CN115028890B - Preparation of composite nano flame retardant and application of composite nano flame retardant in epoxy resin - Google Patents
Preparation of composite nano flame retardant and application of composite nano flame retardant in epoxy resin Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 89
- 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 87
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 56
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002135 nanosheet Substances 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 230000000694 effects Effects 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 15
- 239000000725 suspension Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000005530 etching Methods 0.000 claims description 9
- 238000005119 centrifugation Methods 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229960005070 ascorbic acid Drugs 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000010335 hydrothermal treatment Methods 0.000 claims description 3
- 230000002829 reductive effect Effects 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 229960000999 sodium citrate dihydrate Drugs 0.000 claims description 3
- 239000002211 L-ascorbic acid Substances 0.000 claims description 2
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000002091 nanocage Substances 0.000 abstract description 14
- 239000002114 nanocomposite Substances 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 6
- 239000000779 smoke Substances 0.000 abstract description 5
- 231100000331 toxic Toxicity 0.000 abstract description 5
- 230000002588 toxic effect Effects 0.000 abstract description 5
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 abstract description 4
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 abstract description 4
- 229940112669 cuprous oxide Drugs 0.000 abstract description 4
- 229910000000 metal hydroxide Inorganic materials 0.000 abstract description 3
- 150000004692 metal hydroxides Chemical class 0.000 abstract description 3
- FQMNUIZEFUVPNU-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co] FQMNUIZEFUVPNU-UHFFFAOYSA-N 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000010949 copper Substances 0.000 description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 20
- 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 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 239000002105 nanoparticle Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
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- 239000002861 polymer material Substances 0.000 description 4
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- 239000011347 resin Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- -1 hydroxide ions Chemical class 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910003321 CoFe Inorganic materials 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 238000004786 cone calorimetry Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
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Images
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- 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
- C08K3/10—Metal compounds
- C08K3/14—Carbides
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method of a composite nano flame retardant and application of the composite nano flame retardant in epoxy resin, wherein the composite nano flame retardant takes a cuprous oxide nanocube as a template, cobalt-iron double metal hydroxide CoFe-LDH grows in situ on the surface of the cuboid, and cuprous oxide is etched to form a hollow CoFe-LDH nano cage; and compounding the CoFe-LDH nanocages with MXene nanosheets to obtain the nano composite flame retardant MX-LDH. The nanometer composite flame retardant MX-LDH can fully exert the flame retardant efficiency of the nanometer flame retardant particles, effectively reduce the thermal hazard and the toxic smoke hazard of epoxy resin fire, and simultaneously enhance the mechanical property of the material.
Description
Technical Field
The invention belongs to the field of flame retardant materials, and particularly relates to a preparation method of a composite nano flame retardant and application of the composite nano flame retardant in epoxy resin.
Background
Epoxy resins (EP) have high transparency and excellent mechanical properties and are widely used in the fields of construction, automotive and aerospace, etc. However, its further use presents an inherent high fire hazard-combustion can release considerable heat and toxic volatiles. At present, the fire safety requirement of the high polymer material is more and more emphasized, and the epoxy resin material needs to be subjected to flame retardant treatment. Therefore, it is of great significance to reduce the fire hazard of EP. The traditional flame retardant additives usually need high addition amount to achieve satisfactory flame retardant effect, but often cause deterioration of mechanical property and thermal stability of the material.
The rapid development of the nano composite technology provides a new idea for the research and development of the flame-retardant high polymer material, has relatively high efficacy in reducing heat release rate and smoke release and enhancing the mechanical property of the polymer, and can effectively solve the contradiction between the flame-retardant property and other properties of the polymer material.
Disclosure of Invention
Aiming at the heat and toxic hazards of high polymer material fire, the invention further optimizes the structural design on the basis of the current nano flame retardant technology, and provides the preparation of a composite nano flame retardant MX-LDH and the application thereof in epoxy resin. The nanometer composite flame retardant MX-LDH can fully exert the flame retardant efficiency of the nanometer flame retardant particles, effectively reduce the thermal hazard and the toxic smoke hazard of epoxy resin fire, and simultaneously enhance the mechanical property of the material.
