CN114058084A - Molybdenum substrate layer modified magnesium hydroxide and preparation method and application thereof - Google Patents
Molybdenum substrate layer modified magnesium hydroxide and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of functional powder, and particularly relates to molybdenum substrate layer modified magnesium hydroxide and a preparation method and application thereof. The molybdenum substrate layer modified magnesium hydroxide provided by the invention comprises a magnesium hydroxide core and a shell formed by a molybdenum substrate layer coating the magnesium hydroxide core; the chemical composition of the molybdenum substrate layer is MoX2And X is O, S, Se or Te. In the invention, the shell formed by the molybdenum substrate layer has higher thermal stability, and can effectively prevent the molybdenum substrate layer modified magnesium hydroxide from degrading in the application process; the shell contains molybdenum element, has stronger catalytic carbonization effect and is in a lamellar shape, and the stability of a carbon layer can be enhanced in the application process, so that the physical resistance is further effectively improvedIsolation effect; the shell formed by the molybdenum substrate layer can adsorb polymer degraded fragments in the polymer combustion process, and a plurality of micro-hole structures formed on the surface of the shell are used as a 'micro-reactor' to promote the carbonization of some polymer degraded fragments, so that the flame retardant property is improved.
Description
Technical Field
The invention belongs to the technical field of functional powder, and particularly relates to molybdenum substrate layer modified magnesium hydroxide and a preparation method and application thereof.
Background
Flame retardants are functional adjuvants that impart flame retardancy to flammable polymers, including additive flame retardants and reactive flame retardants. In the additive flame retardant, the inorganic flame retardant magnesium hydroxide has a cold trap effect, a dilution effect and a similar barrier effect, is beneficial to smoke suppression and carbon layer enhancement, and is widely applied to the field of halogen-free flame-retardant wire and cable protective sleeves and insulating materials. However, when pure magnesium hydroxide is used as a flame retardant, the flame retardant effect can be ensured only by adding a high amount of magnesium hydroxide. Therefore, researchers have proposed modifying magnesium hydroxide to improve the flame retardant properties of the modified magnesium hydroxide.
Chinese patent application CN101787290A discloses a method for modifying magnesium hydroxide with polyimide as a modifier, which can modify magnesium hydroxide with polyimide, a good high temperature resistant and easily processable polymer, but as a polymer-based material, has limited improvement of heat resistance, poor thermal stability, no catalytic effect, and poor flame retardant performance. Chinese patent application CN104804474A provides a double-coated magnesium hydroxide flame retardant and a preparation method thereof, although a magnesium hydroxide modified powder with higher dispersibility and compatibility in a matrix can be obtained, the magnesium hydroxide modified powder serving as a magnesium hydroxide material coated by small organic molecules has limited improvement on heat resistance, poor heat stability and no catalytic carbonization effect; the coated microcapsule wall component contains two layers, is easy to wear, and has further improved flame retardant property.
The flame retardant effect of the existing modified magnesium hydroxide product needs to be improved, and the thermal stability and the catalytic carbonization effect are poor.
Disclosure of Invention
In view of the above, the present invention provides a molybdenum substrate layer modified magnesium hydroxide, which has excellent flame retardant property, high thermal stability and catalytic carbonization effect.
In order to achieve the purpose of the invention, the invention provides the following technical scheme:
the invention provides molybdenum substrate layer modified magnesium hydroxide, which comprises a magnesium hydroxide core and a shell formed by a molybdenum substrate layer coating the magnesium hydroxide core; the chemical composition of the molybdenum substrate layer is MoX2And X is O, S, Se or Te.
Preferably, the particle size of the magnesium hydroxide core is 0.6-1.5 μm; the shell accounts for 5-90 wt% of the molybdenum substrate layer modified magnesium hydroxide.
Preferably, the particle size of the molybdenum substrate layer modified magnesium hydroxide is 0.8-2 μm.
The invention also provides a preparation method of the molybdenum substrate layer modified magnesium hydroxide, which comprises the following steps:
mixing the modified magnesium hydroxide with the molybdenum substrate layer dispersion liquid, and carrying out hybridization reaction to obtain the molybdenum substrate layer modified magnesium hydroxide; the modified magnesium hydroxide is modified by a silane coupling agent.
