
Construction of CS@APP@UiO-66 through self-assembly technology as flame retardant and smoke suppressant for epoxy resins
Siqing Shao, Liping Jin, Siyuan He, Yijing Feng, Wenwen Guo
Front. Chem. Sci. Eng. ›› 2025, Vol. 19 ›› Issue (4) : 25.
Construction of CS@APP@UiO-66 through self-assembly technology as flame retardant and smoke suppressant for epoxy resins
To achieve fire-resistant epoxy resin (EP), a UiO-66-based novel flame retardant coating (CS@APP@UiO-66) was prepared by modifying UiO-66 with chitosan (CS) and ammonium polyphosphate (APP) through a layer-by-layer (LbL) self-assembly method, which was then introduced into an EP system to improve its fire safety. The results of scanning electron microscopy, X-ray diffraction and Fourier transform infrared spectroscopy show that the unsaturated Zr atoms in the UiO-66 framework provide many active sites conducive to modification, so that the UiO-66 particles, which originally had a regular octahedral structure, are more dispersed by LbL modification without causing doping or distortion issues. The thermogravimetric analysis results indicate that the char residue of EP/2% UiO-66 is increased by 2.52% compared with that of pure EP, indicating that the thermal properties of the EP composite are improved after modification. In addition, the cone test results indicate that EP/2%UiO-66-5L has good flame retardancy and smoke suppression properties, and the peak heat release rate, total smoke production and rate of CO generation values are 25.2%, 5.7% and 38.5% lower than those of the unmodified EP. Moreover, it can be concluded from the Raman test that the graphitization degree of the modified EP composite is strengthened. The above results indicated that after the incorporation of CS@APP@UiO-66 into the EP composites, more char layers formed as physical barriers to prevent the transfer of mass and heat, thus reducing the speed of flame propagation. Therefore, the flame resistance and smoke suppression of the EP composites improved. These favorable characteristics, including high flame retardant efficiency and good smoke suppression, make LbL-functionalized UiO-66 promising for flame retardant polymer applications.
epoxy resin composites / metal organic framework (UiO-66) / layer-by-layer self-assembly (LbL) / flame retardant / smoke suppressant
[1] |
Huo S , Song P , Yu B , Ran S , Chevali V S , Liu L , Fang Z , Wang H . Phosphorus-containing flame retardant epoxy thermosets: recent advances and future perspectives. Progress in Polymer Science, 2021, 114: 101366
CrossRef
Google scholar
|
[2] |
Toldy A , Anna P , Csontos I , Szabó A , Marosi G . Intrinsically flame retardant epoxy resin—fire performance and background—Part I. Polymer Degradation & Stability, 2007, 92(12): 2223–2230
CrossRef
Google scholar
|
[3] |
Shieh J- Y , Wang C- S . Synthesis of novel flame retardant epoxy hardeners and properties of cured products. Polymer, 2001, 42(18): 7617–7625
CrossRef
Google scholar
|
[4] |
Zhi M , Yang X , Fan R , Yue S , Zheng L , Liu Q , He Y . A comprehensive review of reactive flame-retardant epoxy resin: fundamentals, recent developments, and perspectives. Polymer Degradation & Stability, 2022, 201: 109976
CrossRef
Google scholar
|
[5] |