The invention relates to a nano composite flame retardant MX-LDH, which takes a cuprous oxide nanocube as a template, cobalt-iron double metal hydroxide (CoFe-LDH) grows in situ on the surface of the cuboid, and the cuprous oxide is etched to form a hollow CoFe-LDH nanocage; mixing CoFe-LDH nanocage with MXene (Ti) 3 C 2 ) And compounding the nano sheets to obtain the nano composite flame retardant MX-LDH.
Wherein the mass ratio of the MXene nanosheets to the CoFe-LDH nanocages is 1.
The preparation method of the nano-composite flame retardant MX-LDH comprises the following steps:
step 1: first of all made of Cu 2+ Formation of Cu (OH) in sodium hydroxide solution 2 Then reduced to Cu with ascorbic acid 2 And (4) an O cube. Preparing Cu (NO) with concentration of 0.01-0.1mol/L 3 ) 2 ·3H 2 O solution, then using a proper amount of sodium citrate dihydrate and polyvinylpyrrolidone as dispersing agents, stirring for 1h, adding NaOH solution with the concentration of 1-2mol/L, stirring for 2h to obtain blue Cu (OH) 2 A suspension; then adding 0.5-2mol/L ascorbic acid solution, stirring for 3-5h to obtain reddish brown Cu 2 Suspending in O suspension, centrifuging (10000rpm, 3min), washing with water for 3 times, washing with ethanol for two times, and vacuum drying at 60 deg.C to obtain Cu 2 And (4) O powder.
Step 2: with Cu 2 O as a template in the presence of Fe 2+ 、Co 2+ To the solution system of (1), sodium thiosulfate (Na) is added 2 S 2 O 3 ) According to the theory of Hard and Soft Acid Base (HSAB), the hollow nano cage of CoFe double metal hydroxide is prepared. Copper oxide nanoparticlesUpon reaction with sodium thiosulfate solution, soluble [ Cu ] is formed 2 (S 2 S 3 ) x ] 2-2x The complexes then release a large number of hydroxide ions at the etched interface. At the same time, co 2+ And Fe 2+ Can be co-precipitated with the hydroxide ions at an etching interface, and generates a CoFe double hydroxide hollow nano cage by inheriting the geometric shape of a copper oxide template, wherein the chemical reaction route is as follows:
(1)Cu 2 O+xS 2 O 3 2- +H 2 O→[Cu 2 (S 2 O 3 ) x ] 2-2x +2OH -
(3)Fe 2+ +Co 2+ +yOH - +O 2 +H 2 O→Co x Fe 1-x (OH) y
mixing Cu 2 Dispersing O powder in a mixed solvent consisting of water and ethanol (volume ratio is 7; adding CoCl 2 ·6H 2 O and FeSO 4 ·7H 2 O，Co 2+ And Fe 2+ Has a total concentration of 0.02mol/L, co 2+ And Fe 2+ The molar ratio of (A) is between 1; then will contain an excess of Na 2 S 2 O 3 ·5H 2 Slowly dripping the water solution of O into the suspension, and stirring for 2-4h at room temperature; the product was collected by centrifugation (10000rpm, 3min), then washed 3 times with distilled water, 2 times with ethanol, and finally dried in a vacuum oven at 60 ℃ for 12 hours to give LDH powder.
And step 3: mixing Ti 3 AlC 2 And (4) obtaining MXene nanosheets by etching and stripping.
1g of lithium fluoride powder is dissolved in 20mL of hydrochloric acid to prepare a mixed solution containing hydrofluoric acid, the concentration of the hydrochloric acid is 9-12mol/L, and 1g of Ti is added into the lithium fluoride mixed solution 3 AlC 2 Powder, stirring, etching in 35 deg.C water bath, and reactionThe reaction time is 24-48h; after the etching reaction was completed, first centrifugation was performed at 3500rpm, and the lower layer was precipitated to obtain Ti 3 C 2 T x Washing with deionized water to pH 6-7, and adding Ti 3 C 2 T X Dispersing in deionized water, carrying out ultrasonic treatment for stripping, and finally carrying out second centrifugal treatment at the rotation speed of 3500rpm to obtain an upper suspension liquid, namely an MXene nanosheet suspension liquid containing the MXene nanosheets.
And 4, step 4: the MXene nano-sheets and the CoFe-LDH nano-cage are combined through a hydrothermal method to prepare the MXene @ LDH composite nano-flame retardant.