Preferably, the particle size of the molybdenum substrate layer in the molybdenum substrate layer dispersion liquid is 0.8-1.5 μm; the dispersion solvent in the molybdenum substrate layer dispersion liquid is one or more of deionized water, methanol, ethanol, ethyl acetate, cyclohexane, isopropanol, tetrahydrofuran and dioxane; the concentration of the molybdenum substrate layer in the molybdenum substrate layer dispersion liquid is 1-40 mol/L.
Preferably, the silane coupling agent includes one or more of gamma- (2, 3-glycidoxy) propyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, and 3-aminopropyltriethoxysilane.
Preferably, the temperature of the hybridization reaction is 20-100 ℃, and the time is 0.5-8 h; the hybridization reaction is carried out under the condition of stirring, and the stirring speed is 100-700 rpm.
Preferably, after the hybridization reaction, the method further comprises: and sequentially washing, solid-liquid separating and drying the obtained hybrid reaction product.
Preferably, the washing liquid in the washing is one or more of deionized water, methanol, ethanol, ethyl acetate and tetrahydrofuran;
the solid-liquid separation is centrifugation; the centrifugation speed of the centrifugation is 1000-8000 rpm, and the time is 10-120 min;
the drying temperature is 45-120 ℃, and the drying time is 1-72 hours.
The invention also provides application of the molybdenum substrate layer modified magnesium hydroxide obtained by the preparation method in the technical scheme or the molybdenum substrate layer modified magnesium hydroxide obtained by the preparation method in the technical scheme as a flame retardant.
The invention provides molybdenum substrate layer modified magnesium hydroxide, which comprises a magnesium hydroxide core and a shell formed by a molybdenum substrate layer coating the magnesium hydroxide core; the chemical composition of the molybdenum substrate layer is MoX2And X is O, S, Se or Te. In the invention, the shell formed by the molybdenum substrate layer has higher thermal stability, can effectively prevent the degradation of the molybdenum substrate layer modified magnesium hydroxide, and has the thermal stability of the molybdenum substrate layer modified magnesium hydroxideHigh; the shell contains molybdenum element, has a strong catalytic carbonization effect and is in a lamellar shape, so that the stability of a carbon layer can be enhanced and the physical barrier effect can be further effectively improved in the application process; and the molybdenum substrate layer shell can adsorb polymer degraded fragments in the polymer combustion process, and a plurality of micro-hole structures are formed on the surface of the molybdenum substrate layer shell and used as a 'micro-reactor' to promote the carbonization of some polymer degraded fragments, so that the molybdenum substrate layer shell and the magnesium hydroxide core can cooperatively play a flame-retardant effect, the limit oxygen index is high, the maximum smoke density is low, and the flame-retardant property is improved. In addition, the surface of the molybdenum substrate layer shell is provided with a fluffy molybdenum adsorption base layer, the polarity is low, the compatibility with a polymer matrix is good during application, and the mechanical property of the polymer composite material obtained by application is ensured.
The test result of the embodiment shows that the specific surface area of the molybdenum substrate layer modified magnesium hydroxide provided by the invention is 19.333-19.848 m2The oil absorption value is 26-28 mL/100 g; a limiting oxygen index of 29.2-30.0% and a maximum smoke density of 86.45-87.88 kg/m3The flame retardant and smoke suppression effect is good; when the method is applied to a PVC matrix, the tensile strength of the obtained sample is 11.56-12.08 MPa, and the mechanical property is good.
Drawings
FIG. 1 is an SEM photograph of molybdenum substrate layer-modified magnesium hydroxide obtained in example 1;
FIG. 2 is a thermogravimetric plot of the molybdenum substrate layer-modified magnesium hydroxide obtained in example 1 in an air atmosphere.
Detailed Description
The invention provides molybdenum substrate layer modified magnesium hydroxide, which comprises a magnesium hydroxide core and a shell formed by a molybdenum substrate layer coating the magnesium hydroxide core; the chemical composition of the molybdenum substrate layer is MoX2And X is O, S, Se or Te.
In the present invention, the molybdenum substrate layer-modified magnesium hydroxide includes a magnesium hydroxide core. In the present invention, the particle size of the magnesium hydroxide core is preferably 0.6 to 1.5 μm, and more preferably 0.65 to 1.4 μm.
In the invention, the molybdenum substrate layer modified magnesium hydroxide comprises an outer shell formed by a molybdenum substrate layer coating the magnesium hydroxide inner core. In the present invention, the molybdenumThe chemical composition of the substrate layer is MoX2And X is O, S, Se or Te. In the invention, the shell preferably accounts for 5-90 wt.%, more preferably 10-80 wt.% of the molybdenum substrate layer modified magnesium hydroxide.
