Research progress in metal⁃organic framework⁃based flame retardants in flame⁃retardant polymers

doi:10.19491/j.issn.1001-9278.2024.02.017

Abstract

Abstract:

This paper introduced the applications of metal⁃organic frameworks and their derivatives in the fire⁃retardant polymer field in recent years. The design of metal⁃organic framework flame retardants and their effects on the fire⁃retardant properties of epoxy resins， polystyrene， polyurethane and other materials were highlighted. The possible flame⁃retardant mechanisms of metal⁃organic framework flame retardants were discussed， and their development direction in future was prospected.

Key words: metal?organic framework, flame retardancy, epoxy resin, polystyrene, polyurethane, flame retardancy mechanism

CLC Number:

TQ322.4

WANG Dong. Research progress in metal⁃organic framework⁃based flame retardants in flame⁃retardant polymers[J]. China Plastics, 2024, 38(2): 118-125.

Figures/Tables 8

Fig.1. Schematic diagram of preparation of rGO@LDH［23］

Fig.2. Preparation of MgAl@NiCo and morphology and strength of char residue of the EP composites after cone calorimetry test［24］

Fig.3. Synthetic route of NiCo⁃LDH@PZS［30］

Fig.4. TEM images of CP and CPPHS and the supposed dispersion mechanism in EP matrix［32］

Fig.5. HRR and total heat release curves of PS and its composites［37］

Fig.6. SEM images of Fe⁃MOF， P⁃Fe⁃MOF and T⁃Fe⁃MOF［41］

Fig.7. Synthesis schematic diagram of Ni⁃MOF and DOPO@Co⁃MOF and mechanical properties of the modified composites［35，46］

Fig.8. Synthesis schematic diagram and flame retardant properties of ZIF⁃8@cellulose composite aerogel［62］