MXene and LDH are dispersed in deionized water, ultrasonic stirring is carried out for 1h, and the mass ratio of MXene to LDH is 1-1; adding the dispersion liquid into a hydrothermal kettle for hydrothermal treatment for 8-12h at the hydrothermal temperature of 100-180 ℃; the product was collected by centrifugation (10000rpm, 3min), then washed 3 times with distilled water, 2 times with ethanol, and finally dried in a vacuum oven at 60 ℃ for 12 hours to obtain MXene @ LDH powder.
The application of the nano-composite flame retardant MX-LDH is to add the nano-composite flame retardant MX-LDH serving as a flame retardant into an epoxy resin matrix so as to improve the flame retardant effect of the composite material.
The molecular chain of the epoxy resin contains two or more epoxy groups, and specifically comprises one or a mixture of more than two of bisphenol A epoxy resin, bisphenol F epoxy resin and phenolic aldehyde epoxy resin.
The weight percentage of the MX-LDH nano composite flame retardant is 1-6%.
The curing agent is one or a mixture of more than two of aliphatic amine, acid anhydride, aromatic amine, dicyandiamide and polyamide.
Compared with the flame retardant effect of the MXene @ LDH composite nanoparticles, the flame retardant effect of the MXene @ LDH composite nanoparticles is better than that of one component added independently, and the MXene and LDH composite nanocages can play a synergistic flame retardant role to obtain higher flame retardant efficiency. The epoxy resin added with 5 percent of MXene @ LDH has the best flame retardant effect, and the flame retardant efficiency is further improved than that of the existing nano flame retardant technology, the addition amount is lower, and the flame retardant effect is better.
The patent with application number CN202111188005.8 discloses a nano composite flame retardant, which compounds several nano materials to have higher flame retardant efficiency, but the flame retardant efficiency of nano flame retardant particles cannot be fully exerted due to the lack of structural design for optimizing the flame retardant effect of nano particles.
Unlike CN202111188005.8, LDH no longer grows in a stacking manner, but forms a hollow cubic nanometer cage, the hollow structure can improve the specific surface area of LDH, and is more beneficial to exerting the decomposition and heat absorption effects of LDH, and in addition, the cage-shaped structure can also effectively capture decomposition products and smoke particles during combustion and inhibit the generation of toxic smoke. The MXene nanosheets are high in thermal stability, the thermal stability of the resin material can be improved, and the layered structure can block the transmission of heat, oxygen and combustible pyrolysis products. The layered MXene and the cage-shaped LDH can be used as a framework and a protective layer to enhance the structural strength of the carbon layer, and in addition, the two components can generate high-activity metal oxide, so that the catalyst has a high-efficiency catalytic carbonization effect, can further strengthen the carbon layer, protect a resin matrix and reduce the combustion degree.
Compared with the flame retardant of CN202111188005.8, the flame retardant of the invention not only compounds nano materials with different flame retardant effects, but also obtains higher flame retardant efficiency by carrying out structural design optimization on the materials, and obtains epoxy resin with better flame retardant effect by lower addition amount.
Drawings
FIG. 1 is a schematic diagram of the preparation process of the present invention.
FIG. 2 (a) shows Cu 2 X-ray diffraction (XRD) patterns of O and CoFe-LDH, cu can be seen 2 The O diffraction peak is consistent with the standard PDF card, after CoFe-LDH is generated, cu 2 O is etched, and a diffraction peak is not seen, so that an amorphous spectral line of LDH is formed; FIG. 2 (b) is the XRD spectrum of MXene and MXene @ LDH, showing Ti 3 AlC 2 The spectral line of the (1) is in accordance with the standard PDF card, after the MXene sheet is prepared, the 002 crystal face is shifted towards a small angle, the etching and stripping are reflected to increase the inter-lamellar distance, and the single-layer nano sheet is formed. After the MXene sheet is compounded with LDH, MXene is covered, and the spectral line of MXene @ LDH is consistent with that of LDH.
