Mildew-proof high and low temperature resistant ethylene polymer material and preparation method thereof
Patent Information
- Application Number
- CN202610880558.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-06-17
- Publication Date
- 2026-08-21
AI Technical Summary
[0003]乙烯类热熔胶在高温、潮湿环境长期服役时，极易滋生霉菌和细菌，不仅导致粘接性能下降、材料表面劣化，还可能引发卫生安全隐患
（1） 本发明同时复配了马来酸酐接枝聚乙烯、热塑性淀粉、聚丙烯，在制备过程中，马来酸酐接枝聚乙烯与聚丙烯等比例混合，共同与热塑性淀粉共挤出，由于马来酸酐接枝聚乙烯和聚丙烯的熔指存在差异，使得两种分子链存在“粘滑”现象，分子链容易缠结，并配合热塑性淀粉自身的三维网结构，进而形成互穿网络结构，获得耐低温抗冲击改性剂，并协同改性铜锰氧化物复合材料，提高乙烯-丙烯共聚物的耐高低温和强度。
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Abstract
Description
Technical Field
[0001] This invention relates to the field of ethylene polymer materials technology, specifically to a mildew-resistant and high / low temperature ethylene polymer material and its preparation method. Background Technology
[0002] Vinyl-based hot melt adhesives are the most widely used and consumed type of hot melt adhesive due to their excellent bonding properties, low melt viscosity, and good electrical properties. They are extensively used in bookbinding, edge banding of panel furniture, and pipe corrosion protection. However, the base resins of existing vinyl-based hot melt adhesives have low softening points, making them prone to softening and deformation at high temperatures, leading to adhesive failure. At low temperatures, the molecular chain movement is frozen, resulting in a sharp decrease in initial tack, a significant reduction in peel strength, and even brittle fracture. Although researchers have attempted to improve their thermal stability through grafting modification and blending, and some methods have improved the adhesive strength and weather resistance of hot melt adhesives through maleic anhydride grafting modification, it is still not possible to simultaneously achieve resistance to both high and low temperatures.
[0003] Vinyl hot melt adhesives are highly susceptible to mold and bacteria growth when used in high-temperature and humid environments for extended periods. This not only leads to decreased bonding performance and material surface deterioration but may also pose hygiene and safety hazards. Existing technologies often employ a simple blending method by directly adding antibacterial agents to achieve anti-mold properties. However, conventional antibacterial agents have poor compatibility with the matrix resin, are unevenly distributed, and are prone to migration and loss during use, making it difficult to achieve long-lasting and stable anti-mold effects.
[0004] While there are modified products on the market optimized for single properties, vinyl hot melt adhesives that combine excellent high and low temperature resistance with long-lasting mildew resistance are still relatively rare. In particular, the introduction of low molecular weight tackifying resins often comes at the cost of sacrificing heat resistance and mildew resistance, making multi-performance synergistic modification a significant challenge.
[0005] Therefore, there is an urgent need to develop a vinyl polymer hot melt adhesive material that combines excellent high and low temperature resistance with long-lasting anti-mildew effect to meet the stringent requirements for bonding performance and service life under extreme temperature conditions and humid environments. Summary of the Invention
[0006] The purpose of this invention is to provide a mildew-resistant and high / low temperature resistant ethylene polymer material and its preparation method, so as to solve the problems existing in the prior art.
[0007] To solve the above-mentioned technical problems, the present invention provides the following technical solution: a mildew-resistant and high / low temperature resistant ethylene polymer material, comprising the following components by mass parts: 100 parts of ethylene-propylene copolymer, 15-35 parts of polypropylene, 15-35 parts of maleic anhydride-grafted polyethylene, 15-35 parts of thermoplastic starch, and 10-20 parts of modified copper-manganese oxide composite material; wherein the modified copper-manganese oxide composite material is modified by aminosilane coupling agent, and then grafted and modified by acylchlorinated 4-maleimide benzoic acid as a modifier, and then polymerized with styrene and diallyl dimethyl ammonium chloride on its surface.
[0008] Furthermore, the polypropylene melt index is 25-30 g / 10 min.
[0009] Furthermore, the melt flow rate of the ethylene-propylene copolymer is 0.8-1.0 g / 10 min, and the ethylene weight content is 16-22%.
[0010] Furthermore, the melt index of the maleic anhydride-grafted polyethylene is 2-10 g / 10 min; more preferably 2 g / 10 min.
