CN114058084B - 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 modified magnesium hydroxide of the molybdenum substrate layer provided by the invention comprises a magnesium hydroxide core and an outer shell formed by the molybdenum substrate layer coating the magnesium hydroxide core; the chemical composition of the molybdenum substrate layer is MoX 2 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 degradation of the modified magnesium hydroxide of the molybdenum substrate layer in the application process; the shell contains molybdenum element, has a strong catalytic carbonization effect, is in a lamellar shape, and can enhance the stability of a carbon layer and further effectively improve the physical barrier effect in the application process; the shell formed by the molybdenum substrate layer can absorb polymer degradation fragments in the polymer combustion process, and a plurality of tiny hole structures formed on the surface are used as microreactors to promote carbonization of some polymer degradation 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. Among the additive flame retardants, magnesium hydroxide, an inorganic flame retardant, has a cold trap effect, a dilution effect and a similar barrier effect, is beneficial to suppressing smoke and enhancing the effect of a carbon layer, and is widely applied to the fields 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 a high addition amount. 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 by using polyimide as a modifier, which can modify magnesium hydroxide through polyimide, namely a good high-temperature-resistant and easily-processed polymer, but is a polymer-based material, has limited improvement of heat resistance, poor thermal stability, no catalytic effect and poor flame retardant property. The Chinese patent application CN104804474A provides a double-coated magnesium hydroxide flame retardant and a preparation method thereof, and the magnesium hydroxide modified powder with higher dispersibility and compatibility in a matrix can be obtained, but the magnesium hydroxide modified powder is used as a magnesium hydroxide material coated by small organic molecules, has limited heat resistance improvement and poor thermal stability, and does not have a catalytic charring 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 current modified magnesium hydroxide product needs to be improved, and the heat stability and the catalytic char formation effect are poor.
Disclosure of Invention
In view of the above, the present invention aims to provide a modified magnesium hydroxide of a molybdenum substrate layer, which has excellent flame retardant property, high thermal stability and catalytic char formation effect.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a 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 MoX 2 X is O, S, se or Te.
Preferably, the particle size of the magnesium hydroxide core is 0.6-1.5 mu m; the shell accounts for 5-90 wt.% of the modified magnesium hydroxide of the molybdenum substrate layer.
Preferably, the particle size of the modified magnesium hydroxide of the molybdenum substrate layer is 0.8-2 mu m.
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 modified magnesium hydroxide of the molybdenum substrate layer; the modified magnesium hydroxide is silane coupling agent modified magnesium hydroxide.
Preferably, the particle size of the molybdenum substrate layer in the molybdenum substrate layer dispersion liquid is 0.8-1.5 mu m; 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 comprises one or more of gamma- (2, 3-glycidoxypropyl) propyl trimethoxysilane, gamma-methacryloxypropyl trimethoxysilane, gamma-mercaptopropyl triethoxysilane, gamma-mercaptopropyl trimethoxysilane, vinyl trimethoxysilane and 3-aminopropyl triethoxysilane.
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 stirring, and the stirring speed is 100-700 rpm.
Preferably, after the hybridization reaction, the method further comprises: and (3) cleaning, solid-liquid separation and drying the obtained hybridization reaction product in sequence.
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 centrifugal 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 h.
The invention also provides the application of the molybdenum substrate layer modified magnesium hydroxide obtained by the technical scheme or the preparation method of the technical scheme as a flame retardant.
The invention provides a 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 MoX 2 X is O, S, se or Te. In the invention, the shell formed by the molybdenum substrate layer has higher thermal stability, so that the degradation of the modified magnesium hydroxide of the molybdenum substrate layer can be effectively prevented, and the thermal stability of the modified magnesium hydroxide of the molybdenum substrate layer is high; the shell contains molybdenum element, has a strong catalytic carbonization effect, is in a lamellar shape, and can enhance the stability of a carbon layer and further effectively improve the physical barrier effect in the application process; the molybdenum substrate layer shell can absorb fragments degraded by the polymer in the combustion process of the polymer, and a plurality of micro-hole structures formed on the surface are used as a micro-reactor to promote carbonization of some polymer degradation fragments, and the micro-reactor cooperates with the magnesium hydroxide kernel to play a flame retardant effect, so that 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 adsorption molybdenum base layer, the polarity is lower, the compatibility with a polymer matrix is better during application, and the mechanical property of the polymer composite material obtained by application is ensured.