FIG. 3 is the XPS spectrum of MXene @ LDHAnd (5) analyzing the spectrogram. Wherein FIG. 3 (a) is a chromatogram showing signals of C, ti, O, fe, co; FIG. 3 (b) is a spectrum of Ti 2p, with peaks at 463.8 and 458.1eV corresponding to Ti 4+ /Ti 3+ (TiO x ) Ti 2p of (a) 1/2 And Ti 2p 3/2 Peaks at 461.6 and 455.9eV correspond to Ti 3+ Ti 2p of 1/2 And Ti 2p 3/2 Peaks at 460.3 and 454.7eV correspond to Ti 2+ Ti 2p of 1/2 And Ti 2p 3/2 The presence of Ti-C was confirmed, and the above results confirmed the presence of MXenes. FIG. 3 (c) is a spectrum of Co 2p, with peaks at 798.6 and 782.6eV corresponding to Co 3+ Co 2p of 1/2 And Co 2p 3/2 The peaks at 796.6 and 780.5eV correspond to Co 2+ Co 2p of 1/2 And Co 2p 3/2 (ii) a FIG. 3 (d) is a spectrum of Fe 2p, with peaks at 726 and 713.8eV corresponding to Fe 3+ Fe 2p of 1/2 And Fe 2p 3/2 Peaks at 724 and 711eV correspond to Fe 2+ Fe 2p of 1/2 And Fe 2p 3/2 . The presence of both cobalt and iron elements, bivalently and trivalently, is evidence of LDH.
Fig. 4 is an electron microscope image of the product of each step. Wherein, FIGS. 4 (a) and (e) are Cu 2 TEM and SEM images of O and Cu were observed 2 O is a cubic morphology; FIGS. 4 (b), (f) are TEM and SEM images of CoFe-LDH, and Cu is visible in (b) 2 The O template is etched, LDH is a hollow cage-shaped structure, and (f) the surface of the nano cage is composed of LDH lamella; FIGS. 4 (c) and (g) are TEM and SEM images of MXene, which is a lamellar two-dimensional structure; fig. 4 (d) and (h) are TEM and SEM images of MXene @ LDH, and it can be seen that the LDH nanocages are bound to the MXene sheets to form the composite nanomaterial.
In conclusion, it can be confirmed that the composition and structure of the intermediate product and the final product of each step are in accordance with the experimental design.
FIG. 5 shows the cone calorimetry results of commercially available epoxy resins and flame retardant epoxy resins prepared in each example. FIGS. 5 (a), (b) are a comparison of Heat Release Rate (HRR) and Total Heat Release (THR), showing that the heat generation behavior of resin combustion is effectively suppressed after the addition of flame retardant particles, with both the heat release rate and the total heat release being substantially reduced; FIGS. 5 (c), (d) are graphs comparing the rate of carbon monoxide production and total production, and it can also be seen that MXene @ LDH has an effect of inhibiting carbon monoxide release due to MXene and LDH. The best EP/5.0MXene @ LDH produced 47.41% peak rate and 63.59% reduction in total carbon monoxide production, respectively, compared to commercially available epoxy resins.
Detailed Description
The technical scheme of the invention is further analyzed and explained by combining the attached drawings and specific examples.
Example 1: preparation of composite flame retardant
1. Preparation of Cu 2 O-nanocube
7.26g of Cu (NO) 3 ) 2 ·3H 2 Dissolving O in 1500mL of water (0.01M), stirring for 10min, adding 12g of sodium citrate dihydrate and 15g of polyvinylpyrrolidone, stirring for 1h, adding 150mL of 2M NaOH solution, and stirring for 2h to obtain blue Cu (OH) 2 A suspension; then 150mL0.8M ascorbic acid solution is added and stirred for 5h to obtain reddish brown Cu 2 O suspension, centrifuging the product (10000rpm, 3min), washing with water 3 times, washing with ethanol twice, and vacuum drying at 60 ℃ to obtain Cu 2 And (4) O powder.
2. Preparation of hollow CoFe-LDH nanocages
1g of Cu 2 Dispersing O powder in 280mL of water and 120mL of ethanol, adding 2.64g of polyvinylpyrrolidone, and ultrasonically stirring for 30min; 1.19g of CoCl was added 2 ·6H 2 O (5 mmol) and 1.39g FeSO 4 ·7H 2 O (5 mmol), and stirring with ultrasound for 30min. 100mL of 1M Na 2 S 2 O 3 ·5H 2 Slowly dripping O (24.8 g) solution into the suspension, and respectively stirring for 4h at room temperature; the product was collected by centrifugation (10000rpm, 3min), then washed 3 times with distilled water, 2 times with ethanol, and finally dried in a vacuum oven at 60 ℃ for 12 hours to give LDH powder.