[0011] Furthermore, the copper-manganese oxide composite material is prepared by heat treatment of copper acetate and manganese acetate.
[0012] Furthermore, the molar ratio of copper acetate to manganese acetate is 1:1-2.
[0013] Furthermore, the heat treatment temperature is 350-380℃, and the heat treatment time is 2-3 hours.
[0014] Furthermore, the aminosilane coupling agent is one of γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, or N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane.
[0015] Furthermore, the preparation method of the mildew-resistant and high / low temperature resistant ethylene polymer material is as follows: after mixing polypropylene and maleic anhydride-grafted polyethylene in equal proportions, thermoplastic starch is added, and after extrusion granulation, it is further blended with ethylene-propylene copolymer and modified copper manganese oxide composite material and extruded granulation to obtain the final product.
[0016] Furthermore, the first extrusion temperature is 160-180℃, and the second extrusion temperature is 160-210℃.
[0017] Compared with the prior art, the beneficial effects achieved by the present invention are: (1) The present invention simultaneously combines maleic anhydride-grafted polyethylene, thermoplastic starch and polypropylene. In the preparation process, maleic anhydride-grafted polyethylene and polypropylene are mixed in equal proportion and co-extruded together with thermoplastic starch. Due to the difference in melt index between maleic anhydride-grafted polyethylene and polypropylene, the two molecular chains have a "sticky slip" phenomenon, and the molecular chains are easy to entangle. Combined with the three-dimensional network structure of thermoplastic starch itself, an interpenetrating network structure is formed to obtain a low temperature resistant and impact-resistant modifier, and synergistically modify copper manganese oxide composite material to improve the high and low temperature resistance and strength of ethylene-propylene copolymer.
[0018] (2) In this invention, copper acetate and manganese acetate are used as precursors to obtain copper manganese oxide composite material through solid-state thermal reaction. Through modification treatment, maleimide-styrene polymer containing quaternary ammonium groups is grafted onto its surface. The introduction of maleimide-styrene polymer improves the compatibility of copper manganese oxide composite material with ethylene-propylene copolymer. At the same time, copper manganese oxide composite material and quaternary ammonium groups have antibacterial properties, which together improve the antifungal effect of ethylene-propylene copolymer. Detailed Implementation
[0019] 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.
[0020] Example 1 A mildew-resistant and high / low temperature resistant ethylene polymer material, by mass parts, comprises the following components: 100 parts of ethylene-propylene copolymer, 15 parts of polypropylene, 15 parts of maleic anhydride-grafted polyethylene, 35 parts of thermoplastic starch, and 20 parts of modified copper-manganese oxide composite material; the polypropylene and maleic anhydride-grafted polyethylene are mixed in equal proportions, then thermoplastic starch is added, extruded and granulated, and then blended with ethylene-propylene copolymer and modified copper-manganese oxide composite material and extruded and granulated again to obtain the final product. The preparation method of the modified copper-manganese oxide composite material is as follows: (1) Mix copper acetate and manganese acetate in a molar ratio of 1:1 and grind for 1 hour. Place the mixture in an alumina crucible and heat it in an air atmosphere at 380°C for 2 hours in a muffle furnace. Grind until the particle size is 15 μm to obtain a copper manganese oxide composite material. (2) The copper manganese oxide composite material was added to an ethanol solution of 10 wt% γ-aminopropyltriethoxysilane, ultrasonically dispersed, kept at 85°C for 3 h, filtered and dried to obtain the pretreated copper manganese oxide composite material; the mass ratio of copper manganese oxide composite material to γ-aminopropyltriethoxysilane was 3:1. (3) Dissolve 4-maleimide benzoic acid in DMF at a ratio of 1g:15mL, add 30% of the mass of 4-maleimide benzoic acid in thionyl chloride, and react at 100℃ for 1h to prepare a mixed solution containing 4-maleimide benzoic acid. (4) The pretreated copper manganese oxide composite material was added to the mixture containing 4-maleimide benzoic acid obtained in step (3), and reacted at 30°C for 8 hours. After the reaction was completed, the mixture was vacuum filtered with filter paper and then vacuum dried at 180°C for 1 hour to obtain the grafted modified copper manganese oxide composite material. The amount of pretreated copper manganese oxide composite material added was 100% of the mass of 4-maleimide benzoic acid. (5) Under a nitrogen atmosphere at room temperature, grafted modified copper manganese oxide composite material, styrene, and diallyl dimethyl ammonium chloride were mixed at a mass ratio of 2.4:1:0.6. Then, tetrahydrofuran (3 times the total mass) and azobisisobutyronitrile (0.001 times the total mass) were added. The mixture was stirred until styrene and diallyl dimethyl ammonium chloride were dissolved. After reacting at 70°C for 24 hours, the temperature was lowered to 0°C. An equal volume of methanol was added to the reaction solution. The mixture was allowed to stand for 1 hour, filtered, and the filter cake was washed three times with methanol. The mixture was then vacuum dried at room temperature for 6 hours.