In the invention, the particle size of the molybdenum substrate layer modified magnesium hydroxide is preferably 0.8-2 μm, and more preferably 0.85-1.9 μm.
The invention also provides a preparation method of the molybdenum substrate layer modified magnesium hydroxide, which comprises the following steps:
mixing the modified magnesium hydroxide with the molybdenum substrate layer dispersion liquid, and carrying out hybridization reaction to obtain the molybdenum substrate layer modified magnesium hydroxide; the modified magnesium hydroxide is modified by a silane coupling agent.
In the present invention, unless otherwise specified, each of the substances is a commercially available product well known to those skilled in the art.
The present invention provides modified magnesium hydroxide. In the invention, the modified magnesium hydroxide is magnesium hydroxide modified by a silane coupling agent. In the present invention, the modified hydroxide is preferably commercially available or autonomously prepared.
In the present invention, the preparation method of the modified magnesium hydroxide preferably comprises: preheating magnesium hydroxide, mixing the preheated magnesium hydroxide with a silane coupling agent, and carrying out modification treatment to obtain the modified magnesium hydroxide.
Before preheating, the magnesium hydroxide is preferably dried; the drying temperature is preferably 60-120 ℃, and more preferably 80-100 ℃; the time is preferably 1 to 48 hours, and more preferably 12 to 36 hours.
In the invention, the preheating temperature is preferably 80-180 ℃, more preferably 90-170 ℃, and further preferably 100-160 ℃.
In the present invention, the mass of the silane coupling agent is preferably 0.5 to 5.0%, more preferably 1 to 4.5%, and still more preferably 1.5 to 4% of the mass of the preheated magnesium hydroxide.
In the present invention, the mixing of the preheated magnesium hydroxide and the silane coupling agent is preferably stirring; the stirring speed is preferably 1000-8000 rpm, more preferably 1500-7500 rpm, and still more preferably 2000-7000 rpm.
In the invention, the temperature of the modification treatment is preferably 80-180 ℃, more preferably 90-170 ℃, and further preferably 100-160 ℃; the time is preferably 3 to 30min, more preferably 5 to 25min, and still more preferably 10 to 20 min. In the present invention, the modification treatment is preferably performed under stirring; the stirring speed is preferably 1000-8000 rpm, more preferably 1500-7500 rpm, and still more preferably 2000-7000 rpm.
After the modification treatment, the reaction product is preferably naturally cooled to room temperature to obtain the modified magnesium hydroxide.
In the present invention, the silane coupling agent preferably includes one or more of gamma- (2, 3-glycidoxy) propyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, and 3-aminopropyltriethoxysilane.
The invention provides a molybdenum substrate layer dispersion. In the present invention, the molybdenum substrate layer dispersion is preferably obtained by mixing a molybdenum substrate layer and a dispersion solvent.
In the present invention, the particle size of the molybdenum substrate layer in the molybdenum substrate layer dispersion is preferably 0.8 to 1.5 μm, and more preferably 0.85 to 1.4 μm. In the present invention, the dispersion solvent in the molybdenum substrate layer dispersion liquid is preferably one or more of deionized water, methanol, ethanol, ethyl acetate, cyclohexane, isopropanol, tetrahydrofuran, and dioxane, more preferably deionized water, methanol, ethanol, ethyl acetate, cyclohexane, isopropanol, tetrahydrofuran, or dioxane, and most preferably ethanol. In the invention, the concentration of the molybdenum substrate layer in the molybdenum substrate layer dispersion liquid is preferably 1-40 mol/L, more preferably 5-35 mol/L, and still more preferably 10-30 mol/L. In the present invention, the mixing manner of the molybdenum substrate layer and the dispersion solvent is preferably ultrasonic and stirring.
The modified magnesium hydroxide and the molybdenum substrate layer dispersion liquid are mixed for hybridization reaction to obtain the molybdenum substrate layer modified magnesium hydroxide.
In the present invention, the mixing of the modified magnesium hydroxide and the molybdenum substrate layer dispersion is preferably carried out by adding the modified magnesium hydroxide to the molybdenum substrate layer dispersion under stirring.
