GB2622099A - Ternary nanocomposite flame retardant, flame retardant epoxy resin and method for preparing the same - Google Patents
Ternary nanocomposite flame retardant, flame retardant epoxy resin and method for preparing the same Download PDFInfo
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- GB2622099A GB2622099A GB2212885.4A GB202212885A GB2622099A GB 2622099 A GB2622099 A GB 2622099A GB 202212885 A GB202212885 A GB 202212885A GB 2622099 A GB2622099 A GB 2622099A
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- flame retardant
- mxene
- epoxy resin
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 110
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 110
- 239000003063 flame retardant Substances 0.000 title claims abstract description 91
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 26
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 46
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002135 nanosheet Substances 0.000 claims abstract description 24
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 19
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000006185 dispersion Substances 0.000 claims abstract description 14
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 12
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 6
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims abstract description 5
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 4
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 239000000843 powder Substances 0.000 claims description 38
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 32
- 239000008367 deionised water Substances 0.000 claims description 32
- 229910021641 deionized water Inorganic materials 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 31
- 239000000047 product Substances 0.000 claims description 25
- 229940112669 cuprous oxide Drugs 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 238000009210 therapy by ultrasound Methods 0.000 claims description 13
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 4
- 238000010335 hydrothermal treatment Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002211 L-ascorbic acid Substances 0.000 claims description 2
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims 1
- 229910017610 Cu(NO3) Inorganic materials 0.000 abstract 1
- 229910009818 Ti3AlC2 Inorganic materials 0.000 abstract 1
- 238000002485 combustion reaction Methods 0.000 description 17
- 239000000779 smoke Substances 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 12
- 230000003247 decreasing effect Effects 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 230000000670 limiting effect Effects 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002131 composite material Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 231100000331 toxic Toxicity 0.000 description 5
- 230000002588 toxic effect Effects 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 239000003517 fume Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 238000004786 cone calorimetry Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 229910002441 CoNi Inorganic materials 0.000 description 1
- 102100024452 DNA-directed RNA polymerase III subunit RPC1 Human genes 0.000 description 1
- 101000689002 Homo sapiens DNA-directed RNA polymerase III subunit RPC1 Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5033—Amines aromatic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/016—Flame-proofing or flame-retarding additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2248—Oxides; Hydroxides of metals of copper
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/54—Inorganic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/66—Substances characterised by their function in the composition
- C08L2666/84—Flame-proofing or flame-retarding additives
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Abstract
A ternary nanocomposite flame retardant comprises 5 wt.% MXene nanosheets, 45 wt.% layered double metal hydroxide (LDH), and 50 wt.% Cu2O nanocubes. In another aspect, a flame retardant epoxy resin composition comprises 80.4 wt.% epoxy resin, 17.6 wt.% curing agent (e.g. 4,4’-diaminodiphenylmethane), and 2 wt.% ternary nanocomposite flame retardant. A method of producing the ternary nanocomposite flame retardant is also disclosed. The method comprises forming MXene nanosheets by dissolving LiF in HCl before adding Ti3AlC2 to obtain a Ti3C2Tx dispersion. This dispersion is combined with Co(NO3)2.6H2O to which dimethylimidazole is introduced to give ZIF-67/MXene. Ni(NO3)2.6H2O is then added to yield CoNi-LDH/MXene. Cu2O nanocubes are formed by mixing Cu(NO3)2.3H2O, NaOH, and ascorbic acid and the nanocubes and CoNi-LDH/MXene are subsequently combined in 1:1 ratio to produce the ternary nanocomposite flame retardant. The layered double metal hydroxide is located on MXene nanosheets and the nanocubes adhere to the layered double metal hydroxide.
Description
Description
TERNARY NANOCOMPOSITE FLAME RETARDANT, FLAME RETARDANT
EPDXY RESIN AND METHOD FOR PREPARING THE SAME
TECHNICAL FIELD
The present invention relates to the technical field of epoxy resins, and in particular to a ternary nanocomposite flame retardant, a flame retardant epoxy resin and a method for preparing the same.
BACKGROUND ART
Epoxy resin (EP) has high flammability and can generate a large amount of toxic and harmful gases in the combustion process. The current practice is to add flame retardant to epoxy resin to inhibit the flammability of epoxy resin. The traditional inorganic flame retardant additives, such as aluminum hydroxide and magnesium hydroxide, need to be added in a lot to achieve satisfactory flame retardant effect, and the traditional flame retardant additives can only inhibit the heat release rate of polymeric materials in the combustion process without inhibiting the toxic gases and smoke generated in the combustion process.
