A wet-heat-resistant electrolytic manganese residue / polyolefin resin composite material and a preparation method thereof

Abstract

The application belongs to the technical field of industrial waste residue recycling and reusing, and particularly relates to a kind of wet and hot electrolytic manganese residue / polyolefin resin composite material and its preparation method. It comprises the following mass parts of raw materials: 100 parts of polyolefin resin, 20-50 parts of modified electrolytic manganese residue, 3-5 parts of lubricant; the modified electrolytic manganese residue is prepared by mixing water-soluble phenolic resin solution, alkyl silane coupling agent and electrolytic manganese residue in water, and then spray drying; the mass ratio of the water-soluble phenolic resin solution, silane coupling agent, electrolytic manganese residue and water is 1:0.05-0.2:0.1-0.3:3-5, preferably 1:0.1-0.15:0.1-0.3:3-5. The core-shell structure of the modified electrolytic manganese residue can fix the soluble salt component and inhibit the migration and precipitation of the soluble salt. At the same time, the silane coupling agent and phenolic resin can improve the interfacial compatibility of the electrolytic manganese residue and the non-polar polyolefin base material, thus fundamentally solving the problems of poor mechanical properties, moisture absorption and migration of the composite material.

Description

Technical Field

[0001] This invention belongs to the field of industrial waste recycling technology, specifically relating to a moisture-heat resistant electrolytic manganese slag / polyolefin resin composite material and its preparation method. Background Technology

[0002] Electrolytic manganese slag is a waste residue produced by the wet electrolysis of metallic manganese, containing large amounts of calcium, manganese, iron, aluminum, and ammonium salts. Currently, electrolytic manganese slag is generally disposed of using primitive and inefficient stockpiling methods. The large amounts of soluble manganese, ammonia nitrogen, and heavy metal ions it contains are easily migrated into the external environment through surface runoff and underground infiltration, causing serious pollution to the surrounding soil and water bodies. Therefore, the large-scale accumulation of manganese slag not only wastes resources but also causes serious secondary pollution. Developing manganese slag utilization technologies is urgently needed, and its resource utilization has become a pressing issue to be addressed.

[0003] Polyolefin resin (PP / PE) possesses a comprehensive set of properties, including low density, excellent chemical resistance, good mechanical toughness, easy processing and molding, and high cost-effectiveness. It is widely used in geotechnical materials, agricultural products, packaging materials, municipal pipes, and daily-use injection-molded components, making it the most widely used general-purpose polymer material in industry. To further improve the rigidity, thermal stability, and dimensional stability of polyolefin materials, inorganic fillers such as calcium carbonate and talc are commonly used in industry for modification. However, traditional inorganic fillers rely on mineral resource extraction, resulting in high resource consumption and rising raw material costs year by year, making resource-based alternatives urgently needed.

[0004] Electrolytic manganese slag is rich in rigid mineral components such as aluminosilicates and gypsum, possessing fundamental modification potential as a polymer filler, and has now attracted industry research attention. For example, patent CN106751142B discloses a method for preparing electrolytic manganese slag-filled polyvinyl chloride composite material using electrolytic manganese slag and polyvinyl chloride. First, the electrolytic manganese slag is dried to constant weight, then initially mixed with polyvinyl chloride resin, plasticizer, heat stabilizer, and hyperbranched polyester in a high-speed mixer, and then extruded and granulated using a twin-screw extruder to obtain the final product. The weight ratio of polyvinyl chloride resin, dried electrolytic manganese slag, plasticizer, heat stabilizer, and hyperbranched polyester is 100:80~140:5~10:1.5~5:0.5~5. Patent CN201910953374.8 discloses a method for reusing electrolytic manganese waste residue. The method involves taking 96-100 parts of electrolytic manganese waste residue and 2-5 parts of fine powdered desulfurizing agent; then, sending the prepared electrolytic manganese waste residue and fine powdered desulfurizing agent to a dispersing device for uniform mixing, followed by drying and crushing in a vertical dryer at 400-500℃; feeding the dried and crushed electrolytic manganese waste residue into a rotary kiln for high-temperature calcination, and then cooling the discharged manganese slag using a rapid cooling method; surface-modifying the cooled electrolytic manganese waste residue; and then melt-blending the surface-modified 900-1100 mesh manganese slag ultrafine powder with PP, HDPE, or PVC to produce corresponding manganese slag ultrafine powder / PP composite material, manganese slag ultrafine powder / HDPE composite material, or manganese slag ultrafine powder / PVC composite material. The above describes the application of electrolytic manganese slag as a polymer filler, which achieves the purpose of recycling electrolytic manganese slag solid waste. However, electrolytic manganese slag has poor compatibility with non-polar polyolefin matrix, resulting in poor mechanical properties of the obtained composite material. In addition, electrolytic manganese slag has a high soluble salt content, is easy to absorb moisture and migrate, which leads to the deterioration of mechanical properties, further limiting its application in polyolefin materials.

