CN112724462B - Titanium carbide nano powder for ABS flame retardation, smoke suppression and toxicity reduction and preparation method thereof - Google Patents

Titanium carbide nano powder for ABS flame retardation, smoke suppression and toxicity reduction and preparation method thereof Download PDF

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CN112724462B
CN112724462B CN202011607902.3A CN202011607902A CN112724462B CN 112724462 B CN112724462 B CN 112724462B CN 202011607902 A CN202011607902 A CN 202011607902A CN 112724462 B CN112724462 B CN 112724462B
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titanium carbide
abs
bodipy
nano powder
smoke
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CN112724462A (en
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杨伟
朱三娥
王奋斗
高田玉
鲁红典
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Suzhou Hexumei Technology Co ltd
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Hefei University
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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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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

Abstract

Titanium carbide nano powder for ABS flame retardation, smoke suppression and toxicity reduction and a preparation method thereof belong to the technical field of nano material preparation. The boron fluoride fluorescent material is formed by combining boron fluoride fluorescence and two-dimensional titanium carbide through interface charge attraction, and has a sheet structure, the thickness of a sheet layer is 5-20nm, and the facing diameter is 0.5-2 mu m. Compared with covalent bond combination, the titanium carbide nano powder for ABS flame retardance, smoke suppression and toxicity reduction of the invention does not damage the surface structure of titanium carbide and can keep the original shape and structure of titanium carbide nano sheets. Good hydrophobicity and good compatibility with ABS, and can be uniformly dispersed in ABS resin. Can improve the oxygen index of ABS, reduce the heat release rate and smoke generation rate in the combustion process, and inhibit HCN and NOx、NH3And release of toxic gases such as CO. The tensile strength of ABS can be improved under the condition of low addition amount, the elongation at break of ABS can be maintained, and better mechanical properties can be embodied.

Description

Titanium carbide nano powder for ABS flame retardation, smoke suppression and toxicity reduction and preparation method thereof
Technical Field
The invention belongs to the technical field of preparation of nano materials, and particularly relates to titanium carbide nano powder for ABS flame retardance, smoke suppression and toxicity reduction and a preparation method thereof.
Background
Acrylonitrile-butadiene-styrene copolymer (ABS for short) is a thermoplastic high polymer material with high strength, good toughness and easy processing and molding, and is widely applied to the industries of machinery, electricity, textile, automobiles, shipbuilding and the like. However, ABS is highly flammable and produces significant amounts of soot and toxic gases (e.g., HCN, NO) during combustionxCO, etc.), which is very likely to cause poisoning and suffocation of people. At present, halogen compounds and phosphorus-nitrogen compounds are commonly used flame retardants for ABS. The flame retardant with the mass percent of 10-30% can effectively inhibit the combustion of ABS, but has very limited inhibiting effect on smoke particles and toxic gases. Therefore, the smoke suppressant is often used in combination with a flame retardant to reduce smoke generated during ABS combustion.
The currently reported smoke suppressants are various in types, such as zinc borate, zinc hydroxystannate, magnesium hydroxide, ferrocene, talcum powder and dimethyl siliconKetones, and the like. Although these smoke suppressants can exert certain smoke suppression function, most of them are micron-sized inorganic substances, and the larger particle size influences the mechanical properties of ABS. In recent years, two-dimensional layered nano materials have received wide attention from scholars at home and abroad. Due to the large specific surface area, excellent dimensional stability and special gas barrier effect, the two-dimensional layered nano material has been used as a flame-retardant smoke suppressant to be applied to the modification of ABS resin. For example, chinese patent CN200810105083.5 reports a perfluorobutyl sulfonate intercalated hydrotalcite layered material and a preparation method thereof, which can reduce the smoke density of ABS, but with a large addition amount. Chinese patent CN201811458067.4 adopts the cooperation of layered alpha-zirconium phosphate nano material (with the addition of 2-4%) and melamine phosphate, and can reduce the smoke density of ABS. Chinese patent CN201810386028.1 reports a lanthanum-loaded organic phosphorus-modified nitrogen-doped graphene and a preparation method thereof, and cone calorimeter test results show that the functionalized graphene nanosheet (with the addition amount of 0.1-10%) can inhibit smoke release during ABS combustion. Although these two-dimensional nanomaterials can reduce soot production during ABS combustion, it does not address HCN, NOxThe inhibition of toxic gases such as CO has been reported.