3. Preparation of MXene nanosheet
1g of lithium fluoride powder is dissolved in 20mL of hydrochloric acid to prepare a mixed solution containing hydrofluoric acid, the concentration of the hydrochloric acid is 9-12mol/L, and 1g of Ti is added into the lithium fluoride mixed solution 3 AlC 2 Powder, kept under stirring, at 35Etching reaction is carried out under the condition of water bath at the temperature of 24-48h; after the etching reaction was completed, the first centrifugation treatment was performed at 3500rpm, and the lower layer was precipitated to obtain Ti 3 C 2 T x Washing with deionized water to pH 6-7, and adding Ti 3 C 2 T X Dispersing in deionized water, carrying out ultrasonic treatment for stripping, and finally carrying out second centrifugal treatment at the rotation speed of 3500rpm to obtain an upper suspension liquid, namely an MXene nanosheet suspension liquid containing the MXene nanosheets.
4. Preparation of MXene @ LDH nano composite particles
Dispersing 1g of MXene and 2g of LDH in 400mL of deionized water, ultrasonically stirring for 1h, adding into a hydrothermal kettle, carrying out hydrothermal treatment at 120 ℃ for 8h to compound the MXene and the LDH, centrifugally collecting the product (10000rpm, 3min), washing with distilled water for 3 times, washing with ethanol for 2 times, and finally drying in a vacuum oven at 60 ℃ for 12 hours to obtain MXene @ LDH powder.
Epoxy resin is used as a polymer matrix, and MXene nanosheets, LDH nanocages and MXene @ LDH are respectively added into the epoxy resin, so that the flame retardant property of each composite epoxy resin is tested and compared.
Example 2: preparation of flame-retardant epoxy resin
Dispersing 1g of MXene powder in acetone, carrying out ultrasonic treatment in a flask for 1h, adding 81.3g of epoxy resin, stirring for 30min, placing the flask in a 90 ℃ oil bath, stirring, volatilizing the acetone, adding 17.7g of molten 4,4' diaminodiphenylmethane, stirring for 30s, pouring the mixture into a mold, placing the mold into an oven for curing, keeping the curing temperature at 100 ℃ for 2h, then heating to 150 ℃ for 2h, and naturally cooling to obtain the flame-retardant epoxy resin EP/1.0MXene. The curing agent in this example was 4,4' diaminodiphenylmethane.
In this embodiment, the doping mass percentage of MXene is 1%, that is, MXene: (epoxy resin + curing agent) =2:98, wherein the mass ratio of the epoxy resin to the curing agent is 4.58.
Example 3: preparation of flame-retardant epoxy resin
The embodiment is also a method for preparing flame-retardant epoxy resin, and is characterized in that the added nanoparticles are LDH nanocages, the doping mass percentage of LDH is 1%, and the method specifically comprises the following steps: dispersing 1g of LDH powder in acetone, carrying out ultrasonic treatment in a flask for 1h, adding 81.3g of epoxy resin, stirring for 30min, placing the flask in a 90 ℃ oil bath, stirring, volatilizing the acetone, adding 17.7g of molten 4,4' diaminodiphenylmethane, stirring for 30s, pouring the mixture into a mold, placing the mold into an oven for curing, keeping the curing temperature at 100 ℃ for 2h, then heating to 150 ℃ for 2h, and naturally cooling to obtain the flame-retardant epoxy resin EP/1.0LDH.
Example 4: preparation of flame-retardant epoxy resin
The embodiment is also a method for preparing flame-retardant epoxy resin, and the difference is that the added nanoparticles are MXene @ LDH composite nanoparticles, the doping mass percentage of the MXene @ LDH is 1%, and the method specifically comprises the following steps: 1g of MXene @ LDH powder is dispersed in acetone, after 1h of ultrasonic treatment in a flask, 81.3g of epoxy resin is added, the mixture is stirred for 30min, the flask is placed in an oil bath at 90 ℃ and stirred, the acetone is volatilized, 17.7g of molten 4,4' diaminodiphenylmethane is added, the mixture is stirred for 30s, the mixture is poured into a mold, the mold is placed into an oven for solidification, the solidification temperature is 100 ℃, the temperature is kept for 2h, then the temperature is raised to 150 ℃, the temperature is kept for 2h, and the flame-retardant epoxy resin EP/1.0MXene @ LDH is prepared by natural cooling.