[0005] Therefore, developing an efficient and stable electrolytic manganese slag modification technology to realize its high-value resource utilization in polyolefin materials has significant economic and environmental value. Summary of the Invention

[0006] To address the aforementioned technical problems, this invention provides a moisture-heat-resistant electrolytic manganese slag / polyolefin resin composite material and its preparation method. The method uses electrolytic manganese slag, water-soluble phenolic resin, and an alkyl silane coupling agent as raw materials, mixes them in water, and spray-dries them to produce a modified electrolytic manganese slag with electrolytic manganese slag as the core and silane coupling agent and phenolic resin as the shell. The core-shell structure of the modified electrolytic manganese slag can fix soluble salt components and inhibit the migration and precipitation of soluble salts. Simultaneously, the silane coupling agent and phenolic resin improve the interfacial compatibility between the electrolytic manganese slag and the non-polar polyolefin substrate, fundamentally solving the problems of poor mechanical properties and moisture absorption and migration-induced mechanical property degradation in the composite material.

[0007] To achieve the above objectives, the following technical solution is adopted:

[0008] A moisture-heat resistant electrolytic manganese slag / polyolefin resin composite material comprises the following raw materials in parts by weight: 100 parts polyolefin resin, 20-50 parts modified electrolytic manganese slag, and 3-5 parts lubricant; the modified electrolytic manganese slag is prepared by adding water-soluble phenolic resin solution, alkylsilane coupling agent, and electrolytic manganese slag to water, mixing, and then spray drying; the mass ratio of water-soluble phenolic resin solution, silane coupling agent, electrolytic manganese slag, and water is 1:0.05-0.2:0.1-0.3:3-5, preferably 1:0.1-0.15:0.1-0.3:3-5.

[0009] Water-soluble phenolic resin is a network prepolymer containing a large number of hydroxymethyl end groups, generated by the reaction of formaldehyde and phenol under alkaline conditions. At room temperature, the network prepolymer is a viscous liquid or solid, soluble in water. Water-soluble phenolic resin does not require additional crosslinking agents. Heating to 120-180℃ can further condense the hydroxymethyl groups and crosslink them into a three-dimensional network structure. Since phenolic resin contains a large number of hydroxyl groups and has a higher polarity than polyolefins, this invention introduces an appropriate amount of alkylsilane coupling agent. The silanol groups generated by the hydrolysis of silane can dehydrate and bond with the hydroxyl groups on the surface of phenolic resin, making the polarity of the shell material of modified electrolytic manganese slag close to that of polyolefin resin, thus improving the interfacial compatibility between modified electrolytic manganese slag and non-polar polyolefin matrix.

[0010] The modified electrolytic manganese slag has an average particle size of 30-50 μm.

[0011] The water-soluble phenolic resin solution has a solid content of 45-70%.

[0012] The alkylsilane coupling agent has 6-12 alkyl carbon atoms. Specifically, the alkylsilane coupling agent is selected from at least one of n-hexyltrimethoxysilane, n-hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, dodecyltrimethoxysilane, and dodecyltriethoxysilane. Preferably, the alkylsilane coupling agent has 10-12 carbon atoms.

[0013] The electrolytic manganese slag has an average particle size of 5-30 μm, preferably 10-15 μm. The electrolytic manganese slag is a solid waste discharged during the electrolytic manganese smelting process, and its chemical composition meets the following requirements: SiO2: 25-40%, CaO: 5-15%, Al2O3: 5-15%, Fe2O3: 0.1-7%, MgO: 0.1-3%, MnO: 0.1-5%, SO3: 20-40%, K2O: 0.1-3%, Na2O: 0.01-1%, P2O5: 0.01-1%, TiO2: 0.01-1%; the mineral composition includes 20-40 wt% CaSO4·nH2O, where n = 0, 0.5, or 2.

