High-molecular fireproof material for distribution box and preparation method of high-molecular fireproof material

Abstract

The invention relates to the technical field of high-molecular materials, and provides a high-molecular fireproof material for a distribution box and a preparation method of the high-molecular fireproof material. The high-molecular fireproof material for the distribution box comprises the following components: PP, maleic anhydride grafted polyolefin, a modified inorganic flame retardant, an organic flame retardant and a processing aid, and the modified inorganic flame retardant comprises compound modified graphene containing pyridine and amino. According to the technical scheme, the problems that in the related technology, the flame retardant effect of graphene on the high polymer material is poor, and the fire resistance is insufficient are solved.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically to a polymer fireproof material for electrical distribution boxes and its preparation method. Background Technology

[0002] Distribution boxes are specialized power distribution devices widely used in various scenarios such as industrial production, civil buildings, and new energy power plants. Their operational safety directly affects the safety of people and property, as well as the stability of the entire electrical system. Electrical faults are one of the leading causes of fires. Overloads and short circuits in the internal wiring of distribution boxes can lead to localized overheating, easily igniting the casing and internal insulation materials. Once the fire spreads, it can not only paralyze the power distribution system but also trigger a chain reaction of disasters. Therefore, distribution boxes must possess excellent fire-resistant properties.

[0003] Polypropylene (PP) has become the mainstream polymer material for electrical distribution boxes due to its advantages such as lightweight, corrosion resistance, good molding and processability, and controllable cost. However, polypropylene is a flammable material; it continues to burn after being removed from the flame and is accompanied by melting and dripping, which can easily cause secondary fires, resulting in poor fire resistance. Graphene has strong barrier properties, high thermal stability, and a large specific surface area for adsorption. Adding it to polypropylene materials can effectively reduce the transfer of heat and oxygen during the combustion process of the composite material, thereby improving the flame retardancy and fire resistance of the material. However, the poor dispersibility of graphene in the polymer matrix limits its effect on improving the flame retardancy of the material, resulting in insufficient fire resistance. Summary of the Invention

[0004] This invention proposes a polymer fire-retardant material for distribution boxes and its preparation method, which solves the problem that graphene has a poor effect on improving the flame retardancy of polymer materials and insufficient fire resistance in related technologies.

[0005] The technical solution of the present invention is as follows: A polymer fire-retardant material for electrical distribution boxes comprises the following components: PP, maleic anhydride-grafted polyolefin, modified inorganic flame retardant, organic flame retardant, and processing aids, wherein the modified inorganic flame retardant includes modified graphene containing pyridine and amino compounds.

[0006] Maleic anhydride-grafted polyolefins, acting as compatibilizers, increase the compatibility of the components in the system, ensuring that the polymer material exhibits excellent overall performance. The maleic anhydride-grafted polyolefin can be any conventional maleic anhydride-grafted polyolefin in the art, such as maleic anhydride-grafted polyethylene or maleic anhydride-grafted polypropylene, preferably maleic anhydride-grafted polypropylene.

[0007] As a further technical solution, the modified inorganic flame retardant also includes sodium tripolyphosphate modified magnesium aluminum hydrotalcite.

[0008] In this invention, in addition to graphene modified with compounds containing pyridine and amino groups, sodium tripolyphosphate-modified magnesium aluminum hydrotalcite is also added. The combination of these two materials improves the flame retardancy and fire resistance of the polymer material. In the sodium tripolyphosphate-modified magnesium aluminum hydrotalcite, the modification of the magnesium aluminum hydrotalcite with sodium tripolyphosphate improves its dispersibility in the polymer matrix. Its use in combination with graphene modified with compounds containing pyridine and amino groups further enhances the flame retardancy and fire resistance of the polymer material.

[0009] As a further technical solution, the mass ratio of the pyridine- and amino-containing modified graphene and sodium tripolyphosphate-modified magnesium aluminum hydrotalcite is 3:2 to 1:4, preferably 1:1 to 2:3, and more preferably 2:3.

[0010] In this invention, when the mass ratio of graphene modified with pyridine and amino compounds to magnesium aluminum hydrotalcite modified with sodium tripolyphosphate is 1:1 to 2:3, the two have a synergistic effect, which significantly improves the flame retardancy of the polymer material.

[0011] As a further technical solution, the raw material for the graphene modified with pyridine and amino compounds includes a pyridine and amino compound and graphene in a mass ratio of 1~2:20.

