A Strategy for Designing Hierarchical Structure Flame Retardant ZM@APP for Improving Flame Retardancy, Mechanical Performance, and Smoke Suppression of Epoxy Resin
Jiankang Wang
College of Environment and Safety Engineering, Qingdao University of Science and Technology, Qingdao, People's Republic of China
Contribution: Conceptualization (lead), Writing - original draft (lead)
Search for more papers by this authorYing Lu
College of Environment and Safety Engineering, Qingdao University of Science and Technology, Qingdao, People's Republic of China
Contribution: Software (equal), Validation (equal)
Search for more papers by this authorJunyu Lin
College of Environment and Safety Engineering, Qingdao University of Science and Technology, Qingdao, People's Republic of China
Contribution: Methodology (equal)
Search for more papers by this authorMeixue Song
College of Environment and Safety Engineering, Qingdao University of Science and Technology, Qingdao, People's Republic of China
Contribution: Formal analysis (equal)
Search for more papers by this authorQingquan Wei
College of Environment and Safety Engineering, Qingdao University of Science and Technology, Qingdao, People's Republic of China
Contribution: Data curation (equal)
Search for more papers by this authorJiaqi Qiu
College of Environment and Safety Engineering, Qingdao University of Science and Technology, Qingdao, People's Republic of China
Contribution: Resources (equal)
Search for more papers by this authorZheng Wang
College of Environment and Safety Engineering, Qingdao University of Science and Technology, Qingdao, People's Republic of China
Contribution: Investigation (equal)
Search for more papers by this authorCorresponding Author
Dan Meng
College of Environment and Safety Engineering, Qingdao University of Science and Technology, Qingdao, People's Republic of China
Correspondence:
Dan Meng ([email protected])
Feng Zhang ([email protected])
Contribution: Writing - review & editing (equal)
Search for more papers by this authorCorresponding Author
Feng Zhang
College of Environment and Safety Engineering, Qingdao University of Science and Technology, Qingdao, People's Republic of China
Correspondence:
Dan Meng ([email protected])
Feng Zhang ([email protected])
Contribution: Writing - review & editing (equal)
Search for more papers by this authorJiankang Wang
College of Environment and Safety Engineering, Qingdao University of Science and Technology, Qingdao, People's Republic of China
Contribution: Conceptualization (lead), Writing - original draft (lead)
Search for more papers by this authorYing Lu
College of Environment and Safety Engineering, Qingdao University of Science and Technology, Qingdao, People's Republic of China
Contribution: Software (equal), Validation (equal)
Search for more papers by this authorJunyu Lin
College of Environment and Safety Engineering, Qingdao University of Science and Technology, Qingdao, People's Republic of China
Contribution: Methodology (equal)
Search for more papers by this authorMeixue Song
College of Environment and Safety Engineering, Qingdao University of Science and Technology, Qingdao, People's Republic of China
Contribution: Formal analysis (equal)
Search for more papers by this authorQingquan Wei
College of Environment and Safety Engineering, Qingdao University of Science and Technology, Qingdao, People's Republic of China
Contribution: Data curation (equal)
Search for more papers by this authorJiaqi Qiu
College of Environment and Safety Engineering, Qingdao University of Science and Technology, Qingdao, People's Republic of China
Contribution: Resources (equal)
Search for more papers by this authorZheng Wang
College of Environment and Safety Engineering, Qingdao University of Science and Technology, Qingdao, People's Republic of China
Contribution: Investigation (equal)
Search for more papers by this authorCorresponding Author
Dan Meng
College of Environment and Safety Engineering, Qingdao University of Science and Technology, Qingdao, People's Republic of China
Correspondence:
Dan Meng ([email protected])
Feng Zhang ([email protected])
Contribution: Writing - review & editing (equal)
Search for more papers by this authorCorresponding Author
Feng Zhang
College of Environment and Safety Engineering, Qingdao University of Science and Technology, Qingdao, People's Republic of China
Correspondence:
Dan Meng ([email protected])
Feng Zhang ([email protected])
Contribution: Writing - review & editing (equal)
Search for more papers by this authorFunding: This work was supported by National Natural Science Foundation of China, 21975138.