In the invention, the temperature of the hybridization reaction is preferably 20-100 ℃, more preferably 30-90 ℃, and further preferably 40-80 ℃; the time is preferably 0.5 to 8 hours, more preferably 1 to 7 hours, and still more preferably 2 to 6 hours. In the present invention, the hybridization reaction is preferably performed under ultrasonic and stirring conditions; the stirring speed in the ultrasonic and stirring process is preferably 100-700 rpm, and more preferably 150-650 rpm; the frequency of the ultrasonic wave is preferably 10-60 kHz, and more preferably 15-55 kHz.
After the hybridization reaction, the present invention preferably further comprises: and sequentially washing, solid-liquid separating and drying the obtained hybrid reaction product.
In the present invention, the washing liquid in the washing is preferably one or more of deionized water, methanol, ethanol, ethyl acetate and tetrahydrofuran. The method removes the residual molybdenum substrate layer which does not participate in the hybridization reaction and the silane coupling agent partially residual on the modified magnesium hydroxide by cleaning.
In the present invention, the solid-liquid separation is preferably centrifugation. In the invention, the centrifugal speed of the centrifugation is preferably 1000-8000 rpm, more preferably 1500-7500 rpm, and still more preferably 2000-7000 rpm; the time is preferably 10 to 120min, more preferably 20 to 100min, and still more preferably 30 to 90 min.
In the invention, the drying temperature is preferably 45-120 ℃, more preferably 50-115 ℃, and further preferably 60-110 ℃; the time is preferably 1-72 h, more preferably 12-60 ℃, and further preferably 24-48 h.
The invention also provides application of the molybdenum substrate layer modified magnesium hydroxide obtained by the preparation method in the technical scheme or the molybdenum substrate layer modified magnesium hydroxide obtained by the preparation method in the technical scheme as a flame retardant.
The present invention is not particularly limited to the use, and may employ the use of flame retardants well known to those skilled in the art. In the invention, the molybdenum substrate layer modified magnesium hydroxide is preferably used as a flame retardant in a system of a polymer with large smoke emission; specifically, the polymer having a large smoke generation amount is preferably a halogen-containing or aromatic ring-containing polymer, and more preferably polyvinyl chloride, a phenol resin, or polystyrene.
In order to further illustrate the present invention, the following examples are provided to describe the molybdenum substrate layer modified magnesium hydroxide and the preparation method and application thereof in detail, but they should not be construed as limiting the scope of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Dispersing 5g of molybdenum substrate layer with the size of 1.0 mu m in ethanol, performing ultrasonic treatment and stirring to obtain 5mol/L molybdenum substrate layer dispersion liquid; drying magnesium hydroxide, preheating to 120 ℃, and mixing the obtained preheated magnesium hydroxide and 3-aminopropyltriethoxysilane according to the mass ratio of 100: 2.5, mixing, stirring at 120 ℃ and 4000rpm for 15min for modification treatment to obtain modified magnesium hydroxide; adding 5g of modified magnesium hydroxide into the obtained molybdenum substrate layer dispersion liquid under the ultrasonic stirring condition, stirring at the rotating speed of 350rpm for 4h at 50 ℃ to perform hybridization reaction, washing the obtained reaction product with ethanol, centrifuging at the rotating speed of 5000rpm for 30min, and drying at 80 ℃ for 12h to obtain the molybdenum substrate layer modified magnesium hydroxide.
Scanning electron microscopy tests were performed on the molybdenum substrate layer modified magnesium hydroxide obtained in example 1, and the SEM image obtained is shown in FIG. 1. As can be seen from fig. 1, the molybdenum substrate layer modified magnesium hydroxide obtained in this embodiment apparently has a typical layer coating morphology, and the coating is relatively complete, which may be because the molybdenum substrate layer itself is a typical sheet structure covering the surface; in addition, after the magnesium hydroxide is subjected to hybridization modification of a molybdenum substrate layer, certain roughness exists on the surface; the particle size of the molybdenum substrate layer modified magnesium hydroxide was about 1.100. mu.m.
Thermogravimetric analysis was performed on the molybdenum substrate layer-modified magnesium hydroxide obtained in example 1, and the thermogravimetric graph in an air atmosphere was shown in fig. 2. As can be seen from FIG. 2, the molybdenum substrate layer modified magnesium hydroxide has excellent thermal stability, high initial degradation temperature, suitability for processing polymer substrates with high temperature, high final carbon residue retention rate and greatly improved final carbon formation rate.