[0012] In this invention, the compound containing pyridine and amino can be any compound containing a pyridine ring and an amino group, such as 2-amino-3-methylpyridine, 3-amino-2-nitropyridine, 3-amino-4-methylpyridine, 2-amino-3-hydroxypyridine, 2-amino-3-acetylpyridine, 2-amino-5-nitropyridine, 2-methyl-4-aminopyridine, etc.

[0013] As a further technical solution, the preparation method of the graphene modified with pyridine and amino compounds includes the following steps: ultrasonically dispersing graphene in an organic solvent, adding a compound containing pyridine and amino and stirring until completely dissolved, continuing to stir for modification, drying, and obtaining graphene modified with pyridine and amino compounds.

[0014] In this invention, the organic solvent can be any solvent capable of dissolving compounds containing pyridine and amino groups, preferably a low-boiling-point organic solvent, such as ethanol, methanol, diethyl ether, chloroform, petroleum ether, etc.

[0015] As a further technical solution, the raw materials for the sodium tripolyphosphate modified magnesium aluminum hydrotalcite include sodium tripolyphosphate and magnesium aluminum hydrotalcite in a mass ratio of 2~3:20.

[0016] As a further technical solution, the preparation method of sodium tripolyphosphate modified magnesium aluminum hydrotalcite includes the following steps: dispersing magnesium aluminum hydrotalcite in water, adding sodium tripolyphosphate for modification, washing, filtering, and drying to obtain sodium tripolyphosphate modified magnesium aluminum hydrotalcite.

[0017] As a further technical solution, the processing aid includes at least one of the following characteristics: plasticizer, lubricant, antioxidant, light stabilizer, and antistatic agent.

[0018] In this invention, the processing aid can be any conventional processing aid in the art, such as any one or more of plasticizers, lubricants, heat stabilizers, antioxidants, light stabilizers, antistatic agents, and pigments, preferably plasticizers, lubricants, antioxidants, and light stabilizers in a mass ratio of 1~3:1:0.5:0.5.

[0019] The plasticizer can be any conventional plasticizer in the art, such as any one or more of diisodecyl phthalate, dibutyl phthalate, dioctyl phthalate, and dioctyl sebacate, preferably diisodecyl phthalate.

[0020] The lubricant can be any conventional lubricant in the art, such as any one or more of fatty acids, hard fatty acid soaps, esters, amides, and paraffin, preferably hard fatty acid soaps.

[0021] The antioxidant can be any conventional antioxidant in the art, such as any one or more of antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant 264, and antioxidant 3114. The light stabilizer can be any conventional light stabilizer in the art, such as any one or more of ultraviolet absorber UV-9, ultraviolet absorber UV-531, and ultraviolet absorber UV-327.

[0022] As a further technical solution, the mass ratio of PP, maleic anhydride grafted polyolefin, modified inorganic flame retardant, organic flame retardant, and processing aid is 100:5~10:15~25:30:3~5.

[0023] The present invention also proposes a method for preparing a polymer fire-retardant material for distribution boxes, which includes the following steps: mixing the components evenly, melting and extruding, granulating, and obtaining the polymer fire-retardant material for distribution boxes.

[0024] The working principle and beneficial effects of this invention are as follows: Compared to the traditional method of directly adding graphene, this invention modifies graphene by incorporating compounds containing pyridine and amino groups. Modifying graphene with these compounds improves its dispersibility within the polymer matrix. Simultaneously, the amino groups on the surface of the pyridine- and amino-containing graphene can interact with the anhydrides in maleic anhydride-grafted polyolefins, enhancing the compatibility between graphene and the polymer matrix. This, in turn, improves the flame retardancy of the polymer material, providing a polymer fire-retardant material for electrical distribution boxes. Detailed Implementation

[0025] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0026] In the following embodiments and comparative examples: PP: PP Dushanzi Petrochemical S1003; Maleic anhydride-grafted polypropylene: Mitsui QF551 (Japan); Graphene: Model: LN-2P, Manufacturer: Shanghai Liwusheng Nanotechnology Co., Ltd. Magnesium aluminum hydrotalcite: Model: D200, Manufacturer: Hefei Anyuhe New Material Technology Co., Ltd.