ABSTRACT
Improving flame retardancy without compromising mechanical properties is a significant challenge in epoxy resin (EP) applications. In this study, an inorganic–organic hybrid flame retardant (ZM@APP) with a hierarchical structure was designed by loading the compounds with a shell-core structure ZM (a complex of ZIF-67 and melamine) on the surface of ammonium polyphosphate (APP) through hydrogen bonding. When the loading of ZM@APP was 10.0 wt.%, the tensile strength, flexural strength, and flexural modulus of the EP composites increased by 13.7%, 16.7%, and 87.6%, respectively, compared to pure EP. Surprisingly, modified APP also resulted in the promotion of mechanical performances while APP triggered the decreases in mechanical properties. The 10ZM@APP/EP passed the V-0 rating in the vertical combustion test and achieved the limiting oxygen index of 28.2%. The peak heat release rate and total heat release decreased by 68.4% and 58.5%, respectively; the peak smoke release rate and total smoke production were reduced by 60.0% and 67.5%, respectively, compared to pure EP. The reason was that the triazine ring, cobalt oxide, and pyrophosphoric acid promoted the formation of contact and continuous char. This study offers a new method for preparing EP composites with enhanced flame retardancy, high mechanical properties, and low smoke release.
Conflicts of Interest
The authors declare no conflicts of interest.
Open Research
Data Availability Statement
The data that support the findings of this study are available from the corresponding author upon reasonable request.
Supporting Information
| Filename | Description |
|---|---|
| app57299-sup-0001-Supporting_Information.docxWord 2007 document , 716.8 KB |
Data S1. Supporting Information. |
Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.
References
- 1X. Y. Lu and X. L. Gu, “A Review on Lignin-Based Epoxy Resins: Lignin Effects on Their Synthesis and Properties,” International Journal of Biological Macromolecules 229 (2023): 778–790.
- 2K. P. Song, Y. T. Pan, J. Zhang, et al., “Metal-Organic Frameworks-Based Flame-Retardant System for Epoxy Resin: A Review and Prospect,” Chemical Engineering Journal 468 (2023): 143653.
- 3S. Huang, L. Wang, Y. C. Li, C. B. Liang, and J. L. Zhang, “Novel Ti3C2Tx MXene/Epoxy Intumescent Fire-Retardant Coatings for Ancient Wooden Architectures,” Journal of Applied Polymer Science 138, no. 27 (2021): 50649.
- 4Y. D. Wang, L. Ma, J. Yuan, et al., “Furfural-Based P/N/S Flame Retardant Towards High-Performance Epoxy Resins With Flame Retardancy, Toughness, Low Dielectric Properties and UV Resistance,” Polymer Degradation and Stability 212 (2023): 110343.
- 5Q. S. Yang, J. Wang, X. Chen, et al., “A Phosphorus-Containing Tertiary Amine Hardener Enabled Flame Retardant, Heat Resistant and Mechanically Strong Yet Tough Epoxy Resins,” Chemical Engineering Journal 468 (2023): 143811.
- 6C. Liu, P. Li, Y. J. Xu, Y. Liu, and P. Zhu, “Nickel Alginate-Enhanced Fire Safety of Aluminum Diethylphosphinate on Epoxy Resin,” Journal of Applied Polymer Science 140, no. 9 (2023): 53552.
- 7S. Q. Huo, T. Sai, S. Y. Ran, et al., “A Hyperbranched P/N/B-Containing Oligomer as Multifunctional Flame Retardant for Epoxy Resins,” Composites Part B-Engineering 234 (2022): 109701.
- 8Y. D. Wang, Y. G. Zhang, L. Ma, et al., “Facile Synthesis of Phosphorus-Containing Benzotriazole Flame Retardant for Enhancement of Mechanical and Fire Properties of Epoxy Resins,” European Polymer Journal 202 (2024): 112610.
- 9M. A. Rashid, W. S. Liu, Y. Wei, and Q. R. Jiang, “Review on Intrinsically Recyclable Flame Retardant Thermosets Enabled Through Covalent Bonds,” Journal of Applied Polymer Science 139, no. 27 (2022): 52493.
- 10Y. R. Sun, B. H. Yuan, S. Shang, et al., “Surface Modification of Ammonium Polyphosphate by Supramolecular Assembly for Enhancing Fire Safety Properties of Polypropylene,” Composites Part B-Engineering 181 (2020): 107588.
- 11K. S. Lim, S. T. Bee, L. T. Sin, et al., “A Review of Application of Ammonium Polyphosphate as Intumescent Flame Retardant in Thermoplastic Composites,” Composites Part B-Engineering 84 (2016): 155–174.
