CN112745610A - Modified Mxene/PVA flame-retardant composite material and preparation method thereof - Google Patents
Modified Mxene/PVA flame-retardant composite material and preparation method thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 67
- 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 66
- 239000002131 composite material Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 47
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 47
- 238000003756 stirring Methods 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 31
- 238000005406 washing Methods 0.000 claims abstract description 27
- 239000008367 deionised water Substances 0.000 claims abstract description 26
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 239000011259 mixed solution Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000002244 precipitate Substances 0.000 claims abstract description 16
- 239000006185 dispersion Substances 0.000 claims abstract description 15
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000003760 magnetic stirring Methods 0.000 claims abstract description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 60
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000000654 additive Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 abstract description 7
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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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
- C08K3/10—Metal compounds
- C08K3/14—Carbides
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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
- C08K7/26—Silicon- containing compounds
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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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
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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Abstract
The invention discloses a modified Mxene/PVA flame-retardant composite material and a preparation method thereof. Dispersing the Mxene in deionized water, and performing ultrasonic treatment to obtain an Mxene dispersion liquid; adding CTAB, and magnetically stirring for reaction to obtain a mixed solution; adjusting the pH value of the mixed solution, adding tetraethoxysilane after magnetic stirring reaction, and performing magnetic stirring reaction to obtain a precipitate; dissolving the precipitate in ethanol water solution, dripping a silane coupling agent, magnetically stirring for reaction, and washing to obtain modified MXene; dispersing polyvinyl alcohol in deionized water to obtain a polyvinyl alcohol solution; adding modified MXene; the multifunctional flame-retardant composite material is prepared by uniformly dispersing and drying. The composite material has excellent flame retardant property, good conductive property and electromagnetic shielding property, and can be used in the field of coatings such as building coatings.
Description
Technical Field
The invention belongs to the technical field of composite materials, relates to a flame-retardant composite material, and particularly relates to a multifunctional flame-retardant composite material and a preparation method thereof.
Background
At present, a large amount of combustible or inflammable materials are closely related to production and life of people, potential hidden dangers of fire disasters threaten life safety of people, and the method for converting inflammable materials into flame-retardant materials by using additives is a common method. However, usually, a large amount of flame retardant is required to achieve the desired flame retardant effect, which has a great influence on the mechanical properties and other properties of the material; meanwhile, with the rapid development of wireless electronic devices, electromagnetic radiation becomes a non-negligible pollution, which not only affects the health of people, but also has a certain effect on the normal operation of electronic devices. Materials with high electromagnetic shielding effectiveness can effectively solve this contamination problem. The two-dimensional nano material has small damage to the mechanical property of the composite material as an additive of the composite material due to the unique geometric characteristics and special properties, and meanwhile, the composite material can be endowed with multiple functions such as electromagnetic shielding property and the like by partial two-dimensional materials, so that the two-dimensional nano material is an ideal additive of the composite material.
When the two-dimensional material is used as a flame retardant, the surface of the two-dimensional material is modified or the traditional flame retardant is deposited, so that the two-dimensional material can become a low-addition-amount and high-efficiency flame retardant additive. The two-dimensional transition metal carbide (MXene) is a novel two-dimensional material, has excellent conductivity and a unique two-dimensional mechanism, and becomes a material which can be used for electromagnetic shielding, and in addition, the MXene has a large number of functional groups such as hydroxyl groups on the surface, so that the MXene has the possibility of being modified. Therefore, MXene is modified to become a flame retardant with excellent performance, and the prepared flame-retardant composite material not only has excellent flame-retardant performance, but also can improve the mechanical property, the electric conductivity and the electromagnetic shielding performance, thereby providing possibility for preparing the flame-retardant composite material with multifunction.
Disclosure of Invention
The invention aims to provide a modified Mxene/PVA flame-retardant composite material which has the characteristics of excellent mechanical property, conductive performance, electromagnetic shielding performance, strong flame-retardant performance and the like.
The invention also aims to provide a preparation method of the flame-retardant composite material
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a modified Mxene/PVA flame-retardant composite material is compounded by a flame-retardant additive and a resin matrix, wherein the mass of the flame-retardant additive accounts for 1-10% of the total mass of the composite material; the resin matrix is polyvinyl alcohol resin, the flame retardant additive is modified MXene, and the modifier is nano silicon dioxide and a silane coupling agent.