References 64

1	Samiee R， Montazeri S， Ramezanzadeh B， et al. Ce⁃MOF nanorods/aluminum hydroxide （AlTH） synergism effect on the fire⁃retardancy/smoke⁃release and thermo⁃mechanical properties of a novel thermoplastic acrylic intumescent composite coating［J］. Chem Eng J， 2022， 428： 132533.
2	Feng C， Liu X， Zhu T， et al. Catalytic oxidation of CO on noble metal⁃based catalysts ［J］. Environ Sci Pollut Res， 2021， 28： 24 847⁃24 871.
3	Chen P， Wang M， Li G， et al. Construction of ZIF-67⁃On⁃UiO-66 catalysts as a platform for efficient overall water splitting ［J］. Inorg Chem， 2022， 61（46）：18 424⁃18 433.
4	Sun T， Zhang S， Xu L， et al. An efficient multifunctional hybrid electrocatalyst： Ni₂P nanoparticles on MOF⁃derived Co，N⁃doped porous carbon polyhedrons for oxygen reduction and water splitting ［J］. Chem Commun， 2018， 54： 12 101⁃12 104.
5	Peralta R A， Huxley M T， Evans J D， et al. Highly active gas phase organometallic catalysis supported within metal⁃organic framework pores ［J］. J Am Chem Soc， 2020， 142： 13 533⁃13 543.
6	Pan Y T， Zhang Z， Yang R. The rise of MOFs and their derivatives for flame retardant polymeric materials： A critical review ［J］. Compos Part B⁃Eng， 2020， 199： 108265.
7	Song K， Zhang H， Pan Y T， et al. Metal⁃organic framework⁃derived bird's nest⁃like capsules for phosphorous small molecules towards flame retardant polyurea composites ［J］. J Colloid Interface Sci， 2023， 643： 489⁃501.
8	Song K， Li X， Pan Y T， et al. The influence on flame retardant epoxy composites by a bird's nest⁃like structure of Co⁃based isomers evolved from zeolitic imidazolate framework-67 ［J］. Polym Degrad Stab， 2023， 211： 110318.
9	Hou Y， Xu Z， Chu F， et al. A review on metal⁃organic hybrids as flame retardants for enhancing fire safety of polymer composites ［J］. Compos Part B⁃Eng， 2021， 221： 109014.
10	Song K， Pan Y T， Zhang J， et al. Metal⁃organic frameworks⁃based flame⁃retardant system for epoxy resin： a review and prospect ［J］. Chem Eng J， 2023， 468： 143653.
11	Zhang J， Li Z， Qi X， et al. Size tailored bimetallic metal⁃organic framework （MOF） on graphene oxide with sandwich⁃like structure as functional nano⁃hybrids for improving fire safety of epoxy ［J］. Compos Part B⁃Eng， 2020， 188： 107881.
12	Hou Y， Qiu S， Xu Z， et al. Which part of metal⁃organic frameworks affects polymers' heat release， smoke emission and CO production behaviors more significantly， metallic component or organic ligand？［J］. Compos Part B⁃Eng， 2021， 223： 109131.
13	Chu H， Wu M， Liu X， et al. Uniformly⁃dispersed black phosphorene as flame⁃retardant epoxy composites via iterative dispersion strategy ［J］. ACS Appl Nano Mater， 2023， 6： 17 548⁃17 559.
14	Tian P X， Li Y D， Weng Y， et al. Reprocessable， chemically recyclable， and flame⁃retardant biobased epoxy vitrimers［J］. Eur Polym J， 2023， 193： 112078.
15	Mahajan D S， Sonawane S A， Bari M L， et al. Stannate and surface functionalized molybdate of zinc for enhanced flame retardancy of epoxy nanocomposites ［J］. J Appl Polym Sci， 2023， 140： e53610.
16	Petit C， Bandosz T J. MOF⁃graphite oxide composites： combining the uniqueness of graphene layers and metal⁃organic frameworks ［J］. Adv Mater， 2009， 21： 4 753⁃4 757.
17	Yoo D K， Lee G， Mondol M M H， et al. Preparation and applications of metal⁃organic frameworks composed of sulfonic acid ［J］. Coord Chem Rev， 2023， 474： 214868.
18	Sun M， Hanif A， Wang T， et al. Ambient temperature NO₂ removal by reversible NO₂ adsorption on copper⁃based metal⁃organic frameworks （MOFs）⁃derived nanoporous adsorbents ［J］. Sep Purif Technol， 2023， 314： 123563.
19	Petit C， Mendoza B， Bandosz T J. Hydrogen sulfide adsorption on MOFs and MOF/graphite oxide composites ［J］. Chem Phys Chem， 2010， 11： 3 678⁃3 684.
20	Xu B， Xu W， Wang G， et al. Zeolitic imidazolate frameworks-8 modified graphene as a green flame retardant for reducing the fire risk of epoxy resin ［J］. Polym Adv Technol， 2018， 29： 1 733⁃1 743.
21	Wang J， Zheng X， Zhu Y， et al. Covalently functionalized hierarchical MnO₂@LDH nanostructure as building blocks for fire⁃safe and mechanic⁃robust epoxy composites ［J］. Appl Surf Sci， 2022： 153262.
22	Nyambo C， Kandare E， Wilkie C A. Thermal stability and flammability characteristics of ethylene vinyl acetate （EVA） composites blended with a phenyl phosphonate⁃intercalated layered double hydroxide （LDH）， melamine polyphosphate and/or boric acid ［J］. Polym Degrad Stab， 2009， 94： 513⁃520.