SUMMARY
It is an object of the present invention to provide a ternary nanocomposite flame retardant and a flame retardant epoxy resin, wherein the ternary nanocomposite flame retardant can achieve good flame retardancy of the epoxy resin with a low addition amount (< 6% wt), reduce the heat release rate during the combustion of the epoxy resin, inhibit the generation of toxic and harmful fumes and gases during the combustion, and enhance the mechanical properties of the epoxy resin, The technical solution adopted by the present invention is: A ternary nanocomposite flame retardant comprises MXene nanosheets, layered double metal hydroxides(LDH), and cuprous oxide nanocubes; in percentage by mass, 5% MXene nanosheets, 45% layered double metal hydroxides, and 50% cuprous oxide nanocubes.
Mxene nanosheets have a highly thermally stable layered stmcture, which can act as a rigid barrier to prevent the transfer of fragments, thereby improving the fire safety of polymers. LDH decomposes endothennicalbc which reduces the heat release of combustion of the polymer, and the catalytic carbon sequestration effect of cuprous oxide reduces the generation of harmful gases and fumes. All three components produce metal oxides that can reinforce the carbon layer during combustion.Compactcarbon layer can geweas physical barriers, hinder heat and oxygen transfer, and improve flame retardancy.
A method for preparing a ternary nanocompos te flame retardant comprising: step 1, preparation of NIXene nanoshcets; firstly, lithium fluoride powder is dissolved into hydrochloric acid, Ti3A1C2 powder is added into the mixed solution, kept stirring, and reacted in a water bath; the product is then centrifuged and washed with deionized water; finally, the product is dispersed in deionizedwater for ultrasonic treatment, and then placed in a centrifuge for centrifugal separation to prepare a dispersion of Ti3C2Tx; step 2, preparation of CoNi-LDH/MXene; the Ti3C2Tx dispersion prepared in step 1 and cobalt nitrate hexahydrate are dispersed in deionized water, and are ultrasonically stirred in a three-neck flask, then a methanol solution containing dimethylimidazole is added to the three-neck flask, and is stirred to prepare a ZW-67/MXene solution; an ethanol solution containing nickel nitrate hexahydrate is added into the Z1F-67/1MXene solution, stiffed, then placed same into a centrifuge for centrifugal treatment, washed with deionizedwater for three times after centrifugation, and washed with ethanol for three times, and vacuum-dried the product to prepare a CoNi-LDH/MXene powder; step 3, preparation of Cu/O/CoNi-LDH/MXene; a copper nitrate trilaydrate solution and a sodium hydroxide solution are mixed and stirred, then an ascorbic acid aqueous solution is added, stirred under water bath conditions, and then centrifuged to obtain a precipitate, the precipitate is washed with deionized water and ethanol, and finally the product is dried in vacuum to prepare a cuprous oxide Cu20 nanocube powder; the Cu/0 powder and the CoNi-LDH/MXene powder prepared in step 2 are mixed in a mass ratio of 1: 1, dispersed same in deionized water, and the two arc combined through hydrothermal 30 treatment; the product is placed into a centrifuge for centrifugal treatment, then the precipitate is taken out, washed with deionizedwater for three times, ethanol for three times, and then vacuum dried to prepare a Cu20/CoNi-LDH/Mxene ternary nanocomposite flame retardant with a structure in which a layered double metal hydroxide grows on MXcne nanoshcets, and cuprous oxide nanocubes adhere to the surface of the layered double metal hydroxide.
The bimetallic hydroxide grows on the MXene nanosheets, and the cuprous oxide nanocubes attach to the layered bimetallic hydroxide surface, forming a unique "sheet + sheet + dot" structure, which can make the three components exert synergistic flame retardant effect and improve the mechanical properties of the polymer As a preferred example, a method for preparing a ternary nanocomposite flame retardant 10 comprises: step 1, preparation of MXene nanosheets; Firstly. Ig of lithium fluoride powder is dissolved in 20 mL of hydrochloric acid, with the hydrochloric acid concentration being 9 mol/L, and lg of Ti3A1C2 powder is added into the mixed solution, kept stirring, and reacted for 24h at 35 °C in a water bath; the product is then centrifuged and washed with deionized water until the pH reached 6-7; finally, the product is dispersed in deionizedwater for ultrasonic treatment for lh, and then placed in a centrifuge for centrifugal separation at a rotation speed of 3500 rpm to prepare a dispersion of Ti3C2Tx; step 2, preparation of CoNi-LDH/MXene; the Ti3C2Tx dispersion prepared in step 1 and 5g of cobalt nitrate hexahydrate are dispersed in 200 mL of deionized water, ultrasonically stirred 10min in a three-neck flask, wherein the Ti3C2Tx dispersion comprises 0.2g Ti3C2Tx, then 200 mL of a methanol solution containing 6g of dimethylimidazole is added to the three-neck flask, and is stirred for 12h to prepare a LIT-67/MXene solution; 200 mL of an ethanol solution containing 58 of nickel nitrate hexahydrate is added into the Z1F-67/MXene solution, stirred for 10h, then placed same into a centrifuge for centrifugal treatment, with the centrifugal rotation speed being 10000 rpm, washed with deionizedwater for three times after centrifugation, and washed with ethanol for three times, and vacuum-dried the product to prepare a CoNi-LDH/MXene powder; step 3, preparation of Cu20/CoNi-LDH/MXene; 300 mL of a 0.01 mol/L copper nitrate trihydrate solution and 60 mL of a 1 mol/L sodium 30 hydroxide solution are mixed, stirred for 30 min, then 60 mL of a 0.5 mon ascorbic acid aqueous solution is added, stirred for 3h at 50 °C under water bath conditions, centrifuged at the rotation speed of 10000 rpm to obtain a precipitate, the precipitate is washed with dcionized water and ethanol, and finally the product is dried in vacuum at 60 °C to prepare a cuprous oxide Cu20 nanocube powder; the Cu20 powder and the CoNi-TDH/MXene powder prepared in step 2 are mixed in a mass ratio of 1: 1, dispersed same in deionized water, and the two are combined through a hydrothermal treatment at 120 °C; the product is placed into a centrifuge for centrifugal treatment at the rotation speed of 10000 rpm, then the precipitate is taken out, washed with deionizedwater for three times, ethanol for three times, and then vacuum-dried to prepare a Cu20/CoNi-LDH/MXene nanocomposite flame retardant material, namely, preparing CLMXene with the mass ratio of MXene nanosheets, layered double metal hydroxide and cuprous oxide nanocubes being I: 9: 10.