The other technical scheme adopted by the invention is as follows: the preparation method of the flame-retardant composite material comprises the following steps:
1) dispersing the Mxene in deionized water, and carrying out ultrasonic treatment for 20-30 min to obtain an Mxene dispersion liquid with the mass volume concentration of 2 mg/mL;
preparation of Mxene:
A. adding 30mL of hydrochloric acid and 10mL of deionized water into a polytetrafluoroethylene beaker, then adding 3.5-4.5 g of lithium fluoride, and fully stirring at the rotating speed of 300-400 r/min for 25-30 min to obtain a mixed solution;
B. slowly adding 3.5-4.5 g of titanium aluminum carbide (MAX phase) into the mixed solution obtained in the step A, stirring at the temperature of 45-55 ℃ and the rotating speed of 400-600 r/min for constant-temperature reaction for 24-48 h to obtain reacted solution, washing the reacted solution with deionized water until the pH value of the reacted solution is neutral, centrifuging at the rotating speed of 3500-5000 r/min for 10-30 min, and taking supernatant to obtain MXene.
2) According to the proportion that 1g of Cetyl Trimethyl Ammonium Bromide (CTAB) and 2mL of tetraethoxysilane are required to be added into 100mL of MXene dispersion liquid, cetyl trimethyl ammonium bromide and tetraethoxysilane are respectively taken; adding the obtained hexadecyl trimethyl ammonium bromide into MXene dispersion liquid, and carrying out magnetic stirring reaction for 10-20 min at the rotating speed of 200-300 r/min to obtain a mixed solution;
3) adjusting the pH value of the mixed solution to 9.0-9.5 by using sodium hydroxide, and magnetically stirring and reacting at the temperature of 40 ℃ at the rotating speed of 200-300 r/min for 8 hours; slowly adding the obtained tetraethoxysilane, and magnetically stirring at the rotating speed of 300-500 r/min for reaction for 8 hours; centrifugally washing the reactant for 4-5 min by using ethanol at the rotating speed of 8000-10000 r/min, and washing for 3-5 times to obtain a precipitate;
4) dissolving the precipitate into an ethanol aqueous solution according to the proportion of adding 2g of the precipitate into 100mL of the ethanol aqueous solution, slowly dripping a silane coupling agent with the mass of 0.5-2% of the mass of the ethanol aqueous solution, magnetically stirring for reaction for 4 hours at the temperature of 50-60 ℃ and the rotating speed of 200-300 r/min, centrifugally washing a reaction product for 4-5 minutes at the rotating speed of 9000-11000 r/min by using ethanol, washing for 3-5 times, and vacuum drying for 10-12 hours at the temperature of 50-70 ℃ to obtain the modified MXene;
the silane coupling agent is preferably KH-550.
The ratio of the ethanol aqueous solution is ethanol: water = 7-8: 3-2 (volume ratio).
5) Dispersing polyvinyl alcohol into deionized water according to the proportion of adding 2-3 g of polyvinyl alcohol into 40-50 mL of deionized water, and magnetically stirring for 1-2 hours at the temperature of 90 ℃ and the rotating speed of 100-500 r/min to obtain a polyvinyl alcohol solution;
the polymerization degree of polyvinyl alcohol was 1750.
6) And (2) adding 0.02-0.06 g of modified Mxene obtained in the step 4) into 40-50 mL of the polyvinyl alcohol solution obtained in the step 5), dispersing the modified MXene into the polyvinyl alcohol solution, magnetically stirring at the rotating speed of 300-500 r/min for 20-30 min, uniformly dispersing, transferring into a mold, drying at normal temperature for 24-48 h, drying at the temperature of 40-60 ℃ for 10-20 min, and demolding to obtain the multifunctional flame-retardant composite material. The mass of the modified MXene in the composite material accounts for 1-10% of the total mass of the composite material.
SEM and TEM images of the MXene obtained are shown in FIG. 1, which shows that MXene after ultrasonic stripping is a typical single-layer or few-layer lamellar structure. The successful preparation of MXene is demonstrated.