Liang B , Cao J , Hong X , Wang C . Synthesis and properties of a novel phosphorous-containing flame-retardant hardener for epoxy resin. Journal of Applied Polymer Science, 2013, 128(5): 2759–2765
CrossRef
Google scholar
|
[6] |
Song K , Pan Y- T , Zhang J , Song P , He J , Wang D- Y , Yang R . Metal-organic frameworks- based flame-retardant system for epoxy resin: a review and prospect. Chemical Engineering Journal, 2023, 468: 143653
CrossRef
Google scholar
|
[7] |
Wang H , Qiao H , Guo J , Sun J , Li H , Zhang S , Gu X . Preparation of cobalt-based metal organic framework and its application as synergistic flame retardant in thermoplastic polyurethane (TPU). Composites Part B: Engineering, 2020, 182: 107498
CrossRef
Google scholar
|
[8] |
Guo W , Nie S , Kalali E N , Wang X , Wang W , Cai W , Song L , Hu Y . Construction of SiO2@UiO-66 core-shell microarchitectures through covalent linkage as flame retardant and smoke suppressant for epoxy resins. Composites Part B: Engineering, 2019, 176: 107261
CrossRef
Google scholar
|
[9] |
Nabipour H , Wang X , Song L , Hu Y . Metal-organic frameworks for flame retardant polymers application: a critical review. Composites Part A: Applied Science and Manufacturing, 2020, 139: 106113
CrossRef
Google scholar
|
[10] |
Pan Y T , Zhang Z , Yang R . The rise of MOFs and their derivatives for flame retardant polymeric materials: a critical review. Composites Part B: Engineering, 2020, 199: 108265
CrossRef
Google scholar
|
[11] |
Hou Y , Xu Z , Chu F , Gui Z , Song L , Hu Y , Hu W . A review on metal-organic hybrids as flame retardants for enhancing fire safety of polymer composites. Composites Part B: Engineering, 2021, 221: 109014
CrossRef
Google scholar
|
[12] |
Shen R , Yan T- H , Ma R , Joseph E , Quan Y , Zhou H- C , Wang Q . Flammability and thermal kinetic analysis of UiO-66-based PMMA polymer composites. Polymers, 2021, 13(23): 4113
CrossRef
Google scholar
|
[13] |
Cao M , Xiao G , Chen C , Chen C , Yang Z , Zhong F , Shang S , Wang M , Zou R . Synergetic modification of graphitic carbon nitride by Zr-based metal-organic framework and tetraethoxysilane for improving fire performance in composite coatings. Progress in Organic Coatings, 2023, 183: 107756
CrossRef
Google scholar
|
[14] |
Feng W , Zhang J , Yusuf A , Ao X , Shi D , Etacheri V , Wang D- Y . Quasi-solid-state sodium-ion hybrid capacitors enabled by UiO-66@PVDF-HFP multifunctional separators: selective charge transfer and high fire safety. Chemical Engineering Journal, 2022, 427: 130919
CrossRef
Google scholar
|
[15] |
Yang Z , Xiao G , Chen C , Chen C , Zhong F , Cao M , Wang M , Zou R , Li R , Shang S . A novel P, N doped organic-inorganic hierarchical core-shell nanostructures: reducing the fire risk of epoxy resin. Progress in Organic Coatings, 2023, 183: 107776
CrossRef
Google scholar
|
[16] |
Wu X , Qin Z , Zhang X , Yu Z , Zhang W , Yang R , Li D . Micro-nanometer particle composition and functional design of surface nano-structured ammonium polyphosphate and its application in intumescent flame-retardant polypropylene. Nanomaterials, 2022, 12(4): 606
CrossRef
Google scholar
|
[17] |
Unnikrishnan V , Zabihi O , Li Q , Ahmadi M , Yadav R , Kalali E N , Tanwar K , Kiziltas A , Blanchard P , Wang D- Y .