Titanium carbide (Ti)3C2Tx) Is a novel two-dimensional layered nano material, and can be prepared from typical ternary layered carbide titanium aluminum carbide (Ti) by hydrofluoric acid3AlC2) In which an aluminum (Al) atomic layer is stripped. In recent years, two-dimensional titanium carbide has been reported for flame retardancy of polymers, mainly based on its lamellar barrier effect and catalytic effect, but has not been reported to have an effect on soot and toxic gases during combustion of polymers. In addition, after the two-dimensional titanium carbide is synthesized by a chemical method, because the surface energy of the nanoparticles is higher, the nanoparticles tend to aggregate thermodynamically and are difficult to disperse in a polymer matrix. Meanwhile, the titanium carbide surface etched by hydrofluoric acid contains functional groups such as hydroxyl, oxygen and the like, so that the titanium carbide surface has strong hydrophilicity and poor compatibility with hydrophobic polymers, thereby affecting the full play of the performance of the titanium carbide. Therefore, the preparation of the high-quality two-dimensional titanium carbide nano powder for ABS flame retardance, smoke suppression and attenuation is a difficult point in research and development at present.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides titanium carbide nano powder for ABS flame retardance, smoke suppression and toxicity reduction and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a titanium carbide nano-powder for ABS flame-retarding, smoke-suppressing and toxicity-reducing is prepared from fluoboron and two-dimensional titanium carbide through attracting and combining them together to obtain fluoboron modified titanium carbide BODIPY-Ti3C2TxIt has a sheet structure, the thickness of the sheet layer is 5-20nm, and the facing diameter is 0.5-2 μm.
A process for preparing nm-class titanium carbide powder includes such steps as selectively etching aluminium layer from titanium carbonate to obtain titanium carbide, oxidizing 2, 3-dichloro-5, 6-dicyan-p-benzoquinone by 2, 3-dichloro-5, 6-dicyan-p-benzoquinone, coordinating boron trifluoride by ethyl ether, reducing to obtain fluoroboro-fluor containing amino group, and combining titanium carbide with fluoroboro-fluor by interface charge attraction to obtain fluoromodified titanium carbide BODIPY-Ti3C2Tx。
As a preferred technical scheme of the preparation method, the preparation method comprises the following specific steps:
1) etching an aluminum atomic layer in the aluminum titanium carbide by using a mixed solution of lithium fluoride and hydrochloric acid to prepare a titanium carbide precipitate;
2) re-dispersing the titanium carbide precipitate obtained in the step 1) in water, performing ultrasonic treatment and centrifugation, removing the precipitate, and taking supernatant to obtain a titanium carbide nanosheet suspension;
3) 2, 4-dimethylpyrrole and p-nitrobenzaldehyde are used as raw materials, oxidized by 2, 3-dichloro-5, 6-dicyan p-benzoquinone, coordinated by boron trifluoride diethyl etherate, and reduced to obtain amino-containing borofluoride fluorescence;
4) dissolving the fluoborate obtained in the step 3) in ethanol, and adjusting the pH value to 1-3 to obtain a transparent solution;
5) adding the fluoboron fluorescent solution obtained in the step 4) into the titanium carbide nanosheet suspension obtained in the step 2), and obtaining a nano powder precipitate after reaction, namely fluoboron fluorescent modified titanium carbide BODIPY-Ti3C2Tx。
As a further preferable technical scheme of the preparation method, the preparation method comprises the following specific steps:
1) placing 0.5g of titanium aluminum carbide and 0.5g of lithium fluoride in a plastic beaker, adding 10-15mL of hydrochloric acid with the concentration of 7-10mol/L, stirring and reacting at 35-50 ℃ for 36-60h at the stirring speed of 400-600rpm, repeatedly centrifuging and washing after the reaction is finished until the pH value is 7, and drying to obtain a titanium carbide precipitate;
2) taking 0.2g of the titanium carbide precipitate obtained in the step 1), dispersing in 50mL of deionized water, performing ultrasonic treatment at 0-5 ℃ for 30-60min and the ultrasonic power of 100-;
3) dissolving 2.9g of 2, 4-dimethylpyrrole and 1.8g of p-nitrobenzaldehyde in 180-mL of tetrahydrofuran, introducing nitrogen for protection, adding 1-3mL of trifluoroacetic acid, reacting at 25-30 ℃ for 12-18h, then adding 2.8g of 2, 3-dichloro-5, 6-dicyan-p-benzoquinone, continuing to react at 25-30 ℃ for 4-6h, respectively adding 70-80mL of triethylamine and 75-85mL of boron trifluoride diethyl ether at 0-5 ℃, reacting at 25-30 ℃ for 10-12h, extracting with dichloromethane and water, drying the organic phase with anhydrous sodium sulfate, filtering to remove a drying agent, removing an organic solvent by rotary evaporation, separating by column chromatography, then adding 90-120mL of anhydrous ethanol, 1-5mL of hydrazine hydrate and 0.1-0.5g of palladium carbon, reacting for 2-4h at 90-100 ℃, and finally purifying and drying to obtain the amino-containing fluoborate.
4) Dissolving 0.2g of the fluoborate obtained in the step 3) in 20-50mL of ethanol, and adding hydrochloric acid to adjust the pH value of the solution to 1-3 to obtain a transparent solution;
5) and (3) dropwise adding 20mL of the fluoboric fluorescent solution obtained in the step 4) into 20mL of the titanium carbide nanosheet suspension obtained in the step 2), stirring and reacting for 15-30min under the condition of the rotation speed of 400-600rpm, repeatedly centrifuging and washing after the reaction is finished, and drying to obtain a product, namely the titanium carbide nano powder for ABS flame retardance, smoke suppression and attenuation.