The test results of the examples show that the specific surface area of the modified magnesium hydroxide of the molybdenum substrate layer provided by the invention is 19.333-19.848 m 2 Per gram, the oil absorption value is 26-28 mL/100g; the limiting oxygen index is 29.2-30.0% and the maximum smoke density is 86.45-87.88kg/m 3 The flame-retardant smoke-suppressing 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 image of the modified magnesium hydroxide of the molybdenum substrate layer obtained in example 1;
FIG. 2 is a graph showing the thermogravimetric profile of the molybdenum substrate layer-modified magnesium hydroxide obtained in example 1 in an air atmosphere.
Detailed Description
The invention provides a 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 MoX 2 X is O, S, se or Te.
In the present invention, the molybdenum substrate layer modified magnesium hydroxide comprises a magnesium hydroxide core. In the present invention, the particle diameter of the magnesium hydroxide core is preferably 0.6 to 1.5. Mu.m, more preferably 0.65 to 1.4. Mu.m.
In the present 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 invention, the chemical composition of the molybdenum substrate layer is MoX 2 X is O, S, se or Te. In the present invention, the shell preferably occupies 5 to 90wt.%, more preferably 10 to 80wt.% of the molybdenum substrate layer-modified magnesium hydroxide.
In the present invention, the particle size of the molybdenum substrate layer-modified magnesium hydroxide is preferably 0.8 to 2. Mu.m, more preferably 0.85 to 1.9. Mu.m.
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 modified magnesium hydroxide of the molybdenum substrate layer; the modified magnesium hydroxide is silane coupling agent modified magnesium hydroxide.
In the present invention, each of the substances is commercially available as known to those skilled in the art unless otherwise specified.
The invention provides modified magnesium hydroxide. In the invention, the modified magnesium hydroxide is silane coupling agent modified magnesium hydroxide. In the present invention, the modified hydroxide is preferably commercially available or prepared autonomously.
In the present invention, the preparation method of the modified magnesium hydroxide preferably comprises: and preheating magnesium hydroxide, mixing the obtained preheated magnesium hydroxide with a silane coupling agent, and carrying out modification treatment to obtain the modified magnesium hydroxide.
The magnesium hydroxide is preferably dried before being preheated; the drying temperature is preferably 60 to 120 ℃, more preferably 80 to 100 ℃; the time is preferably 1 to 48 hours, more preferably 12 to 36 hours.
In the present invention, the temperature of the preheating is preferably 80 to 180 ℃, more preferably 90 to 170 ℃, still more preferably 100 to 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%, still more preferably 1.5 to 4% of the mass of the preheated magnesium hydroxide.
In the present invention, the mixing of the pre-heated magnesium hydroxide and the silane coupling agent is preferably stirring; the stirring speed is preferably 1000 to 8000rpm, more preferably 1500 to 7500rpm, still more preferably 2000 to 7000rpm.
In the present invention, the temperature of the modification treatment is preferably 80 to 180 ℃, more preferably 90 to 170 ℃, still more preferably 100 to 160 ℃; the time is preferably 3 to 30 minutes, more preferably 5 to 25 minutes, still more preferably 10 to 20 minutes. In the present invention, the modification treatment is preferably performed under stirring; the stirring speed is preferably 1000 to 8000rpm, more preferably 1500 to 7500rpm, still more preferably 2000 to 7000rpm.
After the modification treatment, the obtained reaction product is 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) propyl trimethoxysilane, gamma-methacryloxypropyl trimethoxysilane, gamma-mercaptopropyl triethoxysilane, gamma-mercaptopropyl trimethoxysilane, vinyl trimethoxysilane and 3-aminopropyl triethoxysilane.
The present invention provides a molybdenum substrate layer dispersion. In the present invention, the molybdenum substrate layer dispersion liquid is preferably obtained by mixing a molybdenum substrate layer and a dispersion solvent.
In the present invention, the particle diameter of the molybdenum substrate layer in the molybdenum substrate layer dispersion is preferably 0.8 to 1.5. Mu.m, more preferably 0.85 to 1.4. Mu.m. 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 present invention, the concentration of the molybdenum substrate layer in the molybdenum substrate layer dispersion is preferably 1 to 40mol/L, more preferably 5 to 35mol/L, still more preferably 10 to 30mol/L. In the present invention, the mixing means of the molybdenum substrate layer and the dispersion solvent is preferably ultrasonic and stirring.