23	Pan Y T， Wan J， Zhao X， et al. Interfacial growth of MOF⁃derived layered double hydroxide nanosheets on graphene slab towards fabrication of multifunctional epoxy nanocomposites ［J］. Chem Eng J， 2017， 330： 1 222⁃1 231.
24	Zhang Z， Qin J， Zhang W， et al. Synthesis of a novel dual layered double hydroxide hybrid nanomaterial and its application in epoxy nanocomposites ［J］. Chem Eng J， 2020， 381： 122777.
25	Han D， Wang H， Lu T， et al. Scalable manufacturing green core–shell structure flame retardant， with enhanced mechanical and flame⁃retardant performances of polylactic acid ［J］. J Polym Environ， 2022， 30： 2 516⁃2 533.
26	He T， Guo J， Qi C， et al. Core⁃shell structure flame retardant Salen⁃PZN⁃Cu@Ni⁃Mof microspheres enhancing fire safety of epoxy resin through the synergistic effect ［J］. J Polym Res， 2021， 29： 27.
27	Guo W， Nie S， Kalali E N， et al. Construction of SiO₂@UiO-66 core–shell microarchitectures through covalent linkage as flame retardant and smoke suppressant for epoxy resins ［J］. Compos Part B⁃Eng， 2019， 176： 107261.
28	Song K， Wang Y， Ruan F， et al. Synthesis of a reactive template⁃induced core–shell PZS@ZIF-67 composite microspheres and its application in epoxy composites ［J］. Polymers， 2021， 13： 2646.
29	Lv X， Zeng W， Yang Z， et al. Fabrication of ZIF-8@polyphosphazene core⁃shell structure and its efficient synergism with ammonium polyphosphate in flame⁃retarding epoxy resin ［J］. Polym Adv Technol， 2020， 31： 997⁃1 006.
30	Zhou X， Mu X， Cai W， et al. Design of hierarchical NiCo⁃LDH@PZS hollow dodecahedron architecture and application in high⁃performance epoxy resin with excellent fire safety ［J］. ACS Appl Mater Inter， 2019， 11： 41 736⁃41 749.
31	Hou B， Song K， Ur Rehman Z， et al. Precise control of a yolk⁃double shell metal⁃organic framework⁃based nanostructure provides enhanced fire safety for epoxy nanocomposites ［J］. ACS Appl Mater Inter， 2022， 14： 14 805⁃14 816.
32	Song X， Hou B， Han Z， et al. Dual nucleation sites induced by ZIF-67 towards mismatch of polyphosphazene hollow sub⁃micron polyhedrons and nanospheres in flame retardant epoxy matrix ［J］. Chem Eng J， 2023， 470： 144278.
33	Hou B， Wang Y， Li B， et al. Bio⁃based flame⁃retardant plasticizers derived from L⁃lactic acid： Effects of valence states of phosphorus structure on fire safety， flexibility and transparency of poly（lactic acid）［J］. Chem Eng J， 2023， 474： 145563.
34	Zhang J， Li Z， Zhang L， et al. Green synthesis of biomass phytic acid⁃functionalized UiO-66⁃NH₂ hierarchical hybrids toward fire safety of epoxy resin ［J］. ACS Sustainable Chem Eng， 2019， 8： 994⁃1 003.
35	Huang R， Guo X， Ma S， et al. Novel phosphorus⁃nitrogen⁃containing ionic liquid modified metal⁃organic framework as an effective flame retardant for epoxy resin ［J］. Polymers， 2020， 12： 108.
36	Huang J， Zhao Z， Chen T， et al. Preparation of highly dispersed expandable graphite/polystyrene composite foam via suspension polymerization with enhanced fire retardation ［J］. Carbon， 2019， 146： 503⁃512.
37	Hou Y， Hu W， Gui Z， et al. Preparation of Metal⁃organic frameworks and their application as flame retardants for polystyrene ［J］. Industrial & Engineering Chemistry Research， 2017， 56： 2 036⁃2 045.
38	Hou Y， Hu W， Zhou X， et al. Vertically aligned nickel 2⁃methylimidazole metal⁃organic framework fabricated from graphene oxides for enhancing fire safety of polystyrene ［J］. Industrial & Engineering Chemistry Research， 2017， 56： 8 778⁃8 786.
39	Chen W， Jiang Y， Qiu R， et al. Investigation of UiO-66 as flame retardant and its application in improving fire safety of polystyrene ［J］. Macromol Res， 2020， 28： 42⁃50.
40	Wang X， Wu T， Hong J， et al. Organophosphorus modified hollow bimetallic organic frameworks： Effective adsorption and catalytic charring of pyrolytic volatiles ［J］. Chem Eng J， 2021， 421： 129697.
41	Zhao H， Yuan B， Zhan Y， et al. Upgrading the pore⁃size scale of MIL-53 from microporous to macroporous for adsorbing triethyl phosphate and reducing the fire risk of polystyrene ［J］. Compos Part A⁃Appl S， 2022， 159： 107003.
42	Baochai L， Bakar A A， Mohamad Z. An overview of the recent advances in flame retarded poly（lactic acid）［J］. Polym Adv Technol， 2023， 34： 1 435⁃1 450.
43	Cheng X W， Guan J P， Tang R C， et al. Improvement of flame retardancy of poly（lactic acid） nonwoven fabric with a phosphorus⁃containing flame retardant ［J］. J Ind Text， 2015， 46： 914⁃928.