Further preferably, the mass ratio of the fluoboron fluorescent powder to the titanium carbide in the step 5) of the preparation method is 1: 0.5-1.
The invention provides an application of titanium carbide nano powder as an ABS flame-retardant smoke-suppression and toxicity-reduction agent, and particularly relates to a composite material prepared by liquid-phase mixing of boron-fluorine fluorescent modified titanium carbide and ABS, wherein the addition proportion of the boron-fluorine fluorescent modified titanium carbide in the composite material is 0.5-2 wt%.
As a preferred technical scheme of the application, the step of preparing the composite material by liquid phase mixing comprises the following steps: dissolving 0.1-0.4g of fluoboron fluorescence modified titanium carbide nano powder and 19.6-19.9g of ABS in 250mL of N, N-dimethylformamide of 200-.
Compared with the prior art, the titanium carbide nano powder for ABS flame retardation, smoke suppression and toxicity reduction and the preparation method thereof have the following advantages:
1) the titanium carbide nano powder for flame retardation, smoke suppression and toxicity reduction of ABS is formed by combining fluoboron fluorescence and two-dimensional titanium carbide through interface charge attraction, compared with covalent bond combination, the surface structure of the titanium carbide nano powder cannot be damaged, and the original shape and structure of the titanium carbide nano sheet can be maintained.
2) The titanium carbide nano powder for ABS flame retardation, smoke suppression and toxicity reduction has uniform size, large specific surface area, lamella thickness of about 5-20nm and facing diameter of about 0.5-2 μm.
3) The titanium carbide nano powder for flame retardation, smoke suppression and toxicity reduction of ABS has good hydrophobicity and good compatibility with ABS, and can be uniformly dispersed in ABS resin.
4) The titanium carbide nano powder for ABS flame retardation, smoke suppression and toxicity reduction can improve the oxygen index of ABS, reduce the heat release rate and smoke generation rate in the combustion process, and inhibit HCN and NOx、NH3And release of toxic gases such as CO.
5) The titanium carbide nano powder for flame retardation, smoke suppression and toxicity reduction of ABS can improve the tensile strength of ABS under low addition amount, maintain the elongation at break of ABS and embody better mechanical properties.
Drawings
Fig. 1 is a Transmission Electron Microscope (TEM) image of the exfoliated titanium carbide nanoplates prepared in example 1.
FIG. 2 is a scheme showing the fluoroborate prepared in example 11H NMR spectrum.
FIG. 3 shows a schematic view of a titanium aluminum carbide (Ti)3AlC2) Raw material and exfoliated titanium carbide nanoplates (Ti) prepared in example 13C2Tx) Boron fluoride fluorescence modified titanium carbide (BODIPY-Ti)3C2Tx) X-ray diffraction pattern (XRD).
FIG. 4 shows the boron fluoride phosphor (BODIPY) and titanium carbide nanosheets (Ti) prepared in example 13C2Tx) And boron fluoride fluorescent modified titanium carbide (BODIPY-Ti)3C2Tx) Thermogravimetric plot (TGA) of (a).
FIG. 5 shows the boron fluoride fluorescence modified titanium carbide (BODIPY-Ti) prepared in example 13C2Tx) Scanning Electron Microscope (SEM) picture (a) and corresponding energy spectrum (EDS) (b).
FIG. 6 shows the boron fluoride fluorescence modified titanium carbide (BODIPY-Ti) prepared in example 13C2Tx) SEM images at high magnification.
FIG. 7 shows the boron fluoride fluorescence modified titanium carbide (BODIPY-Ti) prepared in example 13C2Tx) Performing ultrasonic standing in different solvents to obtain digital photos (corresponding to a, b and c, ultrasonic standing for 1min, 6h and 24 h; a1-a5, b1-b5 and c1-c5 correspond to different solvents: deionized water, tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide, dichloromethane).
FIG. 8 is the ABS/BODIPY-Ti prepared in example 53C2TxTEM images of the nanocomposites.
FIG. 9 shows two ABS/BODIPY-Ti formulations prepared in examples 5 and 63C2TxAnd the Heat Release Rate (HRR), smoke generation rate (SPR), and toxic gas concentration curves for the ABS/BODIPY and pure ABS prepared in comparative example 1.
FIG. 10 shows two ABS/BODIPY materials prepared in examples 5 and 6Ti3C2TxAnd tensile property test curves for ABS/BODIPY and neat ABS prepared in comparative example 1.
Detailed Description
The titanium carbide nano powder for flame retardation, smoke suppression and attenuation of ABS and the preparation method thereof of the present invention are further described in detail with reference to the following embodiments and the accompanying drawings.
Example 1
1) And (3) putting 0.5g of titanium aluminum carbide and 0.5g of lithium fluoride in a plastic beaker, adding 10mL of hydrochloric acid with the concentration of 10mol/L, stirring and reacting for 48 hours at 40 ℃, wherein the stirring speed is 400rpm, repeatedly centrifuging and washing after the reaction is finished until the pH value is 7, and drying to obtain the titanium carbide precipitate.