Example 2
Dispersing 5g of molybdenum substrate layer with the size of 1.0 mu m in ethanol, performing ultrasonic treatment and stirring to obtain 40mol/L molybdenum substrate layer dispersion liquid; drying magnesium hydroxide, preheating to 100 ℃, and mixing the obtained preheated magnesium hydroxide and 3-aminopropyltriethoxysilane according to the mass ratio of 100: 5, mixing, stirring at 100 ℃ and 2000rpm for 20min for modification treatment to obtain modified magnesium hydroxide; adding 95g of modified magnesium hydroxide into the obtained molybdenum substrate layer dispersion liquid under the ultrasonic stirring condition, stirring at the rotating speed of 700rpm at 20 ℃ for 8h to perform hybridization reaction, washing the obtained reaction product with ethanol, centrifuging at the rotating speed of 1000rpm for 120min, and drying at 45 ℃ for 72h to obtain the molybdenum substrate layer modified magnesium hydroxide.
Example 3
Dispersing 5g of molybdenum substrate layer with the size of 1.0 mu m in ethanol, performing ultrasonic treatment and stirring to obtain 1mol/L molybdenum substrate layer dispersion liquid; drying magnesium hydroxide, preheating to 160 ℃, and mixing the obtained preheated magnesium hydroxide and 3-aminopropyltriethoxysilane according to the mass ratio of 100: 0.5, stirring at 160 ℃ and 7000rpm for 10min for modification treatment to obtain modified magnesium hydroxide; adding 0.55g of modified magnesium hydroxide into the obtained molybdenum substrate layer dispersion liquid under the ultrasonic stirring condition, stirring for 0.5h at the rotating speed of 100rpm at 100 ℃ for hybridization reaction, washing the obtained reaction product with ethanol, centrifuging for 10min at the rotating speed of 8000rpm, and drying for 1h at 120 ℃ to obtain the molybdenum substrate layer modified magnesium hydroxide.
Example 4
Dispersing 5g of molybdenum substrate layer with the size of 1.0 mu m in ethanol, performing ultrasonic treatment and stirring to obtain 10mol/L molybdenum substrate layer dispersion liquid; drying magnesium hydroxide, preheating to 140 ℃, and mixing the obtained preheated magnesium hydroxide and 3-aminopropyltriethoxysilane according to a mass ratio of 100: 1.5, mixing, stirring at 140 ℃ and 5000rpm for 12min for modification treatment to obtain modified magnesium hydroxide; and adding 10g of modified magnesium hydroxide into the obtained molybdenum substrate layer dispersion liquid under the ultrasonic stirring condition, stirring at the rotating speed of 500rpm at 80 ℃ for 2h to perform hybridization reaction, washing the obtained reaction product with ethanol, centrifuging at the rotating speed of 6000rpm for 60min, and drying at 60 ℃ for 24h to obtain the molybdenum substrate layer modified magnesium hydroxide.
Example 5
Dispersing 5g of molybdenum substrate layer with the size of 1.0 mu m in ethanol, performing ultrasonic treatment and stirring to obtain 2mol/L molybdenum substrate layer dispersion liquid; drying magnesium hydroxide, preheating to 120 ℃, and mixing the obtained preheated magnesium hydroxide and 3-aminopropyltriethoxysilane according to the mass ratio of 100: 3.5, mixing, stirring at 120 ℃ and 3000rpm for 17min for modification treatment to obtain modified magnesium hydroxide; adding 1g of modified magnesium hydroxide into the obtained molybdenum substrate layer dispersion liquid under the condition of ultrasonic stirring, stirring for 6h at the rotating speed of 250rpm at 40 ℃ for hybridization reaction, washing the obtained reaction product with ethanol, centrifuging for 90min at the rotating speed of 4000rpm, and drying for 6h at 100 ℃ to obtain the molybdenum substrate layer modified magnesium hydroxide.
Comparative example 1
Drying magnesium hydroxide, preheating to 120 ℃, and mixing the obtained preheated magnesium hydroxide and 3-aminopropyltriethoxysilane according to the mass ratio of 100: 8, mixing, stirring at 120 ℃ and 4000rpm for 15min for modification treatment to obtain the modified magnesium hydroxide.
Comparative example 2
Drying magnesium hydroxide, preheating to 120 ℃, and mixing the obtained preheated magnesium hydroxide and 3-aminopropyltriethoxysilane according to the mass ratio of 100: 0.1, stirring at 120 ℃ and 4000rpm for 15min for modification treatment to obtain the modified magnesium hydroxide.