[0014] The spray drying conditions are as follows: feed rate of 30-60 mL / min, inlet temperature of 180-250℃, outlet temperature of 100-160℃, and atomizer rotation speed of 8000-12000 rpm.

[0015] The lubricant is selected from at least one of silicone powder, paraffin wax, stearic acid, calcium stearate, magnesium stearate, zinc stearate, and polyethylene wax.

[0016] The polyolefin resin is selected from at least one of high-density polyethylene, linear low-density polyethylene, and polypropylene.

[0017] The melt index of the polyolefin resin is 0.1-3 g / 10 min.

[0018] The electrolytic manganese slag / polyolefin resin composite material also includes 1-10 parts of additives.

[0019] The additives are selected from at least one of antioxidants, UV stabilizers, heat stabilizers, and plasticizers.

[0020] There are no particular limitations on the antioxidants used; any commonly used antioxidants in the field may be used, including but not limited to at least one of antioxidant 1010, antioxidant 168, and antioxidant 1076.

[0021] There are no particular limitations on the UV-resistant agent mentioned above; any commonly used agent in the field may be used, including but not limited to at least one of benzoic acid UV-resistant agents, xylene ketone UV-resistant agents, and benzotriazole UV-resistant agents.

[0022] There are no particular limitations on the heat stabilizer; any commonly used one in the art is acceptable, including but not limited to at least one of metal soaps, lead salts, organotin compounds, and magnesium salts.

[0023] There are no particular limitations on the plasticizers used; any commonly used plasticizers in the field are acceptable, including but not limited to at least one of dioctyl phthalate, diisodecyl phthalate, and diisononyl phthalate.

[0024] The present invention also provides a method for preparing the above-mentioned moisture-heat resistant electrolytic manganese slag / polyolefin resin composite material, comprising the following steps:

[0025] Polyolefin resin, modified electrolytic manganese slag, and lubricant are mixed and then fed into a twin-screw extruder for extrusion granulation to obtain an electrolytic manganese slag / polyolefin resin composite material.

[0026] The twin-screw extruder operates at a temperature of 150-230℃. The length-to-diameter ratio of the screw in the twin-screw extruder is 36-48:1.

[0027] An application of a moisture-heat resistant electrolytic manganese slag / polyolefin resin composite material for the preparation of home and decoration materials, personal protective equipment, transportation materials, building and engineering materials, industrial application materials, electronic and electrical product materials, and fire-resistant materials.

[0028] Compared with the prior art, the beneficial effects of the present invention are:

[0029] I. This invention uses electrolytic manganese slag, water-soluble phenolic resin, and alkyl silane coupling agents as raw materials. These are mixed in water and spray-dried to produce modified electrolytic manganese slag with the core of the slag and the shell of the silane coupling agent and phenolic resin. The core-shell structure of the modified electrolytic manganese slag can fix soluble salt components and inhibit the migration and precipitation of soluble salts. Simultaneously, the silane coupling agent and phenolic resin improve the interfacial compatibility between the electrolytic manganese slag and the non-polar polyolefin substrate, fundamentally solving the problems of poor mechanical properties of the composite material and the deterioration of mechanical properties due to moisture absorption and migration. Furthermore, the inventors discovered that the compounding of modified electrolytic manganese slag and phenolic resin can further improve the flame retardant properties of the composite material, speculating that the manganese and other metal elements in the electrolytic manganese slag promote the formation of a barrier carbon layer by the phenolic resin.

[0030] Second, this invention can recycle industrial bulk electrolytic manganese solid waste, which has both environmental and economic benefits and is suitable for industrial mass production. Attached Figure Description

[0031] Figure 1 The sample after the flexural strength test of the electrolytic manganese slag / polyolefin resin composite material in Example 1;

[0032] Figure 2 The sample is a specimen before the flexural strength test of the electrolytic manganese slag / polyolefin resin composite material in Example 1. Detailed Implementation

[0033] The present invention will be further described below with reference to specific embodiments, but is not limited to the contents of the specification. Unless otherwise specified, all "parts" mentioned in the embodiments of the present invention are parts by weight. All reagents used are commercially available in the art.

[0034] Electrolytic manganese slag is a solid waste generated during the electrolytic manganese smelting process. It has an average particle size of 10.2 μm and comes from Guangxi Huiyuan Manganese Industry Co., Ltd. Its chemical composition is as follows: SiO2: 32.3%, CaO: 12.47%, Al2O3: 8.77%, Fe2O3: 5.46%, MgO: 2.96%, MnO: 2.93%, SO3: 30.82%, K2O: 2.33%, Na2O: 0.75%, P2O5: 0.63%, TiO2: 0.45%. The mineral composition contains 20-40 wt% CaSO4·nH2O, where n = 0, 0.5, or 2.

