhang, Y. L.; Qiu, H.; Ruan, K. P.; Gu, J. W. Mechanically strong and folding-endurance Ti3C2T x MXene/PBO nanofiber films for efficient electromagnetic interference shielding and thermal management. Carbon Energy 2022, 4, 200–210.