Comparative example 3
The magnesium hydroxide prepared by the precipitation method has a lamellar structure.
Comparative example 4
Magnesium hydroxide by precipitation.
The particle size, specific surface area and oil absorption value of the magnesium hydroxide products provided in examples 1 to 5 and comparative examples 1 to 4 were measured, and the test methods and test results are shown in table 1.
TABLE 1 results of particle diameter, specific surface area and oil absorption value test in examples 1 to 5 and comparative examples 1 to 4
As can be seen from Table 1, the molybdenum substrate layer modified magnesium hydroxide provided in the embodiment of the invention has a median particle diameter D50 of 1.055-1.187 μm and a small median particle diameter; the specific surface area is 19.333-19.848 m2The specific surface area is high; the oil absorption value is 26-28 mL/100g, and the oil absorption value is small. Compared with comparative examples 1-2, the molybdenum substrate layer modified magnesium hydroxide powder obtained by hybridization of magnesium hydroxide reasonably modified by silane coupling agent and molybdenum substrate layer has relatively small D50 and relatively high specific surface area; meanwhile, the oil absorption value of the molybdenum substrate layer modified magnesium hydroxide provided by the embodiment of the invention is lower than that of the comparative examples 1-4, which is probably because the effect of the magnesium hydroxide modified by the silane coupling agent with reasonable parts is better, when the silane coupling agent is added too much or too little, the magnesium hydroxide cannot be effectively modified, and finally the particle performance of the molybdenum substrate layer hybridized magnesium hydroxide powder is influenced, so that the particle size of the molybdenum substrate layer modified magnesium hydroxide is increased, the specific surface area is reduced, and the oil absorption value is increased; compared with comparative examples 3-4 (magnesium hydroxide powder produced by some domestic and foreign companies), the molybdenum substrate layer modified magnesium hydroxide powder provided by the invention is better in granularity and specific surface area, and the oil absorption value is obviously reduced, which is probably because the magnesium hydroxide powder of the comparative examples 3-4 has more hydrophilic groups and larger polarity on the surface, so that the oil absorption value is larger, the processing fluidity of a polymer matrix material during application can be reduced, and the processing cost of downstream manufacturers can be increased, thereby showing that the molybdenum substrate layer has obvious effect on changing the oil absorption value of the magnesium hydroxide powder.
The molybdenum substrate layer modified magnesium hydroxide obtained in the examples 1-5 and the magnesium hydroxide obtained in the comparative examples 1-4 are respectively used as flame retardants to perform a flame retardance and smoke suppression test and a tensile property test, and the test method comprises the following steps: 50g of polyvinyl chloride (SG5), 25g of dioctyl phthalate, 2g of barium-cadmium-zinc stabilizer, 30g of calcium carbonate (GY-616), 2g of antimony trioxide and 4g of flame retardant are blended, mechanically stirred, mixed for 10min at 170 ℃ by using a double-roll open mill, and subjected to compression molding to prepare corresponding standard test samples for subsequent performance tests:
the test method comprises the following steps:
and (3) oxygen index test: the test standard is GB/T2406.2-2009;
testing the smoke density: a building material smoke density tester is adopted, and the test standard is GB/T8627-;
and (3) testing tensile strength: the test standard is GB/T1040-;
the test results are shown in Table 2.