A flame retardant epoxy resin comprises a ternary nanocomposite flame retardant or a single component thereof, an epoxy resin and a curing agent, in percentage by mass, the ternary nanocomposite flame retardant or a single component thereof accounts for 2%, the epoxy resin accounts for 80.4% and the curing agent accounts for 17.6%, and the components of the ternary nanocomposite flame retardant comprises 5% MXene nanosheets, 45% layered double metal hydroxide and 50% cuprous oxide nanocubcs.
The epoxy resin incorporated with 2% CLMXene composite flame retardant had the best comprehensive performance, increased the combustion residual carbon rate and the limiting oxygen index of epoxy resin, reduced the maximum mass loss rate, and reduced the corresponding temperature.
Preferably, the curing agent is 4, 4'diaminodiphenyl methane, which is capable of imparting excellent electrical properties, corrosion resistance, heat resistance, impact resistance and the like to the epoxy resin.
A method for preparing a flame retardant epoxy resin specifically comprises: dispersing a powder of CLMXene or Cu20 or CoNi-LDH or MXene in acetone, after ultrasonic treatment in a flask, adding an epoxy resin for stirring, placing the flask in an oil bath for stirring, evaporating the acetone, adding a curing agent in a molten state for stirring, pouring the mixture into a mould, placing the mould in an oven for curing, and then naturally cooling to prepare a flame retardant epoxy resin.
Specifically, CLMXene is incorporated in an amount of 2% to 6% by mass. The high flame retardancy of epoxy resin can be achieved with lower content (< 6% wt). The residual carbon rate and limiting oxygen index at 2%, 4% and 6% are increased, the maximum mass loss rate and the temperature corresponding to the maximum mass loss rate are decreased. The tensile strength, elongation at break, flexural strength and flexural modulus are increased.
As a preferred example, the CLMXene is incorporated in an amount of 2% by mass, namely, CLMXene: (epoxy resin -1 curing agent) = 2: 98, wherein the mass ratio of epoxy resin to curing agent is 4.58:1.
The composite flame retardant incorporated with 2% CLMXene showed better flame retardancy and mechanical properties than the composite flame retardant with 2% single-component Cu20 or CoNi-LDH or MXene. When 4% and 6% CLMXene incorporated in the composite flame retardant, the flame retardancy was better, but more flame retardant could destroy the network structure of epoxy resin, resulting in the decrease of mechanical properties.
Specifically, the mold is placed in an oven and cured by: the temperature was maintained at 100°C for 211. and then increased to 150°C for 2h.
Advantageous effects of the present invention are: 1. According to the method for preparing the composite flame retardant of the present invention, a Cu20/CoNi-LDH/MXene flame retardant with a "sheet + sheet + dot" structure is prepared, and the composite flame retardant has a very good flame retardant effect on an epoxy resin, can greatly increase the combustion residual carbon rate and the limiting oxygen index of the epoxy resin, lower the decomposition rate of the epoxy resin, arid can also improve the mechanical properties of the epoxy resin, including tensile strength and flexural strength, and can also greatly inhibit the release of heat and toxic fumes when the epoxy resin is burned.
2. The flame retardant epoxy resin of the present invention can achieve high flame retardancy at a relatively low addition amount of flame retardant (< 6% wt), and the flame retardant epoxy resin obtained by the preparation method has good flame retardancy, a slow heat release rate during combustion, less toxic smoke generation, excellent performance in reducing polymer fire toxicity, and high tensile strength and flexural strength.