[0021] Example 2 A mildew-resistant and high / low temperature resistant ethylene polymer material, by mass parts, comprises the following components: 100 parts of ethylene-propylene copolymer, 35 parts of polypropylene, 35 parts of maleic anhydride-grafted polyethylene, 15 parts of thermoplastic starch, and 10 parts of modified copper-manganese oxide composite material; the polypropylene and maleic anhydride-grafted polyethylene are mixed in equal proportions, then thermoplastic starch is added, extruded and granulated, and then blended with ethylene-propylene copolymer and modified copper-manganese oxide composite material and extruded and granulated again to obtain the final product. The preparation method of the modified copper-manganese oxide composite material is as follows: (1) Mix copper acetate and manganese acetate in a molar ratio of 1:2 and grind for 1 hour. Place the mixture in an alumina crucible and heat it in an air atmosphere at 350°C for 3 hours in a muffle furnace. Grind until the particle size is 5 μm to obtain a copper manganese oxide composite material. (2) The copper manganese oxide composite material was added to an ethanol solution of 10 wt% N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, ultrasonically dispersed, kept at 75°C for 5 h, filtered and dried to obtain the pretreated copper manganese oxide composite material; the mass ratio of the copper manganese oxide composite material to N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane was 2.5:1; (3) Dissolve 4-maleimide benzoic acid in DMF at a ratio of 1g:30mL, add 120% of phosphorus oxychloride by mass of 4-maleimide benzoic acid, react at 30℃ for 8h to prepare a mixed solution containing 4-maleimide benzoic acid. (4) Add the pretreated copper manganese oxide composite material to the mixture containing 4-maleimide benzoic acid obtained in step (3), react at 100°C for 1 h, after the reaction is completed, filter it with filter paper under vacuum, and then dry it under vacuum at 100°C for 8 h; the amount of pretreated copper manganese oxide composite material added is 70% of the mass of 4-maleimide benzoic acid.
[0022] (5) Under a nitrogen atmosphere at room temperature, grafted modified copper manganese oxide composite material, styrene, and diallyl dimethyl ammonium chloride were mixed at a mass ratio of 2.4:1:0.6. Then, tetrahydrofuran (3 times the total mass) and azobisisobutyronitrile (0.001 times the total mass) were added. The mixture was stirred until styrene and diallyl dimethyl ammonium chloride were dissolved. After reacting at 70°C for 24 hours, the temperature was lowered to 0°C. An equal volume of methanol was added to the reaction solution. The mixture was allowed to stand for 1 hour, filtered, and the filter cake was washed three times with methanol. The mixture was then vacuum dried at room temperature for 6 hours.
[0023] Example 3 A mildew-resistant and high / low temperature resistant ethylene polymer material, by mass parts, comprises the following components: 100 parts of ethylene-propylene copolymer, 15 parts of polypropylene, 15 parts of maleic anhydride-grafted polyethylene, 35 parts of thermoplastic starch, and 10 parts of modified copper-manganese oxide composite material; the polypropylene and maleic anhydride-grafted polyethylene are mixed in equal proportions, then thermoplastic starch is added, extruded and granulated, and then blended with ethylene-propylene copolymer and modified copper-manganese oxide composite material and extruded and granulated again to obtain the final product. The preparation method of the modified copper-manganese oxide composite material is as follows: (1) Mix copper acetate and manganese acetate in a molar ratio of 1:1 and grind for 1 hour. Place the mixture in an alumina crucible and heat it in an air atmosphere at 380°C for 3 hours in a muffle furnace. Grind until the particle size is 5 μm to obtain a copper manganese oxide composite material. (2) The copper manganese oxide composite material was added to an ethanol solution of 10 wt% γ-aminopropyltriethoxysilane, ultrasonically dispersed, kept at 75°C for 5 h, filtered and dried to obtain the pretreated copper manganese oxide composite material; the mass ratio of copper manganese oxide composite material to γ-aminopropyltriethoxysilane was 2.5:1. (3) Dissolve 4-maleimide benzoic acid in DMF at a ratio of 1g:30mL, add 120% phosphorus pentachloride of 4-maleimide benzoic acid mass, react at 100℃ for 1h to prepare a mixed solution containing 4-maleimide benzoic acid. (4) Add the pretreated copper manganese oxide composite material to the mixture containing 4-maleimide benzoic acid obtained in step (3), react at 30°C for 8 hours, after the reaction is completed, filter it with filter paper under vacuum, and then dry it under vacuum at 100°C for 8 hours; the amount of pretreated copper manganese oxide composite material added is 100% of the mass of 4-maleimide benzoic acid.
[0024] (5) Under a nitrogen atmosphere at room temperature, grafted modified copper manganese oxide composite material, styrene, and diallyl dimethyl ammonium chloride were mixed at a mass ratio of 2.4:1:0.6. Then, tetrahydrofuran (3 times the total mass) and azobisisobutyronitrile (0.001 times the total mass) were added. The mixture was stirred until styrene and diallyl dimethyl ammonium chloride were dissolved. After reacting at 70°C for 24 hours, the temperature was lowered to 0°C. An equal volume of methanol was added to the reaction solution. The mixture was allowed to stand for 1 hour, filtered, and the filter cake was washed three times with methanol. The mixture was then vacuum dried at room temperature for 6 hours.
[0025] Example 4 A mildew-resistant and high / low temperature resistant ethylene polymer material, by mass parts, comprises the following components: 100 parts of ethylene-propylene copolymer, 20 parts of polypropylene, 20 parts of maleic anhydride-grafted polyethylene, 35 parts of thermoplastic starch, and 10 parts of modified copper-manganese oxide composite material; the polypropylene and maleic anhydride-grafted polyethylene are mixed in equal proportions, then thermoplastic starch is added, extruded and granulated, and then blended with ethylene-propylene copolymer and modified copper-manganese oxide composite material and extruded and granulated again to obtain the final product. The preparation method of the modified copper-manganese oxide composite material is as follows: (1) Mix copper acetate and manganese acetate in a molar ratio of 1:2 and grind for 1 hour. Place the mixture in an alumina crucible and heat it in an air atmosphere at 350°C for 2 hours in a muffle furnace. Grind until the particle size is 15 μm to obtain a copper manganese oxide composite material. (2) The copper manganese oxide composite material was added to an ethanol solution of 10 wt% N-β(aminoethyl)-γ-aminopropylmethyldimethoxysilane, ultrasonically dispersed, kept at 85°C for 3 h, filtered and dried to obtain the pretreated copper manganese oxide composite material; the mass ratio of the copper manganese oxide composite material to N-β(aminoethyl)-γ-aminopropylmethyldimethoxysilane was 3:1. (3) Dissolve 4-maleimide benzoic acid in DMF at a ratio of 1g:15mL, add 30% phosphorus oxychloride of the mass of 4-maleimide benzoic acid, react at 30℃ for 8h to prepare a mixed solution containing 4-maleimide benzoic acid. (4) Add the pretreated copper manganese oxide composite material to the mixture containing 4-maleimide benzoic acid obtained in step (3), react at 100°C for 1 h, after the reaction is completed, filter it with filter paper under vacuum, and then dry it under vacuum at 180°C for 1 h; the amount of pretreated copper manganese oxide composite material added is 70% of the mass of 4-maleimide benzoic acid.
[0026] (5) Under a nitrogen atmosphere at room temperature, grafted modified copper manganese oxide composite material, styrene, and diallyl dimethyl ammonium chloride were mixed at a mass ratio of 2.4:1:0.6. Then, tetrahydrofuran (3 times the total mass) and azobisisobutyronitrile (0.001 times the total mass) were added. The mixture was stirred until styrene and diallyl dimethyl ammonium chloride were dissolved. After reacting at 70°C for 24 hours, the temperature was lowered to 0°C. An equal volume of methanol was added to the reaction solution. The mixture was allowed to stand for 1 hour, filtered, and the filter cake was washed three times with methanol. The mixture was then vacuum dried at room temperature for 6 hours.
[0027] Example 5 A mildew-resistant and high / low temperature resistant ethylene polymer material, by mass parts, comprises the following components: 100 parts of ethylene-propylene copolymer, 20 parts of polypropylene, 20 parts of maleic anhydride-grafted polyethylene, 20 parts of thermoplastic starch, and 15 parts of modified copper-manganese oxide composite material; the polypropylene and maleic anhydride-grafted polyethylene are mixed in equal proportions, then thermoplastic starch is added, extruded and granulated, and then blended with ethylene-propylene copolymer and modified copper-manganese oxide composite material and extruded and granulated again to obtain the final product. The preparation method of the modified copper-manganese oxide composite material is as follows: (1) Mix copper acetate and manganese acetate in a molar ratio of 1:1 and grind for 1 hour. Place the mixture in an alumina crucible and heat-treat it in an air atmosphere at 380°C for 2 hours in a muffle furnace. Grind until the particle size is 5 μm to obtain a copper manganese oxide composite material. (2) The copper manganese oxide composite material was added to an ethanol solution of 10 wt% γ-aminopropyltriethoxysilane, ultrasonically dispersed, kept at 75°C for 5 h, filtered and dried to obtain the pretreated copper manganese oxide composite material; the mass ratio of copper manganese oxide composite material to γ-aminopropyltriethoxysilane was 2.5:1. (3) Dissolve 4-maleimide benzoic acid in DMF at a ratio of 1g:15mL, add 30% phosphorus oxychloride of the mass of 4-maleimide benzoic acid, and react at 100℃ for 8h to prepare a mixed solution containing 4-maleimide benzoic acid. (4) Add the pretreated copper manganese oxide composite material to the mixture containing 4-maleimide benzoic acid obtained in step (3), react at 30°C for 1 h, after the reaction is completed, filter it with filter paper under vacuum, and then dry it under vacuum at 180°C for 8 h; the amount of pretreated copper manganese oxide composite material added is 100% of the mass of 4-maleimide benzoic acid.
[0028] (5) Under a nitrogen atmosphere at room temperature, grafted modified copper manganese oxide composite material, styrene, and diallyl dimethyl ammonium chloride were mixed at a mass ratio of 2.4:1:0.6. Then, tetrahydrofuran (3 times the total mass) and azobisisobutyronitrile (0.001 times the total mass) were added. The mixture was stirred until styrene and diallyl dimethyl ammonium chloride were dissolved. After reacting at 70°C for 24 hours, the temperature was lowered to 0°C. An equal volume of methanol was added to the reaction solution. The mixture was allowed to stand for 1 hour, filtered, and the filter cake was washed three times with methanol. The mixture was then vacuum dried at room temperature for 6 hours.
[0029] Example 6 A mildew-resistant and high / low temperature resistant ethylene polymer material, by mass parts, comprises the following components: 100 parts of ethylene-propylene copolymer, 25 parts of polypropylene, 25 parts of maleic anhydride-grafted polyethylene, 35 parts of thermoplastic starch, and 20 parts of modified copper-manganese oxide composite material; the polypropylene and maleic anhydride-grafted polyethylene are mixed in equal proportions, then thermoplastic starch is added, extruded and granulated, and then blended with ethylene-propylene copolymer and modified copper-manganese oxide composite material and extruded and granulated again to obtain the final product. The preparation method of the modified copper-manganese oxide composite material is as follows: (1) Mix copper acetate and manganese acetate in a molar ratio of 1:2 and grind for 1 hour. Place the mixture in an alumina crucible and heat it in an air atmosphere at 350°C for 2 hours in a muffle furnace. Grind until the particle size is 15 μm to obtain a copper manganese oxide composite material. (2) The copper manganese oxide composite material was added to an ethanol solution of 10 wt% N-β(aminoethyl)-γ-aminopropylmethyldimethoxysilane, ultrasonically dispersed, kept at 85°C for 3 h, filtered and dried to obtain the pretreated copper manganese oxide composite material; the mass ratio of the copper manganese oxide composite material to N-β(aminoethyl)-γ-aminopropylmethyldimethoxysilane was 3:1. (3) Dissolve 4-maleimide benzoic acid in DMF at a ratio of 1g:30mL, add 120% of the mass of 4-maleimide benzoic acid in thionyl chloride, react at 30℃ for 1h to prepare a mixed solution containing 4-maleimide benzoic acid. (4) Add the pretreated copper manganese oxide composite material to the mixture containing 4-maleimide benzoic acid obtained in step (3), react at 100°C for 8 hours, after the reaction is completed, filter it with filter paper under vacuum, and then dry it under vacuum at 100°C for 1 hour; the amount of pretreated copper manganese oxide composite material added is 70% of the mass of 4-maleimide benzoic acid.
[0030] (5) Under a nitrogen atmosphere at room temperature, grafted modified copper manganese oxide composite material, styrene, and diallyl dimethyl ammonium chloride were mixed at a mass ratio of 2.4:1:0.6. Then, tetrahydrofuran (3 times the total mass) and azobisisobutyronitrile (0.001 times the total mass) were added. The mixture was stirred until styrene and diallyl dimethyl ammonium chloride were dissolved. After reacting at 70°C for 24 hours, the temperature was lowered to 0°C. An equal volume of methanol was added to the reaction solution. The mixture was allowed to stand for 1 hour, filtered, and the filter cake was washed three times with methanol. The mixture was then vacuum dried at room temperature for 6 hours.
[0031] Comparative Example 1 The difference between Comparative Example 1 and Example 4 is that thermoplastic starch is not added, while the rest of the preparation method is the same as in Example 4.
[0032] Comparative Example 2 The difference between Comparative Example 2 and Example 4 is that polypropylene is not added, while the rest of the preparation method is the same as in Example 4.
[0033] Comparative Example 3 The difference between Comparative Example 3 and Example 4 is that maleic anhydride-grafted polyethylene is not added; the rest of the preparation methods are the same as in Example 4.
[0034] Comparative Example 4 The difference between Comparative Example 4 and Example 4 is that maleic anhydride-grafted polyethylene is not added; the rest of the preparation methods are the same as in Example 4.
[0035] Comparative Example 5 The difference between Comparative Example 5 and Example 4 is that Comparative Example 5 was prepared by blending and extruding polypropylene, maleic anhydride-grafted polyethylene, thermoplastic starch, ethylene-propylene copolymer, and modified copper manganese oxide composite material, while the rest of the preparation methods were the same as in Example 4.
[0036] Comparative Example 6 The difference between Comparative Example 6 and Example 4 is that the copper manganese oxide composite material was only modified by a coupling agent, while the rest of the preparation method was the same as in Example 4.
[0037] Comparative Example 7 The difference between Comparative Example 7 and Example 4 is that diallyl dimethyl ammonium chloride is not added when preparing the modified copper manganese oxide composite material; the rest of the preparation methods are the same as in Example 4.
[0038] Comparative Example 8 The difference between Comparative Example 8 and Example 4 is that styrene is not added when preparing the modified copper manganese oxide composite material, while the rest of the preparation method is the same as in Example 4.
[0039] Comparative Example 9 The difference between Comparative Example 9 and Example 4 is that styrene and diallyl dimethyl ammonium chloride polymerization is not carried out when preparing the modified copper manganese oxide composite material; the rest of the preparation methods are the same as in Example 4.
[0040] Comparative Example 10 The difference between Comparative Example 10 and Example 4 is that no modified copper manganese oxide composite material is added; the rest of the preparation methods are the same as in Example 4.
[0041] Comparative Example 11 The difference between Comparative Example 11 and Example 4 is that copper oxide is used instead of copper manganese oxide composite material, while the rest of the preparation method is the same as in Example 4.
[0042] Comparative Example 12 The difference between Comparative Example 12 and Example 4 is that manganese oxide is used instead of copper manganese oxide composite material, while the rest of the preparation method is the same as in Example 4.
[0043] Example of effect Table 1 below shows the performance analysis results of the ethylene polymer materials of Examples 1 to 6 and Comparative Examples 1 to 12 of the present invention.
[0044] Table 1 It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No markings in the claims should be construed as limiting the scope of the claims.
Claims
1. A mildew-resistant and high / low temperature resistant ethylene polymer material, comprising, by weight parts: 100 parts ethylene-propylene copolymer, 15-35 parts polypropylene, 15-35 parts maleic anhydride-grafted polyethylene, 15-35 parts thermoplastic starch, and 10-20 parts modified copper-manganese oxide composite material; characterized in that, The modified copper manganese oxide composite material is made by modifying the copper manganese oxide composite material with an aminosilane coupling agent, then using acyl-chlorinated 4-maleimide benzoic acid as a modifier to graft the copper manganese oxide composite material, and then polymerizing it with styrene and diallyl dimethyl ammonium chloride on its