Example 5: preparation of flame-retardant epoxy resin
The embodiment is also a method for preparing flame-retardant epoxy resin, wherein the added nanoparticles are MXene @ LDH composite nanoparticles, and the difference is that the doping mass percentage of the MXene @ LDH is 3%, and the method specifically comprises the following steps: dispersing 3g of MXene @ LDH powder in acetone, carrying out ultrasonic treatment in a flask for 1h, adding 79.6g of epoxy resin, stirring for 30min, placing the flask in a 90 ℃ oil bath, stirring, volatilizing the acetone, adding 17.4g of molten 4,4' diaminodiphenylmethane, stirring for 30s, pouring the mixture into a mold, placing the mold into an oven for curing, keeping the curing temperature at 100 ℃ for 2h, then heating to 150 ℃ for 2h, and naturally cooling to obtain the flame-retardant epoxy resin EP/3.0MXene @ LDH.
Example 6: preparation of flame-retardant epoxy resin
The embodiment is also a method for preparing the flame-retardant epoxy resin, and the added nanoparticles are MXene @ LDH composite nanoparticles, which are characterized in that the doping mass percentage of the MXene @ LDH is 5%, and the method specifically comprises the following steps: dispersing 5g of MXene @ LDH powder in acetone, carrying out ultrasonic treatment in a flask for 1h, adding 78g of epoxy resin, stirring for 30min, placing the flask in a 90 ℃ oil bath, stirring, volatilizing the acetone, adding 17g of molten 4,4' diaminodiphenylmethane, stirring for 30s, pouring the mixture into a mold, placing the mold into an oven for curing, keeping the curing temperature at 100 ℃ for 2h, then heating to 150 ℃ for 2h, and naturally cooling to obtain the flame-retardant epoxy resin EP/5.0MXene @ LDH.
TABLE 1 HRR, THR reduction of flame retardant resin samples
TABLE 2 limiting oxygen index test results
Table 1 summarizes the maximum heat release rate and the magnitude of the decrease in total heat release for each example and comparative example relative to pure epoxy. Compared with MXene and LDH, the MXene @ LDH composite particles have higher flame retardant efficiency, and the effect of inhibiting heat release of the MXene @ LDH is higher than that of singly adding MXene and LDH when the addition amount of the MXene @ LDH is 1%. In addition, the flame retardant efficiency of MXene @ LDH is higher than that of the current nano flame retardant technology, the preferable embodiment EP/6.0CLMXene in the patent CN202111188005.8 is taken as a comparative example, the MXene @ LDH achieves better flame retardant effect by using lower addition amount, the MXene @ LDH is added by 5%, and the reduction range of the maximum heat release rate exceeds that of a sample with 6% of CLMXene addition. MXene @ LDH has better effect of inhibiting total heat release, and the THR reduction amplitude of EP3.0MXene @ LDH exceeds that of EP/6.0CLMXene.
Table 2 shows the results of Limiting Oxygen Index (LOI) tests of commercially available epoxy resins and flame retardant epoxy resins prepared in each example. Similarly, the LOI of the MXene @ LDH composite nanoparticles is higher than that of MXene and LDH, and compared with the prior art, the oxygen index of EP3.0MXene @ LDH is higher than that of EP/6.0CLMXene, and the addition amount of MXene @ LDH is less, so that the flame retardant effect is better.
In conclusion, the flame retardant effect of the MXene @ LDH composite nanoparticles is better than that of one component added alone, the synergistic flame retardant effect can be achieved after the MXene and the LDH are compounded, the higher flame retardant efficiency is obtained, the flame retardant effect of the epoxy resin added with 5% of MXene @ LDH is the best, the flame retardant efficiency is further improved than that of the existing nano flame retardant technology, the addition amount is lower, and the flame retardant effect is better.