BRIEF DESCRIPTION OF THEFIGURES
Fig. 1 shows a scanning electron microscope image of a flan, nanocomposite flame retardant and its intermediates; wherein Fig. 1 (a) shows the structure of MXene; Fig. 1 (b) shows the structure of CoNi-LDH/MXene; Fig. 1 (c) shows the overall structure of CLMXene; Fig. 1 (d) shows a partially enlarged structure of FIG. 1 (c); Fig. 1 (e) shows a partially enlarged structure of FIG. 1 (d); Fig. 1(1) shows an energy spectrum scan of CLIMXene.
Fig. 2 is a thennogravimetric curve under nitrogen of a commercially available epoxy resin and a flame retardant epoxy resin prepared in Comparative Examples 1 to 3 and Examples 2 to 4, respectively; wherein, Fig. 2 (a) is a TG curve under nitrogen of the above epoxy resin; Fig. 2 (b) 10 is a DTG plot under nitrogen of the above epoxy resin.
Fig. 3 shows the results of limiting oxygen index tests of commercially available epoxy resins and flame retardant epoxy resins prepared in Comparative Examples I to 3 and Examples 2 to 4, respectively.
Fig. 4 shows results of mechanical property tests of commercially available epoxy resins and flame retardant epoxy resins prepared in Comparative Examples 1 to 3 and Examples 2 to 4, respectively; wherein Fig. 4 (a) shows the tensile strength; Fig. 4 (b) is a bar graph of flexural strength and flexural modulus, where the left column is flexural strength and the right column is flexural modulus.
Fig. 5 is a graph showing cone calorimetry test results of commercially available epoxy resins and flame retardant epoxy resins prepared in Comparative Examples 1 to 3 and Examples 2 to 4, respectively; wherein. Fig. 5 (a) shows the maximum heat release rate: Fig. 5 (b) shows the total heat release; Fig. 5 (c) shows the maximum smoke production rate; Fig. 5 (d) shows the total smoke production.
DETAILED DESCRIPTION OF THE EMBODIMENTS
The invention will be explained in further detail with reference to the accompanying drawings and detailed description, but it should be understood that the scope of the present invention is not limited to the detailed description.
Example 1
This example is a method for preparing a ternary nanocomposite flame retardant, specifically comprising: step 1, preparation of MXene nanosheets; wherein the molecular formula of the MXenc nanosheets is Ti3C2Tx.
Firstly, lg of lithium fluoride powder is dissolved in 20 mL of hydrochloric acid, with the hydrochloric acid concentration being 9 mol/T, and lg of Ti3A1C2 powder is added into the mixed solution, kept stirring, and reacted for 24h at 35 °C in a water bath; the product is then centrithged and washed with deionized water until the pH reached 6-7: finally, the product is dispersed in deionizedwater for ultrasonic treatment for lh, and then placed in a centrifuge for centrifugal separation at a rotation speed of 3500 rpm to prepare a dispersion of Ti3C2Tx.
Step 2, preparation of CoNi-LDH/MXene; wherein CoNi-LDH is a CoNi layer bimetallic hydroxide.
The TIIC2Tx dispersion prepared in step 1 (containing 0.2g Ti3C2Tx) and 5g of cobalt nitrate hexahydrate are dispersed in 200 mL of deionized water, ultrasonically stirred 10min in a three-neck flask, and then 200 mL of a methanol solution containing 6g of dimethylimidazole is added to the three-neck flask and stirred for 1 2h to prepare a ZIF-67/MXene solution. 200 m L of an ethanol solution containing 5g of nickel nitrate hexahydrate is added into the ZIF-67/MXene solution, stirred for 10h, then placed same into a centrifuge for centrifugal treatment, with the centrifugal rotation speed being 10000 rpm, washed withdeionized water for three times after centrifugation, and washed with ethanol for three times, and vacuum dried the product to prepare a CoNi-LDH/MXene powder.
Step 3, preparation of Cu20/CoNi-LDITMXene 300 mL of a 0.01 mol/L copper nitrate trihydrate solution and 60 mL of a 1 rnol/L sodium hydroxide solution are mixed, stirred for 30 nun, then 60 mL of a 0.5 mol/L ascorbic acid aqueous solution is added, stirred for 3h at 50 °C under water bath conditions, centrifuged at the rotation speed of 10000 rpm to obtain a precipitate, the precipitate is washed with deionized water and ethanol, and finally the product is dried in vacuum at 60 °C to prepare a cuprous oxide nanocube powder.
The C160 powder and the CoNi-LDH/MXene powder prepared in step 2 are mixed in a mass ratio of 1: 1, dispersed same in deionized water, and the two arc combined through a 30 hydrothermal treatment at 120 °C; the product is placed into a centrifuge for centrifugal
S
treatment at the rotation speed of 10000 rpm, then the precipitate is taken out, washed with deionizedwatcr for three times, ethanol for three times, and then vacuum-dried to prepare a Cu20/CoNi-LDH/MXene nanocompositc flame retardant material, namely, preparing CLMXene with the mass ratio of MXene nanosheets, layered double metal hydroxide and cuprous oxide nanocubes being 1: 9: 10. The layered double metal hydroxide grows on the MXene nanosheets, and the cuprous oxide nanocubes adhere to the surface of the layered double metal hydroxide, forming a unique "sheet + sheet + dot" structure.