[0027] Example 1 S1. According to the mass fraction, 20 parts of graphene were ultrasonically dispersed in 30 parts of methanol. The ultrasonic frequency was 60kHz, the ultrasonic power was 500W, the ultrasonic temperature was 30℃, and the ultrasonic time was 25min. 1 part of 2-methyl-4-aminopyridine was added and stirred at 350rpm until completely dissolved. After stirring for another 15min for modification, the mixture was dried to obtain modified graphene containing pyridine and amino compounds. S2. According to the mass parts, 100 parts PP, 5 parts maleic anhydride grafted polypropylene, 15 parts graphene modified with pyridine and amino compounds, 20 parts ammonium polyphosphate, 10 parts melamine, 1 part diisodecyl phthalate, 1 part zinc stearate, 1 part antioxidant 168, 0.5 parts antioxidant 1010, and 0.5 parts ultraviolet absorber UV-9 are mixed evenly, melt-extruded, and granulated to obtain a polymer fireproof material for distribution boxes.

[0028] Example 2 S1. According to the mass fraction, 20 parts of graphene were ultrasonically dispersed in 30 parts of ethanol. The ultrasonic frequency was 60kHz, the ultrasonic power was 500W, the ultrasonic temperature was 30℃, and the ultrasonic time was 25min. 2 parts of 2-amino-5-nitropyridine were added and stirred at 350rpm until completely dissolved. Stirring was continued for 20min for modification. After drying, modified graphene containing pyridine and amino compounds was obtained. S2. According to the mass parts, 100 parts PP, 10 parts maleic anhydride grafted polypropylene, 15 parts graphene modified with pyridine and amino compounds, 20 parts ammonium polyphosphate, 10 parts melamine, 3 parts diisodecyl phthalate, 1 part zinc stearate, 1 part antioxidant 168, 0.5 parts antioxidant 1010, and 0.5 parts ultraviolet absorber UV-9 are mixed evenly, melt-extruded, and granulated to obtain a polymer fireproof material for distribution boxes.

[0029] Example 3 S1. According to the mass fraction, 20 parts of graphene were ultrasonically dispersed in 30 parts of ethanol. The ultrasonic frequency was 60kHz, the ultrasonic power was 500W, the ultrasonic temperature was 30℃, and the ultrasonic time was 25min. 2 parts of 2-amino-5-nitropyridine were added and stirred at 350rpm until completely dissolved. Stirring was continued for 20min for modification. After drying, modified graphene containing pyridine and amino compounds was obtained. Disperse 20 parts of magnesium aluminum hydrotalcite in 50 parts of water, stir at 40℃ and 350 rpm for 10 min, raise the temperature to 60℃, add 2.5 parts of sodium tripolyphosphate and continue stirring for 60 min, wash, filter, and dry to obtain sodium tripolyphosphate modified magnesium aluminum hydrotalcite. S2. According to the mass parts, 100 parts PP, 10 parts maleic anhydride grafted polypropylene, 15 parts graphene modified with compounds containing pyridine and amino groups, 10 parts sodium tripolyphosphate modified magnesium aluminum hydrotalcite, 20 parts ammonium polyphosphate, 10 parts melamine, 3 parts diisodecyl phthalate, 1 part zinc stearate, 1 part antioxidant 168, 0.5 parts antioxidant 1010, and 0.5 parts ultraviolet absorber UV-9 are mixed evenly, melt-extruded, and granulated to obtain a polymer fireproof material for electrical distribution boxes.

[0030] Example 4 The only difference from Example 3 is that 15 parts of graphene modified with pyridine and amino compounds and 10 parts of sodium tripolyphosphate modified magnesium aluminum hydrotalcite are replaced with 12.5 parts of graphene modified with pyridine and amino compounds and 12.5 parts of sodium tripolyphosphate modified magnesium aluminum hydrotalcite.

[0031] Example 5 The only difference from Example 3 is that 15 parts of graphene modified with pyridine and amino compounds and 10 parts of sodium tripolyphosphate modified magnesium aluminum hydrotalcite are replaced with 10 parts of graphene modified with pyridine and amino compounds and 15 parts of sodium tripolyphosphate modified magnesium aluminum hydrotalcite.

[0032] Example 6 The only difference from Example 3 is that 15 parts of graphene modified with pyridine and amino compounds and 10 parts of sodium tripolyphosphate modified magnesium aluminum hydrotalcite are replaced with 5 parts of graphene modified with pyridine and amino compounds and 20 parts of sodium tripolyphosphate modified magnesium aluminum hydrotalcite.

[0033] Comparative Example 1 The only difference from Example 2 is that the graphene modified with compounds containing pyridine and amino groups is replaced with an equal amount of graphene.