The modified magnesium hydroxide of the molybdenum substrate layer is obtained by mixing the modified magnesium hydroxide with the molybdenum substrate layer dispersion liquid and carrying out hybridization reaction.
In the present invention, the mixing of the modified magnesium hydroxide and the molybdenum substrate layer dispersion liquid is preferably to add the modified magnesium hydroxide to the molybdenum substrate layer dispersion liquid under stirring.
In the present invention, the temperature of the hybridization reaction is preferably 20 to 100 ℃, more preferably 30 to 90 ℃, still more preferably 40 to 80 ℃; the time is preferably 0.5 to 8 hours, more preferably 1 to 7 hours, still more preferably 2 to 6 hours. In the present invention, the hybridization reaction is preferably performed under ultrasonic and stirring conditions; the speed of stirring in the ultrasonic and stirring process is preferably 100-700 rpm, more preferably 150-650 rpm; the frequency of the ultrasound is preferably 10 to 60kHz, more preferably 15 to 55kHz.
After the hybridization reaction, the present invention preferably further comprises: and (3) cleaning, solid-liquid separation and drying the obtained hybridization reaction product in sequence.
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 invention removes the residual molybdenum substrate layer which does not participate in hybridization reaction and the silane coupling agent which is partially remained on the modified magnesium hydroxide through cleaning.
In the present invention, the solid-liquid separation is preferably centrifugation. In the present invention, the centrifugation rate of the centrifugation is preferably 1000 to 8000rpm, more preferably 1500 to 7500rpm, still more preferably 2000 to 7000rpm; the time is preferably 10 to 120 minutes, more preferably 20 to 100 minutes, still more preferably 30 to 90 minutes.
In the present invention, the drying temperature is preferably 45 to 120 ℃, more preferably 50 to 115 ℃, still more preferably 60 to 110 ℃; the time is preferably 1 to 72 hours, more preferably 12 to 60 ℃, still more preferably 24 to 48 hours.
The invention also provides the application of the molybdenum substrate layer modified magnesium hydroxide obtained by the technical scheme or the preparation method of the technical scheme as a flame retardant.
The present invention is not particularly limited to the application, and may employ the application 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 amount; specifically, the polymer having a large smoke amount is preferably a halogen-containing or aromatic ring-containing polymer, more preferably polyvinyl chloride, a phenolic resin, or polystyrene.
In order to further illustrate the present invention, the following examples are provided to illustrate a modified magnesium hydroxide for a molybdenum substrate layer, a preparation method and an application thereof in detail, but they should not be construed as limiting the scope of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Dispersing 5g of molybdenum substrate layer with the size of 1.0 mu m in ethanol, and carrying out ultrasonic treatment and stirring to obtain a molybdenum substrate layer dispersion liquid with the concentration of 5 mol/L; the magnesium hydroxide is preheated to 120 ℃ after being dried, and the obtained preheated magnesium hydroxide and 3-aminopropyl triethoxysilane are mixed according to the mass ratio of 100:2.5, mixing, stirring for 15min at 120 ℃ and 4000rpm to carry out modification treatment to obtain modified magnesium hydroxide; adding 5g of modified magnesium hydroxide into the obtained molybdenum substrate layer dispersion liquid under the condition of ultrasonic stirring, stirring for 4 hours at the speed of 350rpm at 50 ℃ to carry out hybridization reaction, washing the obtained reaction product with ethanol, centrifuging for 30 minutes at the speed of 5000rpm, and drying for 12 hours at 80 ℃ to obtain the molybdenum substrate layer modified magnesium hydroxide.
Scanning electron microscopy tests were carried out 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 modified magnesium hydroxide with a molybdenum substrate layer obtained in this embodiment has a typical lamellar coating morphology, and the coating is relatively complete, probably because the molybdenum substrate layer itself is a typical lamellar structure covering the surface; in addition, after the magnesium hydroxide is hybridized and modified by the molybdenum substrate layer, certain roughness exists on the surface; the particle size of the modified magnesium hydroxide of the molybdenum substrate layer is about 1.100 μm.