In the flame-retardant composite material, the flame-retardant additive is less in addition amount and low in cost, and the mechanical property of the composite material can be obviously improved. The silane coupling agent and the polyvinyl alcohol have similar polar groups, so the modified MXene has better dispersibility in the matrix than the MXene, and in addition, N-H bonds on the surface of the modified MXene can easily form polar hydrogen with hydroxyl (-OH) of the polyvinyl alcohol (PVA)And the bonds hinder the migration of polymer chains, so that the flame-retardant composite material has excellent tensile property. Due to the special two-dimensional structure of the modified MXene, the modified MXene can maintain the two-dimensional structure at high temperature, plays a good barrier role in flame retardance, and is oxidized into TiO at high temperature2The reason for the modification is that the modified MXene can play a good physical barrier role on polyvinyl alcohol (PVA), and meanwhile, TiO2Plays a certain catalytic effect and improves the quality of the carbon layer. In addition, the modified MXene generates flaky silicon dioxide on the surface at high temperature to form a more stable protective layer, so that the flame retardant property is improved, the flame retardant composite material has excellent flame retardant property,
the flame-retardant composite material has the following advantages:
1) the flame-retardant composite material has the characteristics of no halogen, low smoke, no toxicity, no corrosiveness and the like, does not generate toxic or harmful gas during combustion, has a simple chemical structure of a combustion product, does not generate secondary pollution, and is an environment-friendly flame-retardant composite material.
2) Besides excellent flame retardant property, the flame retardant material also has good conductive property and electromagnetic shielding property.
3) The matrix of the flame-retardant composite material is PVA, the application range is wide, and the flame-retardant composite material can be used in the field of coatings such as building coatings.
Drawings
Fig. 1 is SEM and TEM images of MXene prepared by the present invention.
FIG. 2 is a TEM image of a modified MXene obtained in example 1 of the present invention.
Fig. 3 is an XRD pattern of modified MXene obtained in example 1 of the present invention.
FIG. 4 is a graph showing tensile properties of a flame-retardant composite material prepared by the preparation method of the present invention and a material prepared by a comparative example.
FIG. 5 is a Nyquist plot of the flame retardant composite made by the method of the present invention versus the comparative example.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
Example 1
Adding 30mL of hydrochloric acid and 10mL of deionized water into a polytetrafluoroethylene beaker, then adding 3.5g of lithium fluoride, and fully stirring at the rotating speed of 300r/min for 25 min; slowly adding 3.5g of titanium aluminum carbide (MAX phase), stirring at the rotation speed of 400r/min at the temperature of 45 ℃ for constant-temperature reaction for 48h to obtain reacted liquid, washing the reacted liquid by deionized water until the pH value of the reacted liquid is neutral, centrifuging at the rotation speed of 3500r/min for 30min, and taking supernatant to obtain MXene. Dispersing the Mxene in deionized water, and carrying out ultrasonic treatment for 30min to obtain an Mxene dispersion liquid with the mass volume concentration of 2 mg/mL; adding 1g of CTAB into 100mL of MXene dispersion liquid, and magnetically stirring and reacting for 20min at the rotating speed of 300r/min to obtain a mixed solution; adjusting the pH value of the mixed solution to 9.0 by using sodium hydroxide, and magnetically stirring and reacting at the temperature of 40 ℃ at the rotating speed of 300r/min for 8 hours; slowly adding 2mL of tetraethoxysilane, and magnetically stirring at the rotating speed of 450r/min for reaction for 8 hours; centrifugally washing reactants with ethanol at a rotating speed of 8000r/min for 4min, and washing for 3 times to obtain a precipitate; dissolving 1g of the precipitate in 100mL of ethanol water solution (ethanol: water = 7: 3 (volume ratio)), slowly dripping a silane coupling agent with the mass of 0.5% of the mass of the ethanol water solution, magnetically stirring and reacting for 4h at the temperature of 50 ℃ and the rotating speed of 300r/min, centrifugally washing for 4min at the rotating speed of 9000r/min by using ethanol, washing for 3 times, and drying for 12h at the temperature of 50 ℃ in vacuum to obtain modified MXene; dispersing 3g of polyvinyl alcohol with the polymerization degree of 1750 in 50mL of deionized water, and magnetically stirring for 2 hours at 90 ℃ and 250r/min to obtain a polyvinyl alcohol solution; dispersing 0.03g of modified MXene into 50mL of polyvinyl alcohol solution, magnetically stirring for 20min at 300r/min to uniformly disperse the modified MXene, then transferring the modified MXene into a mold, drying for 48h at normal temperature, drying for 20min at 40 ℃, and demolding to obtain the multifunctional flame-retardant composite material. The mass of the modified Mxene in the composite material accounts for 1 percent of the total mass of the composite material.
TEM image of modified Mxene prepared in example 1, as in fig. 2; it can be seen from the figure that uniform particles exist on the surface of MXene. Indicating the success of the modification. The XRD pattern of the modified MXene obtained in example 1 is shown in fig. 3; as can be seen from the figure, amorphous peaks are present which demonstrate the presence of silica. The modified MXene surface particles are nano silicon dioxide, and the success of preparing the modified MXene is proved.