As shown in Fig. 1, the scanning electron microscope images of ternary nanocomposite flame retardants are shown, wherein (a) is MXene nanosheets. (b) is bimetallic hydroxides grown on MXene nanosheets, and the layered structure of LDH can be clearly seen, and (c) to (f) are structural enlargement and energy spectrum scanning images of CLMXene, and the LDH structure and cuprous oxide nanocubes on MXene nanosheets can be seen.
Example 2
This example is a method for preparing a flame retardant epoxy resin, specifically comprising: 2g of CulO/CoNi-TDH/MXene powder is dispersed in acetone, after ultrasonic treatment for 1 h in a flask, 80.4g of epoxy resin is added, stirred for 30min, the flask is placed in a 90 °C oil bath for stirring, acetone is evaporated, 17.6g of molten 4, 4' diaminodiphenyl methane is added, stirred for 30s, the mixture is poured into a mould, the mould is placed in an oven for curing, the curing temperature is 100 °C and maintained for 2h, then the temperature is increased to 150 °C and maintained for 2h, and the temperature is naturally decreased to prepare a flame retardant epoxy resin. The curing agent in this example is 4, 4'diaminodiphenyl methane.
In this example, the mass percent incorporation of CLMXene is 2%, namely, CLMXene: (epoxy resin + curing agent) = 2: 98, wherein the mass ratio of epoxy resin to curing agent is 4.58: I. Example 3 This example is also a method for preparing a flame retardant epoxy resin, which differs from Example 2 in that CLMXene is incorporated in a mass percentage of 4%, specifically: 4g of Cu20/CoNi-LDH/MXene powder is dispersed in acetone, after ultrasonic treatment for 1 h in a flask, 78.8g of epoxy resin is added, stirred for 30min, the flask is placed in a 90 °C oil bath for stirring, acetone is evaporated, 17.2g of molten 4, 4' diaminodiphenyl methane is added, stirred for 30s, the mixture is poured into a mould, the mould is placed in an oven for curing, the curing temperature is 100 °C and maintained for 2h, then the temperature is increased to 150 °C and maintained for 2h, and the temperature is naturally decreased to prepare a flame retardant epoxy resin.
Example 4
S This example is also a method for preparing a flame retardant epoxy resin, which differs from Example 2 in that CLMXene is incorporated in a mass percentage of 6%, specifically: 6g of Cu20/CoNi-LDH/MXene powder is dispersed in acetone, after ultrasonic treatment for lh in a flask, 77.2g of epoxy resin is added, stirred for 30min, the flask is placed in a 90 °C oil bath for stirring, the acetone is evaporated, 16.8g of 4, 4' diaminodiphenyl methane in a molten state is added, stirred for 30s, the mixture is poured into a mould, the mould is placed in an oven for curing, the curing temperature is 100 °C, the temperature is maintained for 2h, then the temperature is increased to 150 °C, the temperature is maintained for 2h, and the temperature is naturally decreased to prepare a flame retardant epoxy resin.
Comparative Example 1 This example is also a method for preparing a flame retardant epoxy resin, which differs from Example 2 in that Cu20 is incorporated into the epoxy resin, the mass percentage of incorporation of Cui0 being 2%, and the specific method is as follows: 2g of Cu20 powder is dispersed in acetone; after ultrasonic treatment for lh in a flask, 80.4g of epoxy resin is added, stirred for 30min, the flask is placed in a 90°C oil bath and stirred; acetone is evaporated; I7.6g of 4, 4' diaminodiphenyl methane in a molten state is added, and stirred for 30s; the mixture is poured into a mould, and the mould is placed in an oven for curing; the curing temperature is 100 °C and maintained for 2h; then the temperature is increased to 150 °C and maintained for 2h; filially, a flame-retardant epoxy resin is prepared by naturally cooling.
Comparative Example 2 This example is also a method for preparing a flame-retardant epoxy resin, and differs from Example 2 in that CoNi-LDH is incorporated into an epoxy resin for preparation, wherein the mass percentage of incorporation of CoNi-LDH is 2%, and the specific method is as follows: 2g of CoNi-LDH powder is dispersed in acetone; after ultrasonic treatment for lh in a flask, 80.4g of epoxy resin is added, stirred for 30min; the flask is placed in a 90 °C oil bath and stirred; acetone is evaporated; 17.6g of 4, 4' diaminodiphenyl methane in a molten state is added, and stirred for 30s, the mixture is poured into a mould, and the mould is placed in an oven for curing; the curing temperature is 100 °C and maintained for 2h; then the temperature is increased to 150 °C and maintained for 2h finally, a flame-retardant epoxy resin is prepared by naturally cooling.