Table 2 test results of flame retardant and smoke suppressant effects and tensile properties in examples 1 to 5 and comparative examples 1 to 4
| Limiting oxygen index (%) | Maximum smoke density (kg/m)3) | Tensile Strength (MPa) | |
| Example 1 | 30.0 | 87.88 | 12.08 |
| Example 2 | 29.2 | 86.45 | 11.66 |
| Example 3 | 29.7 | 87.08 | 11.89 |
| Example 4 | 29.4 | 86.68 | 11.67 |
| Example 5 | 29.6 | 87.01 | 11.56 |
| Comparative example 1 | 28.2 | 92.07 | 10.18 |
| Comparative example 2 | 27.3 | 97.08 | 9.20 |
| Comparative example 3 | 28.1 | 96.28 | 9.27 |
| Comparative example 4 | 27.8 | 97.18 | 9.08 |
As can be seen from Table 2, the limit oxygen index of the molybdenum substrate layer modified magnesium hydroxide prepared in the embodiment of the invention is 29.2-30.0%, and the maximum smoke density is 86.45-87.88 kg/m3And the flame-retardant and smoke-suppression effect is good. From the limit oxygen index test data, it can be found that the molybdenum substrate layer modified magnesium hydroxide powder prepared in each embodiment of the invention can effectively improve the limit oxygen index of the polyvinyl chloride composite material, so that the limit oxygen index is increased from 25.1% to more than 29%, and the flame retardant property of the polyvinyl chloride composite material can be obviously improved after the molybdenum substrate layer modified magnesium hydroxide provided by the invention is added; meanwhile, compared with comparative examples 1-2, the silane coupling agent coated on the surface is too much or too little, so that the surface modification of magnesium hydroxide is not facilitated, the final modification effect is poor, and the better flame-retardant and smoke-suppressing characteristics of the hybrid powder are difficult to exert; compared with comparative examples 3-4, the molybdenum substrate layer modified magnesium hydroxide provided by the invention has a higher enhanced limiting oxygen index, which is probably because the molybdenum substrate layer exists on the surface of the molybdenum substrate layer modified magnesium hydroxide, so that the carbonization can be promoted, the physical barrier effect can be enhanced, and meanwhile, a plurality of advantages such as a synergistic flame retardant effect of molybdenum and magnesium hydroxide exist. According to the maximum smoke density test data, the molybdenum substrate layer modified magnesium hydroxide provided by the invention is added, so that the smoke release density of the polyvinyl chloride material can be further reduced, the smoke suppression performance is further improved, and the requirements of environmental protection and smoke suppression are better met.
According to tensile strength test data, the polyvinyl chloride-based material added with the molybdenum substrate layer modified magnesium hydroxide provided by the invention shows good tensile strength; after only the coupling agent modified magnesium hydroxide is added, the tensile strength of the polyvinyl chloride material is reduced to be about 10 MPa; when the modified magnesium hydroxide of comparative examples 1-2 is added, the mechanical properties are reduced to a certain extent compared with those of the examples, which may be caused by the unreasonable proportion of silane coupling agent and magnesium hydroxide, so that the surface modification effect of magnesium hydroxide is poor, and finally, the tensile strength is reduced when the magnesium hydroxide is hybridized with a molybdenum substrate layer; when the magnesium hydroxide of comparative examples 3-4 is added, the tensile strength of the polyvinyl chloride-based material is only 9.08-9.27 MPa, which is probably because the particle size of the magnesium hydroxide powder is larger and the compatibility with the polyvinyl chloride-based material is poor due to the surface polarity, and when the magnesium hydroxide powder is subjected to external force stretching action, the polyvinyl chloride polymer is induced to generate defects due to poor dispersibility, so that the mechanical property of the polyvinyl chloride-based material is induced to be reduced; the molybdenum substrate layer modified magnesium hydroxide provided by the invention has small granularity and weak surface polarity, and has a good effect on the mechanical property of a polyvinyl chloride-based material.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The molybdenum substrate layer modified magnesium hydroxide comprises a magnesium hydroxide core and a shell formed by a molybdenum substrate layer coating the magnesium hydroxide core; the chemical composition of the molybdenum substrate layer is MoX2And X is O, S, Se or Te.
2. The molybdenum-substrate-layer-modified magnesium hydroxide according to claim 1, wherein the particle size of the magnesium hydroxide core is 0.6 to 1.5 μm; the shell accounts for 5-90 wt% of the molybdenum substrate layer modified magnesium hydroxide.
3. The molybdenum-substrate-layer-modified magnesium hydroxide according to claim 1, wherein the particle size of the molybdenum-substrate-layer-modified magnesium hydroxide is 0.8 to 2 μm.
4. A method for preparing molybdenum substrate layer-modified magnesium hydroxide according to any one of claims 1 to 3, comprising the steps of:
mixing the modified magnesium hydroxide with the molybdenum substrate layer dispersion liquid, and carrying out hybridization reaction to obtain the molybdenum substrate layer modified magnesium hydroxide; the modified magnesium hydroxide is modified by a silane coupling agent.
5. The method according to claim 4, wherein the particle size of the molybdenum substrate layer in the molybdenum substrate layer dispersion is 0.8 to 1.5 μm; the dispersion solvent in the molybdenum substrate layer dispersion liquid is one or more of deionized water, methanol, ethanol, ethyl acetate, cyclohexane, isopropanol, tetrahydrofuran and dioxane; the concentration of the molybdenum substrate layer in the molybdenum substrate layer dispersion liquid is 1-40 mol/L.