CrossRef
Google scholar
|
[18] |
Deng C- L , Du S- L , Zhao J , Shen Z- Q , Deng C , Wang Y- Z . An intumescent flame retardant polypropylene system with simultaneously improved flame retardancy and water resistance. Polymer Degradation & Stability, 2014, 108: 97–107
CrossRef
Google scholar
|
[19] |
Du B , Ma H , Fang Z . How nano-fillers affect thermal stability and flame retardancy of intumescent flame retarded polypropylene. Polymers for Advanced Technologies, 2011, 22(7): 1139–1146
CrossRef
Google scholar
|
[20] |
Zhang J , Ao X , Zhang X , Wang R , Jin X , Ye W , Xu B , Wang D- Y . Construction of nanomaterials based on molybdenum disulfide decorated onto a metal-organic framework (UiO-66) to improve the fire retardancy of epoxy. ACS Applied Nano Materials, 2022, 5(12): 17731–17740
CrossRef
Google scholar
|
[21] |
Ou M , Cui J , Zhao Z , Li R , Guan H , Liu L , Jiao C , Chen X . Solvent-free intumescent fire protection epoxy coatings with excellent smoke suppression, toxicity reduction, and durability enabled by a micro/nano-structured P/N/Si-containing flame retardant. Progress in Organic Coatings, 2023, 183: 107762
CrossRef
Google scholar
|
[22] |
Sun Q , Wang J , Meng X , Zhang J , Yan H . A novel high-efficient P/N/Si-containing APP-based flame retardant with a silane coupling agent in its molecular structure for epoxy resin. Chinese Journal of Chemical Engineering, 2023, 55: 137–147
CrossRef
Google scholar
|
[23] |
Shen R , Quan Y , Zhang Z , Ma R , Wang Q . Metal-organic framework as an efficient synergist for intumescent flame retardants against highly flammable polypropylene. Industrial & Engineering Chemistry Research, 2022, 61(21): 7292–7302
CrossRef
Google scholar
|
[24] |
Jin X , Wu X , Liu Q , Sun S , Cui S , Zhang S , Chen C . Preparation of a novel Fe-MOF as the flame retardant synergist and its application in polystyrene. Polymers for Advanced Technologies, 2024, 35(1): e6221
CrossRef
Google scholar
|
[25] |
De Villiers M M , Otto D P , Strydom S J , Lvov Y M . Introduction to nanocoatings produced by layer-by-layer (LbL) self-assembly. Advanced Drug Delivery Reviews, 2011, 63(9): 701–715
CrossRef
Google scholar
|
[26] |
Weng G- M , Li J , Alhabeb M , Karpovich C , Wang H , Lipton J , Maleski K , Kong J , Shaulsky E , Elimelech M .
CrossRef
Google scholar
|
[27] |
Li K , Zou G , Jiao T , Xing R , Zhang L , Zhou J , Zhang Q , Peng Q . Self-assembled MXene-based nanocomposites via layer-by-layer strategy for elevated adsorption capacities. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2018, 553: 105–113
CrossRef
Google scholar
|
[28] |
Kotov N A . Layered biomimetic composites from MXenes with sequential bridging. Angewandte Chemie International Edition, 2022, 61(13): e202114140
CrossRef
Google scholar
|
[29] |
Wu Y , Long Y , Li Q- L , Han S , Ma J , Yang Y- W , Gao H . Layer-by-layer (LBL) self-assembled biohybrid nanomaterials for efficient antibacterial applications. ACS Applied Materials & Interfaces, 2015, 7(31): 17255–17263
CrossRef
Google scholar
|
[30] |
Bansal K , Mansouri S , Bajwa D , Swarup S , Quadir M . Synthesis of phytic acid-layered zinc oxide hybrid nanoparticles and their flame-retardant applications in polyurethane coatings. Journal of Coatings Technology and Research, 2024, 21(1): 369–382
CrossRef
Google scholar
|
[31] |
Cavka J H , Jakobsen S , Olsbye U , Guillou N , Lamberti C , Bordiga S , Lillerud K P . A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability. Journal of the American Chemical Society, 2008, 130(42): 13850–13851
CrossRef
Google scholar
|
[32] |
Katz M J , Brown Z J , Colón Y J , Siu P W , Scheidt K A , Snurr R Q , Hupp J T , Farha O K . A facile synthesis of UiO-66, UiO-67 and their derivatives. Chemical Communications, 2013, 49(82): 9449–9451