- 12X. L. Kang, Z. H. Lu, W. L. Feng, et al., “A Novel Phosphorous and Silicon-Containing Benzoxazine: Highly Efficient Multifunctional Flame-Retardant Synergist for Polyoxymethylene,” Advanced Composites and Hybrid Materials 4, no. 1 (2021): 127–137.
- 13W. X. Li, H. J. Zhang, X. P. Hu, W. X. Yang, Z. Cheng, and C. Q. Xie, “Highly Efficient Replacement of Traditional Intumescent Flame Retardants in Polypropylene by Manganese Ions Doped Melamine Phytate Nanosheets,” Journal of Hazardous Materials 398 (2020): 123001.
- 14D. X. Liang, X. J. Zhu, P. Dai, et al., “Preparation of a Novel Lignin-Based Flame Retardant for Epoxy Resin,” Materials Chemistry and Physics 259 (2021): 124101.
- 15L. Yin, K. L. Gong, K. Q. Zhou, et al., “Flame-Retardant Activity of Ternary Integrated Modified Boron Nitride Nanosheets to Epoxy Resin,” Journal of Colloid and Interface Science 608 (2022): 853–863.
- 16J. Chai, Y. X. Hou, Y. H. Zhang, et al., “A Cu-MOF-Decorated Ammonium Polyphosphate for Epoxy Resins With Reduced Smoke Release and Enhanced Char Layer,” Journal of Applied Polymer Science 141, no. 36 (2024): 55918.
- 17C. Chen, W. M. Song, M. M. Jiang, et al., “SiO2/MOFs-Based Synergistic Flame Retardants Provide Enhanced Fire Safety for Epoxy Resins,” Materials Today Communications 35 (2023): 105805.
- 18X. N. Song, B. Y. Hou, Z. D. Han, et al., “Dual Nucleation Sites Induced by ZIF-67 Towards Mismatch of Polyphosphazene Hollow Sub-Micron Polyhedrons and Nanospheres in Flame Retardant Epoxy Matrix,” Chemical Engineering Journal 470 (2023): 144278.
- 19Z. B. Shao, J. Zhang, R. K. Jian, C. C. Sun, X. L. Li, and D. Y. Wang, “A Strategy to Construct Multifunctional Ammonium Polyphosphate for Epoxy Resin With Simultaneously High Fire Safety and Mechanical Properties,” Composites Part A-Applied Science and Manufacturing 149 (2021): 106529.
- 20Z. Q. Yue, J. Lin, D. S. Yang, et al., “In Situ Growth of Nano-MOFs on Ammonium Polyphosphate Particles for Boosting Flame Retardancy, Smoke Suppression and Mechanical Properties of Epoxy,” Journal of Materials Science 57, no. 42 (2022): 20082–20094.
- 21J. J. Ye, Z. L. Fan, S. Zhang, and X. B. Liu, “Optimizing the Dielectric and Mechanical Properties of Melamine Based-Benzoxazine Resin by Copolymerizing With Epoxy Resin,” Journal of Applied Polymer Science 140, no. 24 (2023): 53956.
- 22J. B. Feng, Y. X. Lu, H. Y. Xie, et al., “Atom-Economic Synthesis of an Oligomeric P/N-Containing Fire Retardant Towards Fire-Retarding and Mechanically Robust Polylactide Biocomposites,” Journal of Materials Science and Technology 160 (2023): 86–95.
- 23S. C. Yoo, J. Kim, S. Kim, and D. Lee, “Enhanced Mechanical Properties of Melamine-Functionalized Boron Nitride Nanosheets Reinforced With Epoxy Nanocomposites for Dental Applications,” Journal of Materials Science 57, no. 38 (2022): 18205–18219.
- 24Y. Z. Qi, X. L. Ye, X. Y. Huan, et al., “P/N/S Flame Retardant Based on DOPS-Triazine Groups for Improving the Flame Retardancy, Char Formation Properties and Mechanical Properties of Epoxy Resin,” European Polymer Journal 202 (2024): 112634.
- 25H. Nabipour, X. Wang, L. Song, and Y. Hu, “Organic-Inorganic Hybridization of Isoreticular Metal-Organic Framework-3 With Melamine for Efficiently Reducing the Fire Risk of Epoxy Resin,” Composites Part B-Engineering 211 (2021): 108606.
- 26Y. H. Liu, B. J. Liu, Z. Y. Sun, et al., “Bioinspired Mono-Component Lignin Endowing Epoxy Resin With Simultaneously Improving Flame Retardancy and Mechanical Properties,” Composites Communications 35 (2022): 101306.