Claims (8)
1. The preparation method of the composite nano flame retardant is characterized by comprising the following steps:
step 1: first of all made of Cu 2+ Formation of Cu (OH) in sodium hydroxide solution 2 Then reduced to Cu with ascorbic acid 2 An O cube;
step 2: mixing Cu 2 Dispersing O powder in a mixed solvent consisting of water and ethanol, adding polyvinylpyrrolidone, and ultrasonically stirring and dispersing; adding CoCl 2 •6H 2 O and FeSO 4 •7H 2 O，Co 2+ And Fe 2+ The total concentration of (a) is 0.02mol/L; then will contain excess Na 2 S 2 O 3 •5H 2 Slowly dripping the water solution of O into the suspension, and stirring for 2-4h at room temperature; collecting a product through centrifugation, washing the product with distilled water and ethanol, and drying the product in vacuum to obtain LDH powder;
and 3, step 3: mixing Ti 3 AlC 2 Obtaining MXene nano-sheets by etching and stripping;
and 4, step 4: and combining the MXene nano-sheets with the LDH powder by a hydrothermal method to prepare the MXene @ LDH composite nano-flame retardant.
2. The production method according to claim 1, characterized in that:
in step 1, cu (NO) with a concentration of 0.01-0.1mol/L is prepared 3 ) 2 ·3H 2 O solution, sodium citrate dihydrate and polyvinylpyrrolidone as dispersing agents, stirring for 1h, adding 1-2 mol/mlNaOH solution of L, stirring for 2h to give blue Cu (OH) 2 A suspension; then adding 0.5-2mol/L ascorbic acid solution, stirring for 3-5h to obtain reddish brown Cu 2 Suspending the product in O suspension, centrifuging the product, washing the product with water and ethanol, and drying the product in vacuum to obtain Cu 2 And (4) O powder.
3. The method of claim 1, wherein:
Co 2+ and Fe 2+ The molar ratio of (a) to (b) is 1.
4. The method of claim 1, wherein:
in step 3, 1g of lithium fluoride powder is dissolved in 20mL of hydrochloric acid to prepare a mixed solution containing hydrofluoric acid, the concentration of the hydrochloric acid is 9-12mol/L, and 1g of Ti is added into the lithium fluoride mixed solution 3 AlC 2 Keeping stirring the powder, and carrying out etching reaction for 24-48h under the condition of 35 ℃ water bath; after the etching reaction was completed, the first centrifugation treatment was performed at 3500rpm, and the lower layer was precipitated to obtain Ti 3 C 2 T x Washing with deionized water to pH 6-7, and adding Ti 3 C 2 T X Dispersing in deionized water, carrying out ultrasonic treatment for stripping, and finally carrying out second centrifugal treatment at the rotation speed of 3500rpm to obtain an upper suspension, namely the MXene nanosheet suspension containing the MXene nanosheets.
5. The method of claim 1, wherein:
in the step 4, dispersing MXene nanosheets and LDH powder in deionized water, and ultrasonically stirring for 1h; adding the dispersion liquid into a hydrothermal kettle for hydrothermal treatment for 8-12h at the hydrothermal temperature of 100-180 ℃; the product was collected by centrifugation, then washed with distilled water and ethanol, and dried under vacuum to give MXene @ LDH powder.
6. The production method according to claim 5, characterized in that:
the mass ratio of the MXene nanosheets to the LDH powder is 1 to 1.
7. The application of the composite nanometer flame retardant prepared by the preparation method of any one of claims 1 to 6 is characterized in that:
the composite nano flame retardant is added into an epoxy resin matrix to improve the flame retardant effect of the composite material.
8. Use according to claim 7, characterized in that:
the composite nano flame retardant is added in a mass percentage of 1-6%.
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| CN113845695A (en) * | 2021-10-12 | 2021-12-28 | 南京工业大学 | Ternary nano composite flame retardant, flame-retardant epoxy resin and preparation method thereof |
| CN114539616A (en) * | 2022-02-19 | 2022-05-27 | 南京工业大学 | Nano composite flame retardant, flame-retardant bismaleimide resin and preparation method thereof |
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| CN114539616A (en) * | 2022-02-19 | 2022-05-27 | 南京工业大学 | Nano composite flame retardant, flame-retardant bismaleimide resin and preparation method thereof |
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| Wenwen Guo et al..Multifunctional epoxy composites with highly flame retardant and effective electromagnetic interference shielding performances.《Composites》.2020,第第192卷卷第1-11页. * |
| Yuling Xiao et al..Functional covalent organic framework illuminate rapid and efficient capture of Cu (II) and reutilization to reduce fire hazards of epoxy resin.《Separation andPurificationTechnology》.2020,第第259卷卷第1-12页. * |
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