Thermogravimetric analysis was performed on the molybdenum substrate layer-modified magnesium hydroxide obtained in example 1, and the thermogravimetric graph in the air atmosphere obtained is shown in fig. 2. As can be seen from fig. 2, the obtained molybdenum substrate layer modified magnesium hydroxide has excellent thermal stability, higher initial degradation temperature, suitability for polymer matrixes with higher processing temperature, and higher final carbon residue retention rate, thereby greatly improving the final carbon formation rate.
Example 2
Dispersing 5g of molybdenum substrate layer with the size of 1.0 mu m in ethanol, and carrying out ultrasonic treatment and stirring to obtain a molybdenum substrate layer dispersion liquid with the concentration of 40 mol/L; preheating magnesium hydroxide to 100 ℃ after drying, and mixing the obtained preheated magnesium hydroxide and 3-aminopropyl triethoxysilane according to the mass ratio of 100:5, mixing, stirring at 100 ℃ and 2000rpm for 20min to carry out modification treatment to obtain modified magnesium hydroxide; adding 95g of modified magnesium hydroxide into the obtained molybdenum substrate layer dispersion liquid under the condition of ultrasonic stirring, stirring at the temperature of 20 ℃ for 8 hours at the speed of 700rpm for carrying out hybridization reaction, washing the obtained reaction product with ethanol, centrifuging at the speed of 1000rpm for 120 minutes, and drying at the temperature of 45 ℃ for 72 hours 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, and carrying out ultrasonic treatment and stirring to obtain a molybdenum substrate layer dispersion liquid with the concentration of 1 mol/L; preheating the dried magnesium hydroxide to 160 ℃, and mixing the obtained preheated magnesium hydroxide and 3-aminopropyl triethoxysilane according to the mass ratio of 100:0.5, and stirring at 160 ℃ and 7000rpm for 10min to carry out modification treatment to obtain modified magnesium hydroxide; adding 0.55g of modified magnesium hydroxide into the obtained molybdenum substrate layer dispersion liquid under the condition of ultrasonic stirring, stirring at 100 ℃ for 0.5h at the speed of 100rpm for carrying out hybridization reaction, washing the obtained reaction product with ethanol, centrifuging at 8000rpm for 10min, and drying at 120 ℃ for 1h 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, and carrying out ultrasonic treatment and stirring to obtain 10mol/L molybdenum substrate layer dispersion liquid; the magnesium hydroxide is preheated to 140 ℃ after being dried, and the obtained preheated magnesium hydroxide and 3-aminopropyl triethoxysilane are mixed according to the mass ratio of 100:1.5, mixing, stirring at 140 ℃ and 5000rpm for 12min to carry out modification treatment to obtain modified magnesium hydroxide; adding 10g of modified magnesium hydroxide into the obtained molybdenum substrate layer dispersion liquid under the condition of ultrasonic stirring, stirring at 80 ℃ for 2 hours at the speed of 500rpm for carrying out hybridization reaction, washing the obtained reaction product with ethanol, centrifuging at 6000rpm for 60 minutes, and drying at 60 ℃ for 24 hours 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, and carrying out ultrasonic treatment and stirring to obtain 2mol/L molybdenum substrate layer dispersion liquid; the magnesium hydroxide is preheated to 120 ℃ after being dried, and the obtained preheated magnesium hydroxide and 3-aminopropyl triethoxysilane are mixed according to the mass ratio of 100:3.5, mixing, stirring at 120 ℃ and 3000rpm for 17min to carry out modification treatment, thus obtaining modified magnesium hydroxide; adding 1g of modified magnesium hydroxide into the obtained molybdenum substrate layer dispersion liquid under the condition of ultrasonic stirring, stirring at the speed of 250rpm for 6 hours at the temperature of 40 ℃ to carry out hybridization reaction, washing the obtained reaction product with ethanol, centrifuging at the speed of 4000rpm for 90 minutes, and drying at the temperature of 100 ℃ for 6 hours to obtain the molybdenum substrate layer modified magnesium hydroxide.
Comparative example 1
The magnesium hydroxide is preheated to 120 ℃ after being dried, and the obtained preheated magnesium hydroxide and 3-aminopropyl triethoxysilane are mixed according to the mass ratio of 100:8, mixing, stirring at 120 ℃ and 4000rpm for 15min to carry out modification treatment, thus obtaining modified magnesium hydroxide.