- 27N. Li, G. Chen, J. Zhao, et al., “Self-Cleaning PDA/ZIF-67@PP Membrane for Dye Wastewater Remediation With Peroxymonosulfate and Visible Light Activation,” Journal of Membrane Science 591 (2019): 117341.
- 28X. Y. Liu, P. Y. Guo, B. R. Zhang, and J. X. Mu, “A Novel Ternary Inorganic-Organic Hybrid Flame Retardant Containing Biomass and MOFs for High-Performance Rigid Polyurethane Foam,” Colloids and Surfaces A: Physicochemical and Engineering Aspects 671 (2023): 131625.
- 29Z. W. Wang, L. Sun, L. Ding, et al., “Novel Phosphorus-Free and Core-Shell Structured ZIF-67 for Simultaneously Endowing Epoxy Resin With Excellent Fire Safety, Corrosion and UV Resistance,” European Polymer Journal 194 (2023): 112159.
- 30Z. C. Wu, Z. Z. Wang, J. Liu, J. H. Yin, and S. P. Kuang, “A New Porous Magnetic Chitosan Modified by Melamine for Fast and Efficient Adsorption of Cu(II) Ions,” International Journal of Biological Macromolecules 81 (2015): 838–846.
- 31W. Z. Xu, G. S. Wang, J. Y. Xu, Y. C. Liu, R. Chen, and H. Y. Yan, “Modification of Diatomite With Melamine Coated Zeolitic Imidazolate Framework-8 as an Effective Flame Retardant to Enhance Flame Retardancy and Smoke Suppression of Rigid Polyurethane Foam,” Journal of Hazardous Materials 379 (2019): 120819.
- 32Y. R. Shao, Y. T. Wang, F. Yang, et al., “Sodium Silicate/Urea/Melamine Ternary Synergistic Waterborne Acrylic Acid Flame-Retardant Coating and Its Flame-Retardant Mechanism,” Molecules 29, no. 7 (2024): 29071472.
- 33W. Y. Chen, L. L. Wang, and G. S. Liu, “Synthesis of Ammonium Polyphosphate With Crystalline Form V (APP-V) From Melamine Polyphosphate (MPP),” Polymer Degradation and Stability 97, no. 12 (2012): 2567–2570.
- 34M. Wan, C. L. Shi, L. Chen, et al., “Core-Shell Flame Retardant/APP-PEI@MXene@ZIF-67: A Nanomaterials Self-Assembly Strategy Towards Reducing Fire Hazard of Thermoplastic Polyurethane,” Polymer Degradation and Stability 226 (2024): 110821.
- 35M. Y. Ou, R. C. Lian, J. H. Zhu, et al., “Aromatic P/N/Co-Containing Microsphere Flame Retardant for Enhancing Fire Safety and Mechanical Properties of Epoxy Coating With Lower Curing Temperature,” Progress in Organic Coatings 183 (2023): 107728.
- 36H. Y. Ren, K. L. Qing, Y. Chen, Y. J. Lin, and X. Duan, “Smoke Suppressant in Flame Retarded Thermoplastic Polyurethane Composites: Synergistic Effect and Mechanism Study,” Nano Research 14, no. 11 (2021): 3926–3934.
- 37X. Song, H. B. Lv, M. M. Shi, Z. B. Shao, and Y. Z. Wang, “Calcium Gluconate-Based Flame Retardant Towards Simultaneously High-Efficiency Fire Safety and Mechanical Enhancement for Epoxy Resin,” International Journal of Biological Macromolecules 264 (2024): 130409.
- 38W. Wang, Y. Liu, and Q. Wang, “Synthesis of Melamine Cyanuric Based Flame Retardant via Hydrogen Bond Self-Assembly and In-Situ Dispersion Strategies for Improving Comprehensive Performance of Epoxy Resin,” Composites Part A-Applied Science and Manufacturing 176 (2024): 107826.
- 39S. N. Wei, W. T. Zhong, P. W. Xu, et al., “Synergistic Effect of Co-MOF/Epoxy Modified Tannic Acid/Ammonium Polyphosphate on Flame Retardancy, Anti-Melt Dripping and Mechanical Properties of Polylactic Acid,” Chemical Engineering Journal 500 (2024): 156772.
- 40Y. X. Yang, Z. Li, G. Wu, W. Chen, and G. Y. Huang, “A Novel Biobased Intumescent Flame Retardant Through Combining Simultaneously Char-Promoter and Radical-Scavenger for the Application in Epoxy Resin,” Polymer Degradation and Stability 196 (2022): 109841.