Example 2
Adding 30mL of hydrochloric acid and 10mL of deionized water into a polytetrafluoroethylene beaker, then adding 4.5g of lithium fluoride, fully stirring for 30min at the rotating speed of 400r/min, slowly adding 4.5g of titanium aluminum carbide (MAX phase), stirring at the rotating speed of 600r/min at the temperature of 55 ℃, reacting at a constant temperature for 24h to obtain a reacted liquid, washing the reacted liquid with the deionized water until the pH value of the reacted liquid is neutral, centrifuging at the rotating speed of 5000r/min for 10min, and taking a supernatant to obtain MXene. Dispersing the Mxene in deionized water, and carrying out ultrasonic treatment for 20min to obtain an Mxene dispersion liquid with the mass volume concentration of 2 mg/mL; adding 1g of CTAB into 100ml of MXene dispersion liquid, and magnetically stirring and reacting for 10min at 200r/min to obtain a mixed solution; adjusting the pH value of the mixed solution to 9.5 by using sodium hydroxide, and carrying out magnetic stirring reaction for 8 hours at 40 ℃ and at 200 r/min; slowly adding 2ml of ethyl orthosilicate, and magnetically stirring and reacting for 8 hours at 300 r/min; centrifuging and washing the reactant for 4min by using ethanol at the rotating speed of 10000r/min, and washing for 5 times to obtain a precipitate; dissolving 1g of the precipitate in 100mL of ethanol water solution (ethanol: water = 8: 3 (volume ratio)), slowly dripping a silane coupling agent with the mass of 2% of the mass of the ethanol water solution, reacting for 4 hours under magnetic stirring at 50 ℃ and 200r/min, centrifugally washing the reactant for 4 minutes by using ethanol at the rotating speed of 11000r/min, washing for 4 times, and drying for 10 hours in a vacuum oven at 70 ℃ to obtain modified MXene; dispersing 3g of polyvinyl alcohol with the polymerization degree of 1750 in 50mL of deionized water, and magnetically stirring at 90 ℃ and 500r/min for 1h to obtain a polyvinyl alcohol solution; dispersing 0.06g of modified MXene into 50mL of polyvinyl alcohol solution, magnetically stirring for 30min at 500r/min to uniformly disperse the modified MXene, then transferring the modified MXene into a mold, drying for 24h at normal temperature, drying for 10min in a drying oven at 60 ℃, and demolding to obtain the multifunctional flame-retardant composite material. The mass of the modified Mxene in the composite material accounts for 2 percent of the total mass of the composite material.
Example 3
Adding 30mL of hydrochloric acid and 10mL of deionized water into a polytetrafluoroethylene beaker, then adding 4.0g of lithium fluoride, fully stirring for 27min at the rotating speed of 350r/min, slowly adding 4.0g of titanium aluminum carbide (MAX phase), stirring at the rotating speed of 500r/min at the temperature of 50 ℃, reacting for 36h at constant temperature to obtain reacted liquid, washing the reacted liquid with the deionized water until the pH value of the reacted liquid is neutral, centrifuging for 20min at the rotating speed of 4250r/min, and taking supernatant to obtain MXene. Dispersing the Mxene in deionized water, and carrying out ultrasonic treatment for 25min to obtain an Mxene dispersion liquid with the mass volume concentration of 2 mg/ml; adding 1g of CTAB into 100mL of MXene dispersion solution, and magnetically stirring and reacting for 15min at 250r/min to obtain a mixed solution; adjusting the pH value of the mixed solution to 9.25 by using sodium hydroxide, and carrying out magnetic stirring reaction for 8 hours at 40 ℃ and 250 r/min; slowly adding 2ml of ethyl orthosilicate, and magnetically stirring and reacting for 8 hours at 300 r/min; centrifuging and washing the reactant for 4.5min by using ethanol at the rotating speed of 9000r/min, and washing for 4 times to obtain a precipitate; dissolving 1g of the precipitate in 100mL of ethanol aqueous solution (ethanol: water = 7.5: 2.5 (volume ratio)), slowly dripping a silane coupling agent with the mass of 1.25% of the mass of the ethanol aqueous solution, magnetically stirring at 50 ℃ and 250r/min for reaction for 4h, centrifugally washing the reactant with ethanol at the rotation speed of 10000r/min for 4 times for 4min, and drying in a vacuum oven at 60 ℃ for 11h to obtain modified MXene; dispersing 3g of polyvinyl alcohol with the polymerization degree of 1750 in 50ml of deionized water, and magnetically stirring for 1.5h at 90 ℃ and 100r/min to obtain a polyvinyl alcohol solution; dispersing 0.09g of modified MXene into 50mL of polyvinyl alcohol solution, magnetically stirring for 25min at 400r/min to uniformly disperse the modified MXene, then transferring the modified MXene into a mold, drying for 36h at normal temperature, drying for 15min in a drying oven at 50 ℃, and demolding to obtain the multifunctional flame-retardant composite material. The mass of the modified Mxene in the composite material accounts for 3 percent of the total mass of the composite material.