2) Taking 0.2g of titanium carbide precipitate obtained in the step 1), dispersing in 50mL of deionized water, performing ultrasonic treatment at 0 ℃ for 30min with the ultrasonic power of 300W, then centrifuging at 5000rpm, removing the precipitate, and taking supernatant to obtain the titanium carbide nanosheet suspension.
3) Dissolving 2.9g of 2, 4-dimethylpyrrole and 1.8g of p-nitrobenzaldehyde in 200mL of tetrahydrofuran, introducing nitrogen for protection, adding 1mL of trifluoroacetic acid, reacting at 25 ℃ for 12h, then adding 2.8g of 2, 3-dichloro-5, 6-dicyan-p-benzoquinone, continuing to react at 25 ℃ for 4h, respectively adding 70mL of triethylamine and 75mL of boron trifluoride diethyl ether at 0 ℃, reacting at 25 ℃ for 10h, extracting with dichloromethane and water, drying an organic phase with anhydrous sodium sulfate, filtering to remove a drying agent, removing an organic solvent by rotary evaporation, separating by column chromatography, then adding 90mL of anhydrous ethanol, 1mL of hydrazine hydrate and 0.1g of palladium carbon, reacting at 90 ℃ for 2h, and finally purifying and drying to obtain the amino-containing fluoroboric fluorescence.
4) Dissolving 0.2g of the fluoborate obtained in the step 3) in 50mL of ethanol, and adding hydrochloric acid to adjust the pH value of the solution to 1 to obtain a transparent solution.
5) And (3) dropwise adding 20mL of the fluoboric fluorescent solution obtained in the step 4) into 20mL of the titanium carbide nanosheet suspension obtained in the step 2), stirring and reacting for 30min at the rotation speed of 600rpm, repeatedly centrifuging and washing after the reaction is finished, and drying to obtain a product, namely the titanium carbide nanopowder for flame retardance, smoke suppression and attenuation of the ABS.
Fig. 1 is a TEM image of the exfoliated titanium carbide nanoplates prepared in example 1. As can be seen in fig. 1, the two-dimensional titanium carbide lamellae are translucent, indicating that the titanium carbide is effectively exfoliated into single or few nanosheets.
FIG. 2 shows the fluorescent substance containing the aminofluoroboron prepared in example 11H NMR spectrum. As can be seen from fig. 2, the doublet at chemical shifts 7.02 and 6.80 are both phencyclyl hydrogens, the singlet at 5.99 is pyrrolyl hydrogens, the singlet at 3.86 is amino hydrogens, and the singlets at 2.56 and 1.51 are both methyl hydrogens.
FIG. 3 shows a schematic view of a titanium aluminum carbide (Ti)3AlC2) Raw material and exfoliated titanium carbide nanoplates (Ti) prepared in example 13C2Tx) Boron fluoride fluorescence modified titanium carbide (BODIPY-Ti)3C2Tx) XRD pattern of (a). As can be seen from FIG. 3, with Ti3AlC2Raw material ratio, Ti after exfoliation3C2TxWith completely different structural features. Ti3AlC2The (002) diffraction peak of (1) shifted from 9.5 ° to 6.3 °, corresponding to an increase in the interlayer distance from 0.92nm to 1.40 nm. Further, Ti3AlC2The (104) diffraction peak at 38.8 ° 2 θ is ascribed to Al, and Ti3C2TxAlmost no diffraction peak was observed in the range of 35 to 40 degrees 2 theta, indicating that Ti was present3AlC2The Al layer in (a) was successfully etched away. Modified by BODIPY, Ti3C2TxThe diffraction peak of (002) was further shifted from 6.3 ° to a low angle of 5.0 °, and the corresponding interlayer distance was increased from 1.40nm to 1.77nm, indicating that BODIPY was attached to Ti3C2TxThe interlayer distance of the surface of the sheet layer is further enlarged. In addition, with Ti3C2TxIn contrast, BODIPY-Ti3C2Tx(002) The intensity of the diffraction peak was significantly reduced, indicating that Ti3C2TxThe highly ordered arrangement is disturbed by the introduction of BODIPY, resulting in a decrease in crystallinity.
FIG. 4 shows the boron fluoride phosphor (BODIPY) and titanium carbide nanosheets (Ti) prepared in example 13C2Tx) And boron fluoride fluorescent modified titanium carbide (BODIPY-Ti)3C2Tx) TGA profile of (a). As can be seen from fig. 4, BODIPY started to decompose at 260 ℃ (temperature corresponding to 5% weight loss), with a residual content of 30.5% at 700 ℃, 69.5% weight loss, due to thermal decomposition of the organic matter. Ti3C2TxThe decomposition was started at 135 ℃ and the residual content at 700 ℃ was 90.6%, the weight loss was 9.4%, which is attributed to Ti3C2TxRemoval of adsorbed water and decomposition of organic functional groups (OH, O, F, etc.). BODIPY-Ti3C2TxHas a thermal decomposition temperature significantly higher than that of Ti3C2TxHigh, beginning to decompose at 260 ℃ and residual content at 700 ℃ of 62.2%, weight loss of 37.8%, ascribed to BODIPY and Ti3C2TxDecomposition of surface functional groups. BODIPY and Ti in example 13C2TxThe mass ratio during the reaction is 1: 1, the overall weight loss is 39.5 percent and the actual weight loss is 37.8 percent according to the calculation of complete reaction, which is relatively close to the actual weight loss, and shows that the BODIPY modified Ti is3C2TxThe reaction of (3) was successful.
FIG. 5 shows the boron fluoride fluorescence modified titanium carbide (BODIPY-Ti) prepared in example 13C2Tx) Scanning Electron Microscope (SEM) picture (a) and corresponding energy spectrum (EDS) (b). As can be seen in FIG. 5a, BODIPY-Ti3C2TxHas obvious flaky structure, uniform size, good dispersion and no obvious agglomeration. As can be seen in FIG. 5b, BODIPY-Ti3C2TxThe main elements of Ti, C, O, N, B and F are detected, which indicates that the BODIPY is successfully modified to Ti3C2TxOn the surface.
FIG. 6 shows the boron fluoride fluorescence modified titanium carbide (BODIPY-Ti) prepared in example 13C2Tx) SEM images at high magnification. As can be seen in FIG. 6, BODIPY-Ti3C2TxHas a thickness of about 5 to 20nm and a diameter of about 0.5 to 2 μm.
FIG. 7 shows the boron fluoride fluorescence modified titanium carbide (BODI) prepared in example 1PY-Ti3C2Tx) Performing ultrasonic standing in different solvents to obtain digital photos (corresponding to a, b and c, ultrasonic standing for 1min, 6h and 24 h; a1-a5, b1-b5 and c1-c5 correspond from left to right to different solvents: deionized water, tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide, dichloromethane). As can be seen in FIG. 7, BODIPY-Ti3C2TxAfter ultrasonic treatment in deionized water and standing for 6h, obvious precipitation appears, and after 24h, complete precipitation shows that BODIPY-Ti3C2TxHas hydrophobic property. BODIPY-Ti in contrast to tetrahydrofuran and methylene chloride3C2TxThe dispersibility in dimethyl sulfoxide and N, N-dimethylformamide is better, the product is still uniformly dispersed after 24 hours, no precipitation appears, and the BODIPY-Ti is shown3C2TxIs hydrophobic and oleophilic.
Example 2
1) And (3) putting 0.5g of titanium aluminum carbide and 0.5g of lithium fluoride into a plastic beaker, adding 12mL of hydrochloric acid with the concentration of 8mol/L, stirring and reacting for 40h at 45 ℃, wherein the stirring speed is 450rpm, repeatedly centrifuging and washing after the reaction is finished until the pH value is 7, and drying to obtain the titanium carbide precipitate.
2) Taking 0.2g of titanium carbide precipitate obtained in the step 1), dispersing in 50mL of deionized water, carrying out ultrasonic treatment at 1 ℃ for 40min, wherein the ultrasonic power is 250W, then centrifuging at 4500rpm, removing the precipitate, and taking supernatant to obtain the titanium carbide nanosheet suspension.
3) Dissolving 2.9g of 2, 4-dimethylpyrrole and 1.8g of p-nitrobenzaldehyde in 190mL of tetrahydrofuran, introducing nitrogen for protection, adding 2mL of trifluoroacetic acid, reacting for 16h at 28 ℃, then adding 2.8g of 2, 3-dichloro-5, 6-dicyan-p-benzoquinone, continuing to react for 5h at 28 ℃, respectively adding 75mL of triethylamine and 80mL of boron trifluoride diethyl ether at 1 ℃, reacting for 11h at 28 ℃, extracting an organic phase by using dichloromethane and water, drying the organic phase by using anhydrous sodium sulfate, filtering to remove a drying agent, removing an organic solvent by rotary evaporation, separating by column chromatography, then adding 100mL of anhydrous ethanol, 2mL of hydrazine hydrate and 0.2g of palladium carbon, reacting for 3h at 95 ℃, and finally purifying and drying to obtain the amino-containing fluoroboric fluorescence.
4) Dissolving 0.2g of the fluoborate obtained in the step 3) in 40mL of ethanol, and adding hydrochloric acid to adjust the pH value of the solution to 2 to obtain a transparent solution.
5) And (3) dropwise adding 20mL of the fluoboric fluorescent solution obtained in the step 4) into 20mL of the titanium carbide nanosheet suspension obtained in the step 2), stirring and reacting for 20min at the rotation speed of 500rpm, repeatedly centrifuging and washing after the reaction is finished, and drying to obtain a product, namely the titanium carbide nanopowder for flame retardance, smoke suppression and attenuation of the ABS.
Example 3
1) And (3) putting 0.5g of titanium aluminum carbide and 0.5g of lithium fluoride in a plastic beaker, adding 15mL of hydrochloric acid with the concentration of 7mol/L, stirring and reacting for 60 hours at 50 ℃, wherein the stirring speed is 600rpm, repeatedly centrifuging and washing after the reaction is finished until the pH value is 7, and drying to obtain the titanium carbide precipitate.
2) Taking 0.2g of titanium carbide precipitate obtained in the step 1), dispersing in 50mL of deionized water, performing ultrasonic treatment at 2 ℃ for 50min with the ultrasonic power of 150W, then centrifuging at 4000rpm, removing the precipitate, and taking supernatant to obtain the titanium carbide nanosheet suspension.
3) Dissolving 2.9g of 2, 4-dimethylpyrrole and 1.8g of p-nitrobenzaldehyde in 180mL of tetrahydrofuran, introducing nitrogen for protection, adding 3mL of trifluoroacetic acid, reacting at 30 ℃ for 18h, then adding 2.8g of 2, 3-dichloro-5, 6-dicyan-p-benzoquinone, continuing to react at 30 ℃ for 6h, respectively adding 80mL of triethylamine and 85mL of boron trifluoride diethyl ether at 2 ℃, reacting at 30 ℃ for 12h, extracting with dichloromethane and water, drying an organic phase with anhydrous sodium sulfate, filtering to remove a drying agent, removing an organic solvent by rotary evaporation, separating by column chromatography, then adding 110mL of anhydrous ethanol, 3mL of hydrazine hydrate and 0.3g of palladium carbon, reacting at 100 ℃ for 4h, and finally purifying and drying to obtain the amino-containing fluoroboric fluorescence.
4) Dissolving 0.2g of the fluoborate obtained in the step 3) in 30mL of ethanol, and adding hydrochloric acid to adjust the pH value of the solution to 1 to obtain a transparent solution.
5) And (3) dropwise adding 20mL of the fluoboric fluorescent solution obtained in the step 4) into 20mL of the titanium carbide nanosheet suspension obtained in the step 2), stirring and reacting for 25min under the condition of the rotation speed of 400-600rpm, repeatedly centrifuging and washing after the reaction is finished, and drying to obtain a product, namely the titanium carbide nanopowder for ABS flame retardance, smoke suppression and attenuation.
Example 4
1) And (3) putting 0.5g of titanium aluminum carbide and 0.5g of lithium fluoride into a plastic beaker, adding 11mL of 9mol/L hydrochloric acid, stirring and reacting at 50 ℃ for 36h at the stirring speed of 500rpm, repeatedly centrifuging and washing after the reaction is finished until the pH value is 7, and drying to obtain the titanium carbide precipitate.
2) Taking 0.2g of titanium carbide precipitate obtained in the step 1), dispersing in 50mL of deionized water, performing ultrasonic treatment at 5 ℃ for 60min with ultrasonic power of 200W, centrifuging at 5000rpm, removing the precipitate, and taking supernatant to obtain titanium carbide nanosheet suspension.
3) Dissolving 2.9g of 2, 4-dimethylpyrrole and 1.8g of p-nitrobenzaldehyde in 200mL of tetrahydrofuran, introducing nitrogen for protection, adding 2mL of trifluoroacetic acid, reacting at 25 ℃ for 12h, then adding 2.8g of 2, 3-dichloro-5, 6-dicyan-p-benzoquinone, continuing to react at 25 ℃ for 4h, respectively adding 70mL of triethylamine and 75mL of boron trifluoride diethyl ether at 5 ℃, reacting at 25 ℃ for 10h, extracting with dichloromethane and water, drying an organic phase with anhydrous sodium sulfate, filtering to remove a drying agent, removing an organic solvent by rotary evaporation, separating by column chromatography, then adding 120mL of anhydrous ethanol, 5mL of hydrazine hydrate and 0.5g of palladium carbon, reacting at 90 ℃ for 3h, and finally purifying and drying to obtain the amino-containing fluoroboric fluorescence.
4) Taking 0.2g of the fluoborate obtained in the step 3), dissolving the fluoborate in 20mL of ethanol, and adding hydrochloric acid to adjust the pH value of the solution to 1 to obtain a transparent solution.
5) And (3) dropwise adding 20mL of the fluoboric fluorescent solution obtained in the step 4) into 20mL of the titanium carbide nanosheet suspension obtained in the step 2), stirring and reacting for 15min at the rotation speed of 600rpm, repeatedly centrifuging and washing after the reaction is finished, and drying to obtain a product, namely the titanium carbide nanopowder for flame retardance, smoke suppression and attenuation of the ABS.
Example 5
0.1g of boron fluoride fluorescent modified titanium carbide nano powder (BODIPY-Ti) is taken3C2Tx) And 19.9g of ABS dissolved in 25Stirring and ultrasonic mixing for 60min in 0mL of N, N-dimethylformamide, and mixing the uniformly mixed ABS and BODIPY-Ti3C2TxSlowly adding the mixed solution into deionized water, repeatedly washing with deionized water, and drying to obtain ABS/BODIPY-Ti3C2TxNanocomposite material due to BODIPY-Ti3C2TxThe mass percentage of the composite material is 0.5 percent, so the material is marked as ABS/BODIPY-Ti3C2Tx0.5。
FIG. 8 is the ABS/BODIPY-Ti prepared in example 53C2TxTEM images of the nanocomposites. As can be seen in FIG. 8, BODIPY-Ti3C2TxIs uniformly distributed in the ABS matrix in a single layer or few layers.
Example 6
0.4g of boron fluoride fluorescent modified titanium carbide nano powder (BODIPY-Ti) is taken3C2Tx) And 19.6g of ABS were dissolved in 200mL of N, N-dimethylformamide, stirred and simultaneously ultrasonically mixed for 50min, and the uniformly mixed ABS and BODIPY-Ti were mixed3C2TxSlowly adding the mixed solution into deionized water, repeatedly washing with deionized water, and drying to obtain ABS/BODIPY-Ti3C2TxNanocomposite material due to BODIPY-Ti3C2TxThe mass percentage of the composite material is 2 percent, so the material is marked as ABS/BODIPY-Ti3C2Tx2.0。
Comparative example 1
Dissolving 0.4g of boron fluoride fluorescence (BODIPY) and 19.6g of ABS in 200mL of N, N-dimethylformamide, stirring and ultrasonically mixing for 60min at the same time, slowly adding the uniformly mixed ABS and BODIPY mixed solution into deionized water, repeatedly washing with the deionized water, and drying to obtain the ABS/BODIPY composite material, wherein the material is marked as ABS/BODIPY2.0 because the mass percentage of the BODIPY in the composite material is 2%.
FIG. 9 shows two ABS/BODIPY-Ti formulations prepared in example 5 and example 63C2TxAnd ABS prepared in comparative example 1Heat Release Rate (HRR), Smoke Generation Rate (SPR) and toxic gases (HCN, NO, N) of/BODIPY and pure ABS2O、NH3、CO、CO2HCHO) concentration curve.
Table 1 shows two ABS/BODIPY-Ti prepared in example 5 and example 63C2TxAnd the oxygen index, heat release rate Peak (PHRR), smoke generation rate peak (PSPR), and toxic gas (HCN, NO, N) of the ABS/BODIPY and pure ABS prepared in comparative example 12O、NH3、CO、CO2HCHO). Wherein the oxygen index is measured according to ASTM D2863-77 (model ZRY, Jiangsu Jiangning Instrument analysis Co.). HRR, SPR and toxic gas data were tested using a cone calorimeter in combination with an infrared spectrometer according to ISO-56601 standard (FTT, UK).
As can be seen from FIG. 9 and Table 1, the ABS has an oxygen index of 19.5%, and is highly flammable. The oxygen index of ABS can be increased to 22.0% by adding 2% of BODIPY, and the BODIPY-Ti content3C2TxThe introduction of (2) has more remarkable improvement on the oxygen index, and shows that the flame retardant has more excellent flame retardance. BODIPY has a small effect on the Peak Heat Release Rate (PHRR) of ABS during combustion, while BODIPY-Ti3C2TxThe PHRR value can be reduced more remarkably. For example, 0.5% of BODIPY-Ti is added3C2TxSo that the PHRR of the ABS is from 1174kW/m2Reduced to 886kW/m2The amplitude reduction reaches 24.5 percent. At the same time, ABS/BODIPY-Ti3C2Tx0.5 also has a lower PSPR, a drop of 18.4% compared to pure ABS.
As can be seen from the toxic gas data, BODIPY-Ti was used3C2TxCompared with BODIPY, the nanometer powder can inhibit the release of toxic gas more obviously. For example, 0.5% BODIPY-Ti is added3C2TxSo that HCN, NO and N generated by ABS combustion2O、NH3、CO、CO2And peak concentration of HCHO is reduced by 33.5%, 22.0%, 46.6%, 76.0%, 28.8%, 32.4% and 32.8%, respectively. The above results show that the addition amount of BODIPY-Ti is low3C2TxThe nanometer powder can obviously improve the flame retardant property of ABS, inhibit the soot generation and the toxic gas release of ABS and embody BODIPY-Ti3C2TxThe nano powder has excellent flame retardant, smoke suppression and toxicity reduction effects.
TABLE 1
Figure BDA0002870688290000091
In the table: PHRRa: peak heat release rate; PSPRb: a peak smoke generation rate; HCN, NO, N2O、NH3、CO、CO2Both HCHO and HCHO are peak concentrations.
FIG. 10 shows two ABS/BODIPY-Ti formulations prepared in examples 5 and 63C2TxAnd tensile property test curves for ABS/BODIPY and neat ABS prepared in comparative example 1. As can be seen from fig. 10, BODIPY has little effect on the tensile properties of ABS and the stress-strain curves are nearly identical. While adding 0.5% BODIPY-Ti3C2TxThe tensile strength of ABS is improved by 18.8%, and the elongation at break is slightly reduced. Despite the addition of 2.0% BODIPY-Ti3C2TxCan improve the tensile strength of ABS, but the elongation at break is obviously reduced, probably because of the high addition of BODIPY-Ti3C2TxThe occurrence of agglomeration in the ABS results in an impairment of the continuity of the ABS molecules and thus in an increase in brittleness.
The results of the above combustion performance test and tensile property test were combined, and it was not difficult to see that the amount of BODIPY-Ti added was low3C2TxThe nanometer powder is added into ABS resin, which not only can play the roles of inflaming retarding, smoke suppression and toxicity reduction, but also can improve the mechanical property of ABS. In addition, the BODIPY-Ti prepared by the invention3C2TxThe nano powder can be compounded with various flame retardants for use, is applied to flame-retardant smoke-suppression attenuation treatment of various thermoplastic and thermosetting plastics and other high polymer materials such as polyolefin, polyurethane, polyamide, epoxy resin and the like, and has wide market application prospect.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.

Claims (7)

1. A titanium carbide nano-powder for ABS flame-retarding, smoke-suppressing and toxicity-reducing is prepared from fluoboron and two-dimensional titanium carbide through attracting and combining them together to obtain fluoboron modified titanium carbide BODIPY-Ti3C2TxIt has a sheet structure, the thickness of the sheet layer is 5-20nm, and the facing diameter is 0.5-2 μm.
2. A method for preparing the titanium carbide nanopowder of claim 1, wherein the titanium carbide is prepared by selectively etching an aluminum layer from titanium aluminum carbide, 2, 4-dimethylpyrrole and p-nitrobenzaldehyde are used as raw materials, the raw materials are oxidized by 2, 3-dichloro-5, 6-dicyan-p-benzoquinone, boron trifluoride diethyl etherate is coordinated, the amino-containing borofluoride is obtained by reduction, and finally the titanium carbide and the borofluoride are combined by interface charge attraction to prepare the borofluoride modified titanium carbide BODIPY-Ti through3C2Tx。
3. The method of claim 2, characterized by the steps of:
1) etching an aluminum atomic layer in the aluminum titanium carbide by using a mixed solution of lithium fluoride and hydrochloric acid to prepare a titanium carbide precipitate;
2) re-dispersing the titanium carbide precipitate obtained in the step 1) in water, performing ultrasonic treatment and centrifugation, removing the precipitate, and taking supernatant to obtain a titanium carbide nanosheet suspension;
3) 2, 4-dimethylpyrrole and p-nitrobenzaldehyde are used as raw materials, oxidized by 2, 3-dichloro-5, 6-dicyan p-benzoquinone, coordinated by boron trifluoride diethyl etherate, and reduced to obtain amino-containing borofluoride fluorescence;
4) dissolving the fluoborate obtained in the step 3) in ethanol, and adjusting the pH value to 1-3 to obtain a transparent solution;
5) adding the fluoboron fluorescent solution obtained in the step 4) into the titanium carbide nanosheet suspension obtained in the step 2), and obtaining a nano powder precipitate after reaction, namely fluoboron fluorescent modified titanium carbide BODIPY-Ti3C2Tx。
4. The method as claimed in claim 3, wherein the step 3) of preparing the amino group-containing fluoroborate comprises the following specific steps:
dissolving 2.9g of 2, 4-dimethylpyrrole and 1.8g of p-nitrobenzaldehyde in 180-mL of tetrahydrofuran, introducing nitrogen for protection, adding 1-3mL of trifluoroacetic acid, reacting at 25-30 ℃ for 12-18h, then adding 2.8g of 2, 3-dichloro-5, 6-dicyan-p-benzoquinone, continuing to react at 25-30 ℃ for 4-6h, respectively adding 70-80mL of triethylamine and 75-85mL of boron trifluoride diethyl ether at 0-5 ℃, reacting at 25-30 ℃ for 10-12h, extracting with dichloromethane and water, drying the organic phase with anhydrous sodium sulfate, filtering to remove a drying agent, removing an organic solvent by rotary evaporation, separating by column chromatography, then adding 90-120mL of anhydrous ethanol, 1-5mL of hydrazine hydrate and 0.1-0.5g of palladium carbon, reacting for 2-4h at 90-100 ℃, and finally purifying and drying to obtain the amino-containing fluoborate.
5. The method of claim 3, wherein the mass ratio of the fluoboron fluorescence to the titanium carbide in step 5) is 1: 0.5-1.
6. The application of the titanium carbide nano powder as an ABS flame-retardant smoke-suppressing and toxicity-reducing agent according to claim 1, wherein the boron-fluorine fluorescent modified titanium carbide and the ABS are mixed in a liquid phase to prepare the composite material, and the addition ratio of the boron-fluorine fluorescent modified titanium carbide in the composite material is 0.5-2 wt%.
7. The use according to claim 6, wherein the step of mixing the liquid phases to produce the composite material comprises: dissolving 0.1-0.4g of fluoboron fluorescence modified titanium carbide nano powder and 19.6-19.9g of ABS in 250mL of N, N-dimethylformamide of 200-.
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