- 41C. H. Zhang, H. J. Duan, C. Wan, C. T. Liu, H. J. Zhao, and H. R. Ma, “Simultaneously Improving the Thermal Stability, Mechanical Properties and Flame Retardancy of Epoxy Resin by a Phosphorus/Nitrogen/Sulfur-Containing Reactive Flame Retardant,” Materials Today Communications 30 (2022): 103108.
- 42Y. W. Geng, J. X. Piao, X. L. Liu, X. L. Chen, and C. M. Jiao, “ZIF-67-Derived CuCo-Layered Double Hydroxide/Ammonium Polyphosphate Hybrid for Highly Efficient Flame Retardant Epoxy Resin via Synergistic Catalytic Carbonization,” Construction and Building Materials 453 (2024): 139102.
- 43N. Teng, J. Y. Dai, S. P. Wang, J. Y. Hu, and X. Q. Liu, “Hyperbranched Flame Retardant for Epoxy Resin Modification: Simultaneously Improved Flame Retardancy, Toughness and Strength as Well as Glass Transition Temperature,” Chemical Engineering Journal 428 (2022): 131226.
- 44Y. B. Zou, Z. H. Shi, J. J. Shi, F. B. Luo, and H. Z. Li, “'Honeycomb-Like' Triazine-Based Covalent Organic Framework Derivative for Remarkably Improving Both Flame Retardancy and Mechanical Properties of Epoxy Resin,” Construction and Building Materials 426 (2024): 136166.
- 45W. Cai, T. M. Cai, L. X. He, et al., “Natural Antioxidant Functionalization for Fabricating Ambient-Stable Black Phosphorus Nanosheets Toward Enhancing Flame Retardancy and Toxic Gases Suppression of Polyurethane,” Journal of Hazardous Materials 387 (2020): 121971.
- 46Y. Fang, J. Liang, X. B. Song, L. Feng, H. Zhou, and C. Y. Zhou, “Enhancement of Smoke and Toxic Gas Suppression During Combustion and Improvement of the Mechanical Properties of Epoxy Resin by Incorporation of a Modified MOF Material Containing the Phosphoheterophene Group,” New Journal of Chemistry 48, no. 46 (2024): 19561–19573.
- 47H. Jiang, Y. H. Xie, R. Zhu, et al., “Construction of Polyphosphazene-Functionalized Ti3C2TX With High Efficient Flame Retardancy for Epoxy and Its Synergetic Mechanisms,” Chemical Engineering Journal 456 (2023): 141049.
- 48K. X. Hu, Z. Y. Zhao, P. Lu, S. He, C. Deng, and Y. Z. Wang, “Caffeic Acid Decorated Ammonium Polyphosphate-Based Flame Retardant for Fire Safety and Anti-Aging of Wood Plastic Composites,” Polymer Degradation and Stability 209 (2023): 110275.
- 49H. Z. Fan, X. Y. Gu, S. Zhang, F. Liu, Y. H. Liao, and W. F. Tang, “Synergistic Effect Between Novel Triazine-Based Charring Agent and Modified Kaolinite: An Efficient System for Fire Hazard and Aging Suppression of Epoxy Resin,” Polymer Degradation and Stability 204 (2022): 110109.
- 50R. C. Lian, M. Y. Ou, H. C. Guan, et al., “Cu(II) and Co(II) Complexes Decorated Ammonium Polyphosphate as co-Curing Agents on Improving Fire Safety and Mechanical Properties of Epoxy-Based Building Coatings,” Construction and Building Materials 389 (2023): 131786.
- 51H. X. Dong, Y. X. Wang, T. T. Feng, et al., “Phytic Acid Doped Polyaniline-Coupled g-C3N4 Nanosheets for Synergizing With APP Promoting Fire Safety and Waterproof Performance of Epoxy Composites,” Polymer Degradation and Stability 198 (2022): 109879.
- 52X. Bi, H. Di, J. Liu, et al., “A Core-Shell-Structured APP@COFs Hybrid for Enhanced Flame Retardancy and Mechanical Property of Epoxy Resin (EP),” Advanced Composites and Hybrid Materials 5, no. 3 (2022): 1743–1755.
- 53B. Y. Hou, X. N. Song, K. P. Song, et al., “Synchronous Preparation and Modification of LDH Hollow Polyhedra by Polydopamine: Synthesis and Application,” Journal of Colloid and Interface Science 654 (2024): 235–245.