Comparative Example 3 This example is also a method for preparing a flame retardant epoxy resin, which differs from example 2 in that MXcne is incorporated into the epoxy resin, the mass percentage of incorporation of MXene being 2%, and the specific method is as follows: 2g of NIXene powder is dispersed in acetone; after ultrasonic treatment for lh in a flask, 80.4g of epoxy resin is added, stirred for 30min, the flask is placed in a 90 °C oil bath and stirred; acetone is evaporated; 17.6g of 4, 4' diaminodiphenyl methane in a molten state is added, and stirred for 30s; the mixture is poured into a mould, and the mould is placed in an oven for curing; the curing temperature is 100 °C and maintained for 2h, then the temperature is increased to 150 °C and maintained for 2h, finally, a flame-retardant epoxy resin is prepared by naturally cooling.
Comparison and analysis of examples and comparative examples: Thermogravimetric analysis under nitrogen was carried out on the epoxy resin without ternary nanocomposite flame retardant and the flame retardant epoxy resin samples prepared in comparative Examples 1, 2, 3, examples 2, 3 and 4, respectively. The thermal degradation process of the samples under nitrogen was studied and the limiting oxygen index of the samples was tested. The data arc shown in Table 1.
Table 1 Thennogravimetric analysis and limiting oxygen index of epoxy resin samples under nitrogei atmosphere Sample Residual Maximum Temperature corresponding Limiting oxygen index carbon rate mass loss (wt%) (°41°C) to maximum (%) mass loss ( °C) EP 13.82 1.52 403 24.6 2%Mxene 15.57 1.37 398.67 27.3 2(1/iLDH 12.22 1.68 377.33 28.8 2(1/}0.120 18.95 1.06 399.33 26.5 2%CLMMXene 18.38 1.27 387.33 28.1 4%CiLMXene 19.78 1.35 382 29.3 6%CLMXene 21.32 1.13 381 30 It can be seen from Table 1 that the addition of the flame retardant increases the combustion residual carbon rate and the limiting oxygen index of the epoxy resin, especially the addition of the ternary nanocomposite flame retardant greatly increases the combustion residual carbon rate and the limiting oxygen index of the epoxy resin, which indicates that the ternary nanocomposite flame retardant catalyzes the decomposition of the epoxy resin, resulting in a decrease in the temperature corresponding to die maximum mass loss rate, and the carbon formed by the catalytic decomposition acts as a barrier to hinder the transfer of heat and debris. The residual carbon rate of EP with 2% CLMXene reaches 18.38%, which is higher than that of EP with 2% Mxene and 2% CoNi-LDFT only slightly lower than that of EP with 2% Cit20 (18.96%). The residual carbon rate of EP with 4% CLMXene and 6% CLMXene are improved to 19.78% and 21.32%, respectively.
As shown in the DTG curve of Fig. 2, the maximum mass loss rate decreased from 1.52%/ for the pure epoxy resin to 1.27%/ °C with the addition of 2% CLMXene, indicating that the addition of 2% CLMXene flame retardant can inhibit the decomposition rate of epoxy resin. The temperature corresponding to the maximum mass loss decreased from 403 °C to 387.33 °C for the pure epoxy resin, indicating that the addition of 2% CLMXene flame retardant can greatly inhibit the heat release during the combustion of epoxy resin.
As shown in Fig. 3, the limiting oxygen index of epoxy resin with 2% CLMXene is 28.1%, which was higher than that of epoxy resin with 2% Mxene arid 2% 0.60 alone, indicating that the flame retardant with 2% CLMXene can effectively improve the combustion difficulty of epoxy resin. Although the limiting oxygen index of epoxy resin added with 2% CoNi-LDH is the highest, the thermal grayimetric analysis results of 2% CoNi-LDH epoxy resin are not good, the residual carbon rate is the lowest, and the maximum mass loss rate is also the highest due to the easy decomposition of LDH and rapid collapse of structure.
In conclusion, the flame retardant effect of ternary nanocomposite flame retardant is better than that of singly adding one component, and the effect of epoxy resin with 2% CLMXene is better. The addition of CLMXene can also enhance the mechanical properties of EP, including tensile strength and flexural strength. The results of mechanical tests are shown in Table 2 and Fig. 4.
The mechanical property of the CLMXene composite flame retardant is improved by more than that of a single-component flame retardant by the same addition amount of 2%, and compared with pure epoxy resin, the tensile strength and the flexural strength are respectively improved by 44.97% and 14.72% by adding 2% of CLMXene. The advantage of adding 2% CLMXene was proved.