Example 4
Mxene was prepared as in example 1. Dispersing the Mxene in deionized water, and carrying out ultrasonic treatment for 30min to obtain an Mxene dispersion liquid with the mass volume concentration of 2 mg/mL; adding 1g of hexadecyl trimethyl ammonium bromide into 100mL of MXene dispersion liquid, and magnetically stirring and reacting for 20min at 300r/min to obtain a mixed solution; adjusting the pH value of the mixed solution to 9.0 by using sodium hydroxide, and carrying out magnetic stirring reaction for 8 hours at 40 ℃ and 300 r/min; slowly adding 2mL of tetraethoxysilane, and magnetically stirring and reacting for 8 hours at the speed of 450 r/min; centrifuging and washing the reactant for 4min by using ethanol at the rotating speed of 8000r/min, and washing for 3 times to obtain a precipitate; dissolving 1g of precipitate in 100mL of ethanol water solution (ethanol: water = 7: 2 (volume ratio)), slowly dripping a silane coupling agent with the mass of 0.5% of the mass of the ethanol water solution, reacting for 4h under magnetic stirring at 50 ℃ and 300r/min, centrifugally washing a reaction product for 4min at the rotating speed of 9000r/min by using ethanol, washing for 3 times, and drying for 12h in a vacuum oven at 50 ℃ to obtain modified MXene; dispersing 3g of polyvinyl alcohol in 50mL of deionized water, and magnetically stirring at 90 ℃ and 250r/min for 2h to obtain a polyvinyl alcohol solution; dispersing 0.3g of modified MXene into 50mL of polyvinyl alcohol solution, magnetically stirring for 20min at 300r/min to uniformly disperse the modified MXene, then transferring the modified MXene into a mold, drying for 48h at normal temperature, drying for 20min in a drying oven at 40 ℃, and demolding to obtain the multifunctional flame-retardant composite material. The mass of the modified Mxene in the composite material accounts for 10 percent of the total mass of the composite material.
Comparative example 1
And drying the polyvinyl alcohol solution with the mass volume concentration of 0.06g/mL at normal temperature to obtain a polyvinyl alcohol sample.
Comparative example 2
Mixing MXene and a PVA solution uniformly to obtain a mixed solution, wherein the mass of the Mxene accounts for 1% of the mass of the mixed solution; and drying the mixed solution at normal temperature to obtain the composite material.
The flame-retardant composite materials prepared in examples 1 to 4, the polyvinyl alcohol sample prepared in comparative example 1 and the composite material prepared in comparative example 2 were subjected to Limit Oxygen Index (LOI) test and carbon residue content detection, and the results are shown in table 1.
TABLE 1 test results of limiting oxygen index, carbon residue content, and electromagnetic shielding property
As can be seen from Table 1, the ratio of the limiting oxygen index to the carbon residue content of the multifunctional flame-retardant composite material prepared by the preparation method provided by the invention is obviously improved, and the flame-retardant property is obviously improved compared with that of the composite material prepared by pure polyvinyl alcohol or unmodified MXene. In example 4, after the addition amount of the flame retardant reaches 10%, the limiting oxygen index of the composite material can reach more than 30%, which proves that the flame retardant effect of the composite material can reach an excellent degree along with the increase of the addition amount of the flame retardant. In addition, the electromagnetic shielding effect is increased along with the increase of the addition amount of the modified MXene, and the flame-retardant composite material has great application potential in the field of electromagnetic shielding.