44	Elangovan D， Yuzay I E， Selke S E M， et al. Poly（L⁃lactic acid） metal organic framework composites： optical， thermal and mechanical properties ［J］. Polym Int， 2012， 61： 30⁃37.
45	Zhang M， Shi X， Dai X， et al. Improving the crystallization and fire resistance of poly（lactic acid） with nano⁃ZIF-8@GO ［J］. J Mater Sci， 2018， 53： 7 083⁃7 093.
46	Wang X， Wang S， Wang W， et al. The flammability and mechanical properties of poly （lactic acid） composites containing Ni⁃MOF nanosheets with polyhydroxy groups ［J］. Compos Part B⁃Eng， 2020， 183： 107568.
47	Hou Y， Liu L， Qiu S， el at. DOPo⁃modified two⁃dimensional co⁃based metal–organic framework： preparation and application for enhancing fire safety of poly（lactic acid）［J］. ACS Appl Mater Inter， 2018， 10： 8 274⁃8 286.
48	Zhang M， Gao Y， Zhan Y， et al. Preparing the degradable， flame⁃retardant and low dielectric constant nanocomposites for flexible and miniaturized electronics with poly（lactic acid）， nano ZIF-8@GO and resorcinol di（phenyl phosphate）［J］. Materials 2018， 11（9）： 1756.
49	Chen X， Feng X， Jiao C. Combustion and thermal degradation properties of flame⁃retardant TPU based on EMIMPF6 ［J］. J Therm Anal Calorim， 2017， 129： 851⁃857.
50	Li M， Hao F， Chen Y， et al. Facile alteration of the molecular structure of phosphonamide for efficient flame retardancy in TPU ［J］. Compos Commun， 2023， 44： 101759.
51	Cheng J， Ma D， Li S， et al. Preparation of zeolitic imidazolate frameworks and their application as flame retardant and smoke suppression agent for rigid polyurethane foams ［J］. Polymers 2020， 12（2）： 347.
52	Wang H， Qiao H， Guo J， et al. Preparation of cobalt⁃based metal organic framework and its application as synergistic flame retardant in thermoplastic polyurethane （TPU）［J］. Compos Part B⁃Eng， 2020， 182： 107498.
53	Hou Y， Xu Z， Yuan Y， et al. Nanosized bimetal⁃organic frameworks as robust coating for multi⁃functional flexible polyurethane foam： rapid oil⁃absorption and excellent fire safety ［J］. Compos Sci Technol， 2019， 177： 66⁃72.
54	Zhao S， Yin L， Zhou Q， et al. In situ self⁃assembly of zeolitic imidazolate frameworks on the surface of flexible polyurethane foam： Towards for highly efficient oil spill cleanup and fire safety ［J］. Appl Surf Sci， 2020， 506： 144700.
55	Xu B， Xu W， Liu Y， et al. Surface modification of α⁃zirconium phosphate by zeolitic imidazolate frameworks-8 and its effect on improving the fire safety of polyurethane elastomer ［J］. Polym Adv Technol， 2018， 29： 2，816⁃2，826.
56	Zhang Y， Zeng X， Li H， et al. Zirconium phosphate functionalized by hindered amine： A new strategy for effectively enhancing the flame retardancy of addition⁃cure liquid silicone rubber ［J］. Mater Lett， 2016， 174： 230⁃233.
57	Ahmad H， Rodrigue D. Crosslinked polyethylene： A review on the crosslinking techniques， manufacturing methods， applications， and recycling ［J］. Polymer Engineering & Science， 2022， 62： 2 376⁃2 401.
58	Blake N， Turner Z R， Buffet J C， et al. Flame retardant phosphonate⁃functionalised polyethylenes ［J］. Polym Chem， 2023， 14： 3 175⁃3 185.
59	Xie J， X.Shi， Zhang M， et al. Improving the flame retardancy of polypropylene by nano metal⁃organic frameworks and bioethanol coproduct ［J］. Fire Mater， 2019， 43： 373⁃380.
60	Sai T， Ran S， Guo Z， et al. A Zr⁃based metal organic frameworks towards improving fire safety and thermal stability of polycarbonate ［J］. Compos Part B⁃Eng， 2019， 176： 107198.
61	Zhou S， Apostolopoulou⁃Kalkavoura V， Tavares da Costa M V， et al. Elastic aerogels of cellulose nanofibers@metal⁃organic frameworks for thermal insulation and fire retardancy ［J］. Nano⁃Micro Lett， 2019， 12： 9.
62	Nabipour H， Nie S， Wang X， et al. Highly flame retardant zeolitic imidazole framework-8@cellulose composite aerogels as absorption materials for organic pollutants ［J］. Cellulose， 2020， 27： 2 237⁃2 251.
63	Zhou Z， Li Y， Fang T， et al. MOF⁃derived Co₃O₄ polyhedrons as efficient polysulfides barrier on polyimide separators for high temperature lithium⁃sulfur batteries ［J］. Nanomaterials， 2019， 9（11）： 1574.
64	Zeng G， Zhao J， Feng C， et al. Flame⁃retardant bilayer separator with multifaceted van der waals interaction for lithium⁃ion batteries ［J］. ACS Appl Mater Inter， 2019， 11： 26 402⁃26 411.

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