Table 2 Mechanical property data of epoxy resin samples Sample Tensile strength (MPa) Elongation at break (1)/0 Flexural strength (MPa) Flexural modulus (MPa) EP 45.19 12.62 87.69 1234 2%Mxene 35.53 7.9 69.3 2310 2%LDH 50.02 13.75 84 2363 2%Cui0 56.17 13.1 95.11 2548 2%CLMXene 65.51 14.1 100.6 3592 4%CLMXene 62.57 14.98 109.8 3776 6%CLMXene 51.18 13.53 125.6 3425 The effect of CLMXene composite flame retardants on the combustion hazard of epoxy resins was further investigated by cone calorimetry testing and the results are shown in Fig. 5 and Table 3, Table 3 Cone calorimetly test data for epoxy resin Samples Sample Maximum Total heat Maximum Total smoke heat release release smoke production rate (Kw/m2) (MJ/m2) production (1112) rate (m2/s) EP 2171.73 128.13 0.46 27.44 2%CLMXene 1509.29 98.97 0.42 21.14 4%CLMXene 1340.92 94.85 0.35 18.4 6%CLMXene 1228.80 88.12 0.27 15.88 The maximum heat release rate and total heat release of pure epoxy resin were 2171.73 kW/m2 and 128 MJ/m2, respectively. When 2% CLMXene was added, the maximum heat release rate was 1509.29 kW/m2 and total heat release was 98.97 MJ/m2, which decreased by 30.47% and 22.76%, respectively. With the addition of 4% and 6% CLMXene, the maximum heat release rate decreased by 38.26% and 43.42%, respectively, and the total heat release decreased by 25.97% and 31.22%, respectively, indicating that the addition of CLMXene can greatly inhibit the heat release during the combustion of epoxy resin.
Many studies indicate that in real fires, the release of large amounts of smoke and toxic gases is a major fatal hazard. Therefore, more attention should be paid to the inhibition of toxic volatiles.
The maximum smoke production rate and total smoke production of epoxy resin were 0.46 in2is and 27.44 m2, respectively. When 2% CLMXene was added, the maximum smoke production rate was 0.42 m2/s and total smoke production was 21.14 m2, which decreased by 8.7% and 23%, respectively. With the addition of 4% and 6% CLMXene, the maximum smoke production rate decreased by 23.91% and 41.3%, respectively, and the total smoke production decreased by 32.94% and 42.13%, respectively, indicating that the addition of CLMXcne flame retardant can reduce the emission of toxic smoke during the combustion of epoxy resin, excellent performance in reducing polymer fire toxicity.
The non-illustrated parts involved in the present invention are the same as or implemented using
the prior art.
The foregoing is merely a preferred example of the present invention and the present invention is not limited to the details of the example. It will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the invention, and any changes and modifications made are within the scope of the invention.
Claims (10)
- Claims 1. A ternary nanocomposite flame retardant, characterized by comprising MXene nanosheets, layered double metal hydroxides, and cuprous oxide nanocubes; in percentage by mass, 5% MXene nanosheets, 45% layered double metal hydroxides, and 50% cuprous oxide nanocubes.
- 2. The method for preparing a ternary nanocomposite flame retardant according to claim 1, characterized by comprising: step 1, preparation of MXene nanosheets; firstly, lithium fluoride powder is dissolved into hydrochloric acid. TiiAlCi powder is added into the mixed solution, kept stirring, and reacted in a water bath; the product is then centrifuged and washed with deionized water; finally, the product is dispersed in deionizedwater for ultrasonic treatment, and then placed in a centrifuge for centrifugal separation to prepare a dispersion of T13 Cirx, step 2, preparation of CoNi-LDH/MXcne; the Ti3C2Tx dispersion prepared in step 1 and cobalt nitrate hexahydrate are dispersed in deionized water, and arc ultrasonically stirred in a three-neck flask, then a methanol solution containing dimethylimidazole is added to die three-neck flask, and is stirred to prepare a Z1F-67/MXene solution; an ethanol solution containing nickel nitrate hexalwdrate is added into the ZW-67/MXene solution, stirred, then placed same into a centrifuge for centrifugal treatment, washed with deionizedwater for three times after centrifugation, and washed with ethanol for three times, and vacuum-dried the product to prepare a CoNi-LDH/MXene powder; step 3, preparation of Cu20/CoNi-LDH/MXcnc; a copper nitrate trihydrate solution and a sodium hydroxide solution are mixed and stirred, then an ascorbic acid aqueous solution is added, stirred under water bath conditions, and then centrifuged to obtain a precipitate, the precipitate is washed with deionized water and ethanol, and finally the product is dried in vacuum to prepare a cuprous oxide Cu2O nanocube powder; the Clot/ powder and the CoNi-LDH/MXene powder prepared in step 2 are mixed in a mass ratio of 1: 1, dispersed same in deionized water, and the two are combined through hydrothermal treatment; the product is placed into a centrifuge for centrifugal treatment, then the precipitate is taken out, washed with deionizedwater for three times, ethanol for three times, and then vacuum dried to prepare a Cu20/CoNi-LDH/Mxene ternary nanocomposite flame retardant with a structure in which a layered double metal hydroxide grows on MXcne nanoshccts, and cuprous oxide nanocubes adhere to the surface of the layered double metal hydroxide.