As shown in FIG. 4, the stress-strain curve graphs of the mechanical property tests of the flame-retardant composite materials prepared in the embodiments 1-3 and the flame-retardant composite materials prepared in the comparative examples 1-2 show that the mechanical property of the flame-retardant composite material prepared by the preparation method is obviously improved, because the silane coupling agent and the polyvinyl alcohol have similar polar groups, the dispersibility of the modified MXene in the matrix is better than that of the MXene, and in addition, the N-H bond on the modified surface can easily form a polar hydrogen bond with the hydroxyl (-OH) of PVA to block the migration of a polymer chain, so that the multifunctional flame-retardant composite material prepared by the preparation method has excellent tensile property.
Nyquist plots of the flame-retardant composite materials prepared in examples 1-3 and the flame-retardant composite materials prepared in comparative examples 1-2 are shown in FIG. 5, which shows that the radius of the Nyquist circle of the flame-retardant composite materials prepared in examples 1-3 is smaller, which means that the charge transfer resistance is low, and the flame-retardant composite materials prepared by the preparation method of the invention are proved to have better conductivity.
Claims (3)
1. The modified Mxene/PVA flame-retardant composite material is characterized by being formed by compounding a flame-retardant additive and a resin matrix, wherein the mass of the flame-retardant additive accounts for 1-10% of the total mass of the composite material; the resin matrix is polyvinyl alcohol resin, and the flame retardant additive is modified MXene.
2. A preparation method of the modified Mxene/PVA flame retardant composite material as claimed in claim 1, which is characterized in that the preparation method comprises the following steps:
1) dispersing the Mxene in deionized water, and performing ultrasonic treatment to obtain an Mxene dispersion liquid with the mass volume concentration of 2 mg/mL;
2) adding 1g of hexadecyl trimethyl ammonium bromide and 2mL of ethyl orthosilicate into 100mL of MXene dispersion liquid, and respectively taking hexadecyl trimethyl ammonium bromide and ethyl orthosilicate; adding the obtained hexadecyl trimethyl ammonium bromide into MXene dispersion liquid, and carrying out magnetic stirring reaction for 10-20 min at the rotating speed of 200-300 r/min to obtain a mixed solution;
3) adjusting the pH value of the mixed solution to 9.0-9.5 by using sodium hydroxide, and magnetically stirring and reacting at the temperature of 40 ℃ at the rotating speed of 200-300 r/min for 8 hours; slowly adding the obtained tetraethoxysilane, and magnetically stirring at the rotating speed of 300-500 r/min for reaction for 8 hours; centrifuging and washing reactants by using ethanol to obtain a precipitate;
4) dissolving the precipitate into an ethanol aqueous solution according to the proportion of adding 2g of the precipitate into 100mL of the ethanol aqueous solution, slowly dripping a silane coupling agent with the mass of 0.5-2% of the mass of the ethanol aqueous solution, magnetically stirring for reaction for 4 hours at the temperature of 50-60 ℃ and the rotating speed of 200-300 r/min, centrifugally washing a reaction product with ethanol, and drying in vacuum to obtain modified MXene;
the ethanol aqueous solution is prepared from water and ethanol, wherein the volume ratio of the ethanol to the water is that the ethanol to the water is = 7-8: 3-2;
5) dispersing polyvinyl alcohol into deionized water according to the proportion of adding 2-3 g of polyvinyl alcohol into 40-50 mL of deionized water, and magnetically stirring for 1-2 hours at the temperature of 90 ℃ and the rotating speed of 100-500 r/min to obtain a polyvinyl alcohol solution;
6) adding 0.02-0.06 g of modified Mxene into 40-50 mL of polyvinyl alcohol solution, dispersing the modified MXene into the polyvinyl alcohol solution, magnetically stirring at the rotating speed of 300-500 r/min for 20-30 min, uniformly dispersing, transferring into a mold, drying at normal temperature for 24-48 h, drying at 40-60 ℃ for 10-20 min, and demolding to obtain the multifunctional flame-retardant composite material.
3. A method of preparing a modified Mxene/PVA fire retardant composite material according to claim 2, wherein the Mxene in step 1) is prepared by:
A. adding 30mL of hydrochloric acid and 10mL of deionized water into a polytetrafluoroethylene beaker, then adding 3.5-4.5 g of lithium fluoride, and fully stirring at the rotating speed of 300-400 r/min for 25-30 min to obtain a mixed solution;
B. slowly adding 3.5-4.5 g of titanium aluminum carbide into the mixed solution, stirring at the temperature of 45-55 ℃ and the rotating speed of 400-600 r/min, reacting at a constant temperature for 24-48 h to obtain a reacted solution, washing the reacted solution with deionized water until the pH value of the reacted solution is neutral, centrifuging, and taking supernatant to obtain MXene.
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