[0034] Comparative Example 2 S1. According to the mass fraction, 20 parts of magnesium aluminum hydrotalcite are dispersed in 50 parts of water, stirred at 40℃ and 350rpm for 10min, heated to 60℃, 2.5 parts of sodium tripolyphosphate are added and stirred for another 60min, washed, filtered and dried to obtain sodium tripolyphosphate modified magnesium aluminum hydrotalcite. S2. According to the mass parts, 100 parts PP, 10 parts maleic anhydride grafted polypropylene, 10 parts sodium tripolyphosphate modified magnesium aluminum hydrotalcite, 20 parts ammonium polyphosphate, 10 parts melamine, 3 parts diisodecyl phthalate, 1 part zinc stearate, 1 part antioxidant 168, 0.5 parts antioxidant 1010, and 0.5 parts ultraviolet absorber UV-9 are mixed evenly, melt-extruded, and granulated to obtain a polymer fireproof material for distribution boxes.

[0035] Comparative Example 3 The only difference from Example 2 is that no graphene modified with compounds containing pyridine and amino groups is added.

[0036] The granules were hot-pressed into shape and then subjected to the following performance tests: (1) Flame retardancy: The oxygen index was tested according to the method in GB / T 2406.2-2009. The sample size was: Type IV 100mm×6mm×3mm, Method A; (2) Fire resistance: The vertical fire rating shall be determined by vertical test according to the method in GB / T 2408-2021. The sample size is 130mm long × 13mm wide × 6mm thick. The test results are recorded in Table 1.

[0037] Table 1. Test results of flame retardancy and fire resistance of polymer materials.

[0038] As shown in Table 1, the polymer material provided by this invention has good flame retardancy and fire resistance. Compared with Comparative Example 1, Example 2 has a higher oxygen index and a vertical burning rating of V-1, indicating that the addition of graphene modified with compounds containing pyridine and amino groups improves the flame retardancy and fire resistance of the polymer material.

[0039] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A polymer fire-retardant material for distribution boxes, characterized in that, It includes the following components: PP, maleic anhydride-grafted polyolefin, modified inorganic flame retardant, organic flame retardant, and processing aid, wherein the modified inorganic flame retardant includes graphene modified with compounds containing pyridine and amino groups.

2. The polymer fire-retardant material for a distribution box according to claim 1, characterized in that, The modified inorganic flame retardant also includes sodium tripolyphosphate modified magnesium aluminum hydrotalcite.

3. The polymer fire-retardant material for a distribution box according to claim 2, characterized in that, The mass ratio of the modified graphene containing pyridine and amino compounds to the modified magnesium aluminum hydrotalcite containing sodium tripolyphosphate is 2:

3.

4. The polymer fire-retardant material for a distribution box according to claim 1, characterized in that, The raw materials for the graphene modified with pyridine and amino compounds include pyridine and amino compounds and graphene in a mass ratio of 1~2:

20.

5. The polymer fire-retardant material for a distribution box according to claim 1, characterized in that, The preparation method of the graphene modified with pyridine and amino compounds includes the following steps: ultrasonically dispersing graphene in an organic solvent, adding a compound containing pyridine and amino compounds and stirring until completely dissolved, continuing to stir for modification, and drying to obtain graphene modified with pyridine and amino compounds.

6. The polymer fire-retardant material for a distribution box according to claim 2, characterized in that, The raw materials for the sodium tripolyphosphate modified magnesium aluminum hydrotalcite include sodium tripolyphosphate and magnesium aluminum hydrotalcite in a mass ratio of 2~3:

20.

7. The polymer fire-retardant material for a distribution box according to claim 2, characterized in that, The preparation method of sodium tripolyphosphate modified magnesium aluminum hydrotalcite includes the following steps: dispersing magnesium aluminum hydrotalcite in water, adding sodium tripolyphosphate for modification, washing, filtering, and drying to obtain sodium tripolyphosphate modified magnesium aluminum hydrotalcite.

8. The polymer fire-retardant material for a distribution box according to claim 1, characterized in that, The processing aid includes at least one of the following characteristics: plasticizer, lubricant, antioxidant, light stabilizer, and antistatic agent.

9. A polymer fire-retardant material for a distribution box according to claim 1, characterized in that, The mass ratio of PP, maleic anhydride-grafted polyolefin, modified inorganic flame retardant, organic flame retardant, and processing aid is 100:5~10:15~25:30:3~5.

10. A method for preparing a polymer fire-retardant material for distribution boxes, used to prepare the polymer fire-retardant material for distribution boxes as described in any one of claims 1 to 9, characterized in that, Includes the following steps: After the components are mixed evenly, they are melt-extruded and granulated to obtain a polymer fireproof material for distribution boxes.

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