- 3. The method for preparing a ternary nanocomposite flame retardant according to claim 2, characterized in that the ternary nanocomposite flame retardant comprises 5% M Xene nanosheets, 45% layered double metal hydroxide and 50% cuprous oxide nanocubes in percentage by mass.
- 4. The method for preparing a ternary nanocomposite flame retardant according to claim 3, characterized by comprising: step 1, preparation of MXene nanosheets; Firstly, lg of lithium fluoride powder is dissolved in 20 mL of hydrochloric acid, with the hydrochloric acid concentration being 9 mol/L, and 1 g of Ti3AIC2 powder is added into the mixed solution, kept stirring, and reacted for 24h at 35 °C in a water bath; the product is then centrifuged and washed with deionized water until the pH reached 6-7; finally, the product is dispersed in deionizedwater for ultrasonic treatment for 113, and then placed in a centrifuge for centrifugal separation at a rotation speed of 3500 rpm to prepare a dispersion of Ti3C2Tx; step 2, preparation of CoNi-LDH/MXene; the Ti3C2Tx dispersion prepared in step 1 and 5g of cobalt nitrate hexahydratc are dispersed in 200 mL of deionized water, and are ultrasonically stirred in a three-neck flask for 10 min, wherein the TiaCiTx dispersion comprises 0.2g Ti3C2Tx, then 200 mL of a methanol solution containing 6g of dimetlaylimidazole is added in the three-neck flask, and is stirred for 12h to prepare a ZIT-67/MXene solution; 200 mL of an ethanol solution containing 5g of nickel nitrate hexahydrate is added into the ZIF-67/MXene solution, stirred for 10h, then placed same into a centrifuge for centrifugal treatment, with the centrifugal rotation speed being 10000 rpm, washed with deionizedwater for three times after centrifugation, and washed with ethanol for three times, and vacuum dryied the product to prepare a CoNi-LDH/A4Xene powder; step 3, preparation of Cu20/CoNi-LDH/MXene, 300 mL of a 0.01 mol/L copper nitrate trihydrate solution and 60 mL of a 1 mol/L sodium hydroxide solution arc mixed, stirred for 30min, then 60 mL of a 0.5 mol/L ascorbic acid aqueous solution is added, stirred for 3h at SO 'C in a water bath, and centrifuged at the rotation speed of 10000 rpm to obtain a precipitate, the precipitate is washed with deionized water and ethanol, and finally the product is dried in vacuum at 60 °C to prepare a cuprous oxide Cu20 nanocube powder.the Cu20 powder and the CoNi-LDH/MXene powder prepared in step 2 are mixed in a mass ratio of 1: 1, dispersed same in deionized water, and the two are combined through a hydrothermal treatment at 120 °C; the product is placed into a centrifuge for centrifugal treatment at the rotation speed of 10000 rpm, then the precipitate is taken out, washed with deionizedwater for three times, ethanol for three times, and then vacuum dried to prepare a Cu20/CoNi-LDH/MXene nanocomposite flamc retardant material, namely, preparing CLMXene with the mass ratio of MXene nanosheets, layered double metal hydroxide and cuprous oxide nanocubes being 1:9: 10,
- 5. A flame retardant epoxy resin, characterized by comprising a ternary nanocomposite flame retardant or a single component thereof, an epoxy resin and a curing agent; in percentage by mass, the ternary nanocomposite flame retardant or a single component thereof accounts for 2%, the epoxy resin accounts for 80.4% and the curing agent accounts for 17.6%, and the components of the ternary nanocomposite flame retardant comprise 5% Name nanosheets, 45% layered double metal hydroxide and 50% cuprous oxide nanocubes.
- 6. A flame retardant epoxy resin according to claim 5, characterized in that the curing agent is 4, 4'diaminodiphenyl methane.
- 7. The method for preparing a flame retardant epoxy resin according to claim 5, characterized by specifically comprising: dispersing a powder of CLIMXene or Cu20 or CoNi-LDH or MXene in acetone, after ultrasonic treatment in a flask, adding an epoxy resin for stirring, placing the flask in an oil bath for stirring, evaporating the acetone, adding a curing agent in a molten state for stirring, pouring the mixture into a mould, placing the mould in an oven for curing, and then naturally cooling to prepare a flame retardant epoxy resin.
- 8. The method for preparing a flame retardant epoxy resin according to claim 7, characterized in that the CLMXene is incorporated in an amount of 2% to 6% by mass.
- 9. The method for preparing a flame retardant epoxy resin according to claim 8, characterized in that the CLMXene is incorporated in an amount of 2% by mass, namely, CLMXenc: (epoxy resin + curing agent) = 2: 98, wherein the mass ratio of epoxy resin to curing agent is 4.58: 1.
- 10. The method for preparing a flame retardant epoxy resin according to claim 7, characterized in that the mold is placed in an oven and cured by: the temperature was maintained at 100 °C for 2h and then increased to 150 °C for 2h.
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