CrossRef
Google scholar
|
[33] |
Zou D , Liu D . Understanding the modifications and applications of highly stable porous frameworks via UiO-66. Materials Today Chemistry, 2019, 12: 139–165
CrossRef
Google scholar
|
[34] |
Tan Y , Zhang W , Gao Y , Wu J , Tang B . Facile synthesis and supercapacitive properties of Zr-metal organic frameworks (UiO-66). RSC Advances, 2015, 5(23): 17601–17605
CrossRef
Google scholar
|
[35] |
Semrau A L , Fischer R A . High-quality thin films of UiO-66-NH2 by coordination modulated layer-by-layer liquid phase epitaxy. Chemistry, 2021, 27(33): 8509–8516
CrossRef
Google scholar
|
[36] |
Chen C , Chen D , Xie S , Quan H , Luo X , Guo L . Adsorption behaviors of organic micropollutants on zirconium metal-organic framework UiO-66: analysis of surface interactions. ACS Applied Materials & Interfaces, 2017, 9(46): 41043–41054
CrossRef
Google scholar
|
[37] |
Guo W , Liu J , Zhang P , Song L , Wang X , Hu Y . Multi-functional hydroxyapatite/polyvinyl alcohol composite aerogels with self-cleaning, superior fire resistance and low thermal conductivity. Composites Science and Technology, 2018, 158: 128–136
CrossRef
Google scholar
|
[38] |
Li J , Gong J- L , Zeng G- M , Zhang P , Song B , Cao W- C , Liu H- Y , Huan S- Y . Zirconium-based metal organic frameworks loaded on polyurethane foam membrane for simultaneous removal of dyes with different charges. Journal of Colloid and Interface Science, 2018, 527: 267–279
CrossRef
Google scholar
|
[39] |
Ragon F , Campo B , Yang Q , Martineau C , Wiersum A D , Lago A , Guillerm V , Hemsley C , Eubank J F , Vishnuvarthan M .
CrossRef
Google scholar
|
[40] |
Valenzano L , Civalleri B , Chavan S , Bordiga S , Nilsen M H , Jakobsen S , Lillerud K P , Lamberti C . Disclosing the complex structure of UiO-66 metal organic framework: a synergic combination of experiment and theory. Chemistry of Materials, 2011, 23(7): 1700–1718
CrossRef
Google scholar
|
[41] |
Guo W , Zhao Y , Wang X , Cai W , Wang J , Song L , Hu Y . Multifunctional epoxy composites with highly flame retardant and effective electromagnetic interference shielding performances. Composites Part B: Engineering, 2020, 192: 107990
CrossRef
Google scholar
|
[42] |
Guo W , Wang X , Huang J , Zhou Y , Cai W , Wang J , Song L , Hu Y . Construction of durable flame-retardant and robust superhydrophobic coatings on cotton fabrics for water-oil separation application. Chemical Engineering Journal, 2020, 398: 125661
CrossRef
Google scholar
|
[43] |
Guo W , Wang X , Zhang P , Liu J , Song L , Hu Y . Nano-fibrillated cellulose-hydroxyapatite based composite foams with excellent fire resistance. Carbohydrate Polymers, 2018, 195: 71–78
CrossRef
Google scholar
|
[44] |
Huang Z , Li S , Tsai L- C , Jiang T , Ma N , Tsai F- C . Flame retardant polypropylene with a single molecule intumescent flame retardant based on chitosan. Materials Today Communications, 2022, 33: 104689
CrossRef
Google scholar
|
[45] |
Liu L , Yao M , Zhang H , Zhang Y , Feng J , Fang Z , Song P . Aqueous self-assembly of bio-based flame retardants for fire-retardant, smoke-suppressive, and toughened polylactic acid. ACS Sustainable Chemistry & Engineering, 2022, 10(49): 16313–16323
CrossRef
Google scholar
|
[46] |
Wang X , Qi P , Zhang S , Jiang S , Li Y , Sun J , Fei B , Gu X , Zhang S . A novel flame-retardant modification strategy for UiO66-NH2 by encapsulating triethyl phosphate: preparation, characterization, and multifunctional application in poly(lactic acid). Materials Today Chemistry, 2023, 30: 101550
CrossRef
Google scholar
|
[47] |
Sai T , Ran S , Guo Z , Fang Z . A Zr-based metal organic frameworks towards improving fire safety and thermal stability of polycarbonate. Composites Part B: Engineering, 2019, 176: 107198