[0035] Water-soluble phenolic resin solution P875865, solid content 70%, from Maclean's.

[0036] Water-soluble phenolic resin solution FR-8102, with a solid content of 45%, is from Locke Chemical.

[0037] The high-density polyethylene Marlex® HHM 5502LW is from Shanghai Songhan Plastics Technology Co., Ltd., with a melt index of 0.35g / 10min.

[0038] Polypropylene, melt index 1 g / 10 min, from Shanghai Chuangsai Technology Co., Ltd.

[0039] Beigaer-CaCO3-10W calcium carbonate, with an average particle size of 10μm, is from Ningbo Beigaer New Materials Co., Ltd.

[0040] Example 1

[0041] 1) Add water-soluble phenolic resin solution P875865, dodecyltriethoxysilane, and electrolytic manganese slag to water and mix well. The mass ratio of water-soluble phenolic resin solution, silane coupling agent, electrolytic manganese slag, and water is 1:0.15:0.3:5. The resulting mixture is spray-dried to obtain modified electrolytic manganese slag. The spray drying conditions are: feed rate of 60 mL / min, inlet temperature of 250℃, outlet temperature of 160℃, and atomizer speed of 8000 rpm.

[0042] 2) Mix 100 kg of high-density polyethylene Marlex® HHM 5502LW, 50 kg of modified electrolytic manganese slag, and 5 kg of silicone powder in a high-speed mixer at 800 rpm for 45 minutes. Then, add the mixture to a twin-screw extruder with a length-to-diameter ratio of 48:1 and extrude and granulate to obtain a moisture-resistant electrolytic manganese slag / polyolefin resin composite material. Temperatures from the feed inlet to the die head are: 175℃, 185℃, 190℃, 195℃, 200℃, 205℃, 195℃, 190℃, 190℃, 180℃.

[0043] Example 2

[0044] The rest is the same as in Example 1, except that in step 1), dodecyltriethoxysilane is replaced with an equal mass of n-hexyltrimethoxysilane.

[0045] Example 3

[0046] The rest is the same as in Example 1, except that in step 1), dodecyltriethoxysilane is replaced with an equal mass of n-decyltrimethoxysilane.

[0047] Example 4

[0048] The rest is the same as in Example 1, except that in step 1), dodecyltriethoxysilane is replaced with an equal mass of tetradecyltrimethoxysilane.

[0049] Example 5

[0050] The rest is the same as in Example 1, except that in step 1), the water-soluble phenolic resin solution P875865 is replaced with an equal mass of water-soluble phenolic resin solution FR-8102.

[0051] Example 6

[0052] The rest is the same as in Example 1, except that in step 1), the mass ratio of water-soluble phenolic resin solution, silane coupling agent, electrolytic manganese slag, and water is 1:0.1:0.3:5.

[0053] Example 7

[0054] The rest is the same as in Example 1, except that in step 1), the mass ratio of water-soluble phenolic resin solution, silane coupling agent, electrolytic manganese slag, and water is 1:0.05:0.3:5.

[0055] Example 8

[0056] The rest is the same as in Example 1, except that in step 1), the mass ratio of water-soluble phenolic resin solution, silane coupling agent, electrolytic manganese slag, and water is 1:0.2:0.3:5.

[0057] Example 9

[0058] The rest is the same as in Example 1, except that in step 1), the mass ratio of water-soluble phenolic resin solution, silane coupling agent, electrolytic manganese slag, and water is 1:0.15:0.1:5.

[0059] Example 10

[0060] The rest is the same as in Example 1, except that in step 2), the amount of modified electrolytic manganese slag used is 20 kg.

[0061] Example 11

[0062] 1) Modified electrolytic manganese slag was prepared by adding water-soluble phenolic resin solution P875865, dodecyltriethoxysilane, and electrolytic manganese slag to water in a mass ratio of 1:0.15:0.3:3, mixing the mixture, and spray drying. The spray drying conditions were as follows: feed rate of 60 mL / min, inlet temperature of 180℃, outlet temperature of 100℃, and atomizer speed of 12000 rpm.

[0063] 2) Mix 100 kg of polypropylene, 50 kg of modified electrolytic manganese slag, and 5 kg of silicone powder in a high-speed mixer at 800 rpm for 45 minutes. Then, add the mixture to a twin-screw extruder with a length-to-diameter ratio of 48:1 and extrude and granulate to obtain a moisture-resistant electrolytic manganese slag / polyolefin resin composite material. Temperatures from the feed inlet to the die head are: 160℃, 220℃, 230℃, 230℃, 200℃, 200℃, 230℃, 230℃, 200℃, 220℃.

[0064] Comparative Example 1

[0065] The rest is the same as in Example 1, except that in step 1), the electrolytic manganese slag is replaced with an equal mass of calcium carbonate Beigaer-CaCO3-10W.

[0066] The modified electrolytic manganese slag or the hygrothermal-resistant electrolytic manganese slag / polyolefin resin composite material prepared in the above examples and comparative examples were subjected to the following performance tests:

[0067] Particle size: The particle size of the modified electrolytic manganese slag was detected using an LS-909 laser particle size analyzer.

[0068] Bending strength: Tested in accordance with standard GB / T 9341-2008 Determination of bending properties of plastics.

[0069] Humid heat aging: The flexural strength test specimens were placed under 85℃ / 85%RH conditions for 720h of humid heat aging. The appearance of spots on the surface of the composite material was observed, and the flexural strength was retested. The flexural strength loss rate was calculated using the formula: loss rate = (σ0-σ1) / σ0×100%.

[0070] Wherein, σ0 is the bending strength of the sample before damp heat aging, in MPa; σ1 is the bending strength of the sample after 360h of damp heat aging, in MPa.

[0071] Limiting Oxygen Index (LOI): The test was conducted according to standard GB / T 2406.2-2009, "Determination of Combustion Behavior by Oxygen Index Method for Plastics - Part 2: Room Temperature Test," with a sample thickness of 4.0 mm. The LOI of pure high-density polyethylene Marlex® HHM 5502LW is 18%.

[0072] UL94 test: The vertical burning test is conducted in accordance with the standard GB / T 2408-2021 Determination of the flammability of plastics - Horizontal and Vertical Methods.

[0073] Table 1 Performance Test Results

[0074]

[0075] As shown in Table 1, the modified electrolytic manganese slag prepared in this invention exhibits good compatibility with polyolefins, with a flexural strength of 36.6-39.2 MPa. It does not precipitate or produce spots during wet heat aging, resulting in minimal degradation of the composite material's mechanical properties, with a flexural strength loss rate controlled within 4.1%. Furthermore, the modified electrolytic manganese slag also possesses certain flame-retardant properties, with the limiting oxygen index of the electrolytic manganese slag / polyolefin resin composite reaching 27.4-30.2. As seen in Examples 1 and 5-7, the relative amount of silane coupling agent needs strict control. Too much or too little agent cannot achieve a balance between flexural strength and loss rate. The presumed reason is that too much silane coupling agent makes it more prone to self-condensation polymerization, preventing cross-linking with water-soluble phenolic resin and hindering the formation of a dense cross-linked network on the surface of the electrolytic manganese slag, leading to a higher loss rate. Too little agent cannot effectively reduce the surface polarity of the modified electrolytic manganese slag, resulting in poor compatibility between the modified electrolytic manganese slag and the substrate resin, and lower flexural strength.

[0076] As shown in Examples 1-3 and Comparative Example 1, the overall mechanical properties of the composite material show an increasing trend as the number of alkyl carbon atoms in the silane coupling agent increases from 6 to 10. When the number of alkyl carbon atoms further increases from 10 to 12 and 14, the flexural strength of the composite material gradually decreases. Within the range of 6-12 carbon atoms, the flexural strength of the composite material can reach 37.6-39.1, and the limiting oxygen index (LOI) is 29.8-30.2. The mechanical properties and flame retardant properties remain stable and excellent, indicating that the modified electrolytic manganese slag within this carbon chain length range has good compatibility with the matrix resin, tight interfacial bonding, and few defects. When the number of alkyl carbon atoms in the silane coupling agent increases to 14, the flexural strength of the composite material decreases to 36.4 and the LOI decreases to 27.3. Both mechanical properties and flame retardant properties show significant degradation, indicating that excessively long alkyl chains can lead to a significant deterioration in the interfacial compatibility between the modified electrolytic manganese slag and the substrate, resulting in a decrease in interfacial bonding force and ultimately causing a simultaneous deterioration in the mechanical strength and flame retardant properties of the composite material. The change in the particle size to 52.2 μm is speculated to be due to the fact that excessively long carbon chains can easily cause the modified electrolytic manganese slag to agglomerate during the spray drying process.

[0077] The above detailed description is a specific description of one of the feasible embodiments of the present invention. This embodiment is not intended to limit the patent scope of the present invention. All equivalent implementations or modifications that do not depart from the present invention should be included within the scope of the technical solution of the present invention.

Claims

1. A moisture-heat-resistant electrolytic manganese slag / polyolefin resin composite material, characterized in that, The raw materials include the following parts by weight: 100 parts polyolefin resin, 20-50 parts modified electrolytic manganese slag, and 3-5 parts lubricant; the modified electrolytic manganese slag is prepared by adding water-soluble phenolic resin solution, alkylsilane coupling agent, and electrolytic manganese slag to water, mixing, and spray drying; the mass ratio of water-soluble phenolic resin solution, silane coupling agent, electrolytic manganese slag, and water is 1:0.05-0.2:0.1-0.3:3-5, preferably 1:0.1-0.15:0.1-0.3:3-5.

2. The moisture-heat-resistant electrolytic manganese slag / polyolefin resin composite material according to claim 1, characterized in that, The water-soluble phenolic resin solution has a solid content of 45-70%; the alkyl silane coupling agent has 6-12 alkyl C atoms, specifically, the silane coupling agent is selected from at least one of n-hexyltrimethoxysilane, n-hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, dodecyltrimethoxysilane, and dodecyltriethoxysilane; preferably, the alkyl silane coupling agent has 10-12 alkyl C atoms.

3. The moisture-heat-resistant electrolytic manganese slag / polyolefin resin composite material according to claim 1, characterized in that, The electrolytic manganese slag is a solid waste discharged during the electrolytic manganese smelting process. Its chemical composition meets the following requirements: SiO2: 25-40%, CaO: 5-15%, Al2O3: 5-15%, Fe2O3: 0.1-7%, MgO: 0.1-3%, MnO: 0.1-5%, SO3: 20-40%, K2O: 0.1-3%, Na2O: 0.01-1%, P2O5: 0.01-1%, TiO2: 0.01-1%; the mineral composition contains 20-40wt% CaSO4·nH2O, where n=0, 0.5, 2.

4. The moisture-heat-resistant electrolytic manganese slag / polyolefin resin composite material according to claim 1, characterized in that, The spray drying conditions are as follows: feed rate of 30-60 mL / min, inlet temperature of 180-250℃, outlet temperature of 100-160℃, and atomizer rotation speed of 8000-12000 rpm.

5. The moisture-heat-resistant electrolytic manganese slag / polyolefin resin composite material according to claim 1, characterized in that, The modified electrolytic manganese slag has an average particle size of 30-50 μm; the electrolytic manganese slag has an average particle size of 5-30 μm, preferably 10-15 μm.

6. The moisture-heat-resistant electrolytic manganese slag / polyolefin resin composite material according to claim 1, characterized in that, The lubricant is selected from at least one of silicone powder, paraffin wax, stearic acid, calcium stearate, magnesium stearate, zinc stearate, and polyethylene wax.

7. The moisture-heat-resistant electrolytic manganese slag / polyolefin resin composite material according to claim 1, characterized in that, The polyolefin resin is selected from at least one of high-density polyethylene, linear low-density polyethylene, and polypropylene.

8. The moisture-heat-resistant electrolytic manganese slag / polyolefin resin composite material according to claim 1, characterized in that, The melt flow index of the polyolefin resin is 0.1-3 g / 10 min.

9. The method for preparing the hygrothermal-resistant electrolytic manganese slag / polyolefin resin composite material according to any one of claims 1-8, characterized in that, Includes the following steps: Polyolefin resin, modified electrolytic manganese slag, and lubricant are mixed and then fed into a twin-screw extruder for extrusion granulation to obtain an electrolytic manganese slag / polyolefin resin composite material.

10. The application of the hygrothermal-resistant electrolytic manganese slag / polyolefin resin composite material according to any one of claims 1-8, characterized in that, Used in the preparation of home furnishing and decoration materials, personal protective equipment, transportation materials, building and engineering materials, industrial application materials, electronic and electrical product materials, and fire protection materials.

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