Comparative example 2
The magnesium hydroxide is preheated to 120 ℃ after being dried, and the obtained preheated magnesium hydroxide and 3-aminopropyl triethoxysilane are mixed according to the mass ratio of 100:0.1, and stirring at 120 ℃ and 4000rpm for 15min to carry out modification treatment to obtain modified magnesium hydroxide.
Comparative example 3
Magnesium hydroxide by precipitation method has lamellar structure.
Comparative example 4
Magnesium hydroxide by precipitation.
The magnesium hydroxide products provided in examples 1 to 5 and comparative examples 1 to 4 were tested for particle size, specific surface area and oil absorption value, and the test methods and test results are shown in table 1.
Table 1 results of particle size, specific surface area and oil absorption value tests for examples 1 to 5 and comparative examples 1 to 4
As can be seen from Table 1, the median particle diameter D50 of the molybdenum substrate layer modified magnesium hydroxide provided in the examples of the present invention is 1.055-1.187 μm, and the median particle diameter is small; the specific surface area is 19.333-19.848 m 2 G, the 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 invention is subjected to silane couplingThe D50 of the modified magnesium hydroxide powder of the molybdenum substrate layer after the reasonably modified magnesium hydroxide of the linking agent and the molybdenum substrate layer are hybridized is relatively smaller, and the specific surface area is relatively higher; meanwhile, the oil absorption value of the modified magnesium hydroxide of the molybdenum substrate layer provided by the embodiment of the invention is lower than that of the modified magnesium hydroxide of the comparative examples 1-4, probably because the magnesium hydroxide is better in effect after being modified by a reasonable part of the silane coupling agent, and when the silane coupling agent is excessively added or excessively added, the magnesium hydroxide cannot be effectively modified, so that the particle performance of the hybrid magnesium hydroxide powder of the molybdenum substrate layer is finally influenced, and the particle size of the modified magnesium hydroxide of the molybdenum substrate layer 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 companies at home and abroad), 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, probably because the magnesium hydroxide powder of comparative examples 3-4 is more in surface hydrophilic groups and larger in polarity, so that the oil absorption value is larger, the processing fluidity of the polymer matrix material in application can be reduced, and the processing cost of a downstream manufacturer can be increased, so that the molybdenum substrate layer has obvious effect in changing the oil absorption value of the magnesium hydroxide powder.
The molybdenum substrate layer modified magnesium hydroxide obtained in examples 1 to 5 and the magnesium hydroxide obtained in comparative examples 1 to 4 are respectively used as flame retardants to carry out flame retardant smoke suppression tests and tensile property tests, and the test methods are as follows: 50g of polyvinyl chloride (SG 5), 25g of dioctyl phthalate, 2g of barium-cadmium-zinc stabilizer, 30g of calcium carbonate (GY-616), 2g of antimonous oxide and 4g of flame retardant are mixed, mechanically stirred, and then mixed for 10min at 170 ℃ by a two-roll mill, and molded to prepare a corresponding standard test sample for subsequent performance test:
the test method comprises the following steps:
oxygen index test: the test standard is GB/T2406.2-2009;
smoke density testing: adopting a building material smoke density tester, wherein the test standard is GB/T8627-2007;
tensile strength test: the test standard is GB/T1040-2018, and the stretching rate is 50mm/min;
the test results are shown in Table 2.
TABLE 2 flame retardant smoke suppression effect and tensile Property test results for 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 limiting oxygen index of the modified magnesium hydroxide of the molybdenum substrate layer prepared in the embodiment of the invention is 29.2-30.0%, and the maximum smoke density is 86.45-87.88 kg/m 3 The flame-retardant smoke-suppressing effect is good. From the limiting oxygen index test data, the molybdenum substrate layer modified magnesium hydroxide powder prepared by the embodiments of the invention can be found to effectively improve the limiting oxygen index of the polyvinyl chloride composite material, so that the limiting 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 surface coated silane coupling agent is not beneficial to the surface modification of magnesium hydroxide due to too much or too little,the final modification effect is poor, and the better flame-retardant smoke-suppressing characteristic of the hybrid powder is difficult to develop; compared with comparative examples 3-4, the improved limiting oxygen index of the molybdenum substrate layer modified magnesium hydroxide provided by the invention is higher, probably because the molybdenum substrate layer exists on the surface of the molybdenum substrate layer modified magnesium hydroxide, the molybdenum substrate layer modified magnesium hydroxide not only can promote the formation of carbon, but also can enhance the physical barrier effect, and meanwhile, the molybdenum and magnesium hydroxide have a plurality of advantages such as synergistic flame retardant effect and the like. According to the maximum smoke density test data, the modified magnesium hydroxide with the molybdenum substrate layer provided by the invention can be added to further reduce the smoke release density of the polyvinyl chloride-based material, further improve the smoke suppression performance, and better meet the requirements of environmental protection and smoke suppression.