CrossRef
Google scholar
|
[48] |
Huang J , Guo W , Wang X , Niu H , Song L , Hu Y . Combination of cardanol-derived flame retardant with SiO2@MOF particles for simultaneously enhancing the toughness, anti-flammability and smoke suppression of epoxy thermosets. Composites Communications, 2021, 27: 100904
CrossRef
Google scholar
|
[49] |
Zhang X , Zhang W , Zeng G , Du J , Zhang W , Yang R . The effect of different smoke suppressants with APP for enhancing the flame retardancy and smoke suppression on vinyl ester resin. Polymer Engineering and Science, 2020, 60(2): 314–322
CrossRef
Google scholar
|
[50] |
Jiao C , Wang H , Zhang Z , Chen X . Preparation and properties of an efficient smoke suppressant and flame-retardant agent for thermoplastic polyurethane. Polymers for Advanced Technologies, 2017, 28(12): 1690–1698
CrossRef
Google scholar
|
[51] |
Wu K , Zhou C , Pan Z , Cheng Q , Feng L , Wu H , Zhou H . Flame-retardant epoxy resin with good smoke-suppression endowed by chitosan-cobalt/phosphorus complex. Journal of Applied Polymer Science, 2024, 141(6): e54919
CrossRef
Google scholar
|
[52] |
Duan R , Wu H , Li J , Zhou Z , Meng W , Liu L , Qu H , Xu J . Phosphor nitrile functionalized UiO-66-NH2/graphene hybrid flame retardants for fire safety of epoxy. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2022, 635: 128093
CrossRef
Google scholar
|
[53] |
WangRZhangXYuanMWangD- YZhangJPanY- T. Fire retardancy of epoxy composites: a comparative investigation on the influence of porous structure and transition metal of metal-organic framework. Composites Communications, 2024
|
[54] |
Zhang J , Li Z , Shao Z- B , Zhang L , Wang D- Y . Hierarchically tailored hybrids via interfacial-engineering of self-assembled UiO-66 and Prussian Blue analogue: novel strategy to impart epoxy high-efficient fire retardancy and smoke suppression. Chemical Engineering Journal, 2020, 400: 125942
CrossRef
Google scholar
|
[55] |
Chen C , Song W , Jiang M , Zhang R , Li S , Cai Y , Yao J . SiO2/MOFs-based synergistic flame retardants provide enhanced fire safety for epoxy resins. Materials Today Communications, 2023, 35: 105805
CrossRef
Google scholar
|
[56] |
Zhang G , Dong Y , Yao M , Cui Y , Meng W , Wang S , Qu H , Xu J . Preparation of a MOF flame retardant containing phosphazene ring and its effect on the flame retardant of epoxy resin. Reactive & Functional Polymers, 2023, 191: 105670
CrossRef
Google scholar
|
[57] |
Zhang A , Zhang J , Liu L , Dai J , Lu X , Huo S , Hong M , Liu X , Lynch M , Zeng X .
CrossRef
Google scholar
|
[58] |
ChenQLiuLZhangAWangWWangZZhangJFengJHuoSZengXSongP. An iron phenylphosphinate@graphene oxide nanohybrid enabled flame-retardant, mechanically reinforced, and thermally conductive epoxy nanocomposites. Chemical Engineering Journal, 2022
|
[59] |
Velencoso M M , Battig A , Markwart J C , Schartel B , Wurm F R . Molecular firefighting— how modern phosphorus chemistry can help solve the flame retardancy task. Angewandte Chemie International Edition, 2018, 57(33): 10450–10467
CrossRef
Google scholar
|
[60] |
Guo W , Wang X , Gangireddy C S R , Wang J , Pan Y , Xing W , Song L , Hu Y . Cardanol derived benzoxazine in combination with boron-doped graphene toward simultaneously improved toughening and flame retardant epoxy composites. Composites Part A: Applied Science and Manufacturing, 2019, 116: 13–23
CrossRef
Google scholar
|
[61] |
Zhang J , Li Z , Qi X , Zhang W , Wang D- Y . Size tailored bimetallic metal-organic framework (MOF) on graphene oxide with sandwich-like structure as functional nano-hybrids for improving fire safety of epoxy. Composites Part B: Engineering, 2020, 188: 107881
CrossRef
Google scholar
|
/
〈 |
|
〉 |