6. The method of claim 4, wherein the silane coupling agent comprises one or more of gamma- (2, 3-glycidoxy) propyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, and 3-aminopropyltriethoxysilane.
7. The preparation method according to claim 4, wherein the temperature of the hybridization reaction is 20-100 ℃ and the time is 0.5-8 h;
the hybridization reaction is carried out under the condition of stirring, and the stirring speed is 100-700 rpm.
8. The method according to claim 4 or 7, further comprising, after the hybridization reaction: and sequentially washing, solid-liquid separating and drying the obtained hybrid reaction product.
9. The preparation method according to claim 8, wherein the washing liquid in the washing is one or more of deionized water, methanol, ethanol, ethyl acetate and tetrahydrofuran;
the solid-liquid separation is centrifugation; the centrifugation speed of the centrifugation is 1000-8000 rpm, and the time is 10-120 min;
the drying temperature is 45-120 ℃, and the drying time is 1-72 hours.
10. Use of the molybdenum substrate layer modified magnesium hydroxide according to any one of claims 1 to 3 or the molybdenum substrate layer modified magnesium hydroxide obtained by the preparation method according to any one of claims 4 to 9 as a flame retardant.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116041791A (en) * | 2023-03-02 | 2023-05-02 | 江西广源新材料有限公司 | Naphthalene anhydride microencapsulated magnesium hydroxide composite powder and preparation method and application thereof |
| CN116478056A (en) * | 2023-04-04 | 2023-07-25 | 江西广源新材料有限公司 | Biphenyl derivative, preparation method and application thereof, composite magnesium fertilizer, and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2101811A1 (en) * | 1992-08-05 | 1994-02-06 | Shunichi Setoguchi | Aluminium Pigments |
| CN104312096A (en) * | 2013-10-11 | 2015-01-28 | 南亚塑胶工业股份有限公司 | Inorganic filler with molybdenum compound coated on surface and application thereof |
| CN105646946A (en) * | 2016-03-04 | 2016-06-08 | 广东工业大学 | Carbon-coated zirconium phosphate composite powder, method for preparing same and application of carbon-coated zirconium phosphate composite powder |
| CN106596651A (en) * | 2016-12-05 | 2017-04-26 | 黑龙江大学 | Molybdenum disulfide/magnesium hydroxide nano composite material as well as preparation method and application thereof |
| CN106957454A (en) * | 2017-04-18 | 2017-07-18 | 中国科学技术大学 | A kind of nano material coated fire retardant and preparation method thereof |
| CN107163505A (en) * | 2017-06-27 | 2017-09-15 | 过春明 | A kind of compositions of thermosetting resin and application thereof |
-
2021
- 2021-11-29 CN CN202111434797.2A patent/CN114058084B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2101811A1 (en) * | 1992-08-05 | 1994-02-06 | Shunichi Setoguchi | Aluminium Pigments |
| CN104312096A (en) * | 2013-10-11 | 2015-01-28 | 南亚塑胶工业股份有限公司 | Inorganic filler with molybdenum compound coated on surface and application thereof |
| CN105646946A (en) * | 2016-03-04 | 2016-06-08 | 广东工业大学 | Carbon-coated zirconium phosphate composite powder, method for preparing same and application of carbon-coated zirconium phosphate composite powder |
| CN106596651A (en) * | 2016-12-05 | 2017-04-26 | 黑龙江大学 | Molybdenum disulfide/magnesium hydroxide nano composite material as well as preparation method and application thereof |
| CN106957454A (en) * | 2017-04-18 | 2017-07-18 | 中国科学技术大学 | A kind of nano material coated fire retardant and preparation method thereof |
| CN107163505A (en) * | 2017-06-27 | 2017-09-15 | 过春明 | A kind of compositions of thermosetting resin and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116041791A (en) * | 2023-03-02 | 2023-05-02 | 江西广源新材料有限公司 | Naphthalene anhydride microencapsulated magnesium hydroxide composite powder and preparation method and application thereof |
| CN116041791B (en) * | 2023-03-02 | 2024-05-24 | 江西广源新材料有限公司 | Naphthalene anhydride microencapsulated magnesium hydroxide composite powder and preparation method and application thereof |
| CN116478056A (en) * | 2023-04-04 | 2023-07-25 | 江西广源新材料有限公司 | Biphenyl derivative, preparation method and application thereof, composite magnesium fertilizer, and preparation method and application thereof |
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