From 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-based material is reduced to about 10 MPa; when the modified magnesium hydroxide of comparative examples 1 to 2 is added, the mechanical properties are reduced to a certain extent compared with the examples, which is probably because the unreasonable part ratio of the silane coupling agent to the magnesium hydroxide leads to poor surface modification effect of the magnesium hydroxide and finally leads to reduced tensile strength when the molybdenum substrate layer is hybridized; when magnesium hydroxide of comparative examples 3 to 4 is added, the tensile strength of the polyvinyl chloride-based material is only 9.08 to 9.27MPa, which is probably because magnesium hydroxide powder has larger particle size and poor compatibility with a polyvinyl chloride matrix due to surface polarity, and when the polyvinyl chloride-based material is subjected to external force stretching, defects are generated in the polyvinyl chloride polymer due to poor dispersibility, so that the mechanical property of the polyvinyl chloride-based material is induced to be reduced; the modified magnesium hydroxide of the molybdenum substrate layer provided by the invention has small granularity and weak surface polarity, and has a good effect on maintaining the mechanical properties of polyvinyl chloride-based materials.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. A modified magnesium hydroxide of a molybdenum substrate layer comprises a magnesium hydroxide core and a shell formed by the molybdenum substrate layer coating the magnesium hydroxide core; the chemical composition of the molybdenum substrate layer is MoX 2 X is O, S, se or Te;
the particle size of the magnesium hydroxide kernel is 0.6-1.5 mu m;
the particle size of the modified magnesium hydroxide of the molybdenum substrate layer is 0.8-2.0 mu m;
the preparation method of the molybdenum substrate layer modified magnesium hydroxide comprises the following steps:
mixing the modified magnesium hydroxide with the molybdenum substrate layer dispersion liquid, and carrying out hybridization reaction to obtain the modified magnesium hydroxide of the molybdenum substrate layer; the modified magnesium hydroxide is silane coupling agent modified magnesium hydroxide.
2. The molybdenum substrate layer-modified magnesium hydroxide according to claim 1, wherein said shell comprises 5-90 wt.% of the molybdenum substrate layer-modified magnesium hydroxide.
3. The method for preparing the molybdenum substrate layer-modified magnesium hydroxide according to any one of claims 1 to 2, comprising the steps of:
mixing the modified magnesium hydroxide with the molybdenum substrate layer dispersion liquid, and carrying out hybridization reaction to obtain the modified magnesium hydroxide of the molybdenum substrate layer; the modified magnesium hydroxide is silane coupling agent modified magnesium hydroxide.
4. The method according to claim 3, wherein the particle diameter 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.
5. The method of claim 3, wherein the silane coupling agent comprises one or more of gamma- (2, 3-glycidoxypropyl) propyl trimethoxysilane, gamma-methacryloxypropyl trimethoxysilane, gamma-mercaptopropyl triethoxysilane, gamma-mercaptopropyl trimethoxysilane, vinyl trimethoxysilane, and 3-aminopropyl triethoxysilane.
6. The method according to claim 3, wherein the hybridization is carried out at a temperature of 20 to 100℃for a period of 0.5 to 8 hours;
the hybridization reaction is carried out under stirring, and the stirring speed is 100-700 rpm.
7. The method according to claim 3 or 6, wherein after the hybridization reaction, further comprising: and (3) cleaning, solid-liquid separation and drying the obtained hybridization reaction product in sequence.
8. The method of claim 7, wherein the wash liquid in the washing is one or more of deionized water, methanol, ethanol, ethyl acetate, and tetrahydrofuran;
the solid-liquid separation is centrifugation; the centrifugal 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 h.
9. Use of the modified magnesium hydroxide of molybdenum substrate layer according to any one of claims 1 to 2 or the modified magnesium hydroxide of molybdenum substrate layer obtained by the preparation method according to any one of claims 3 to 8 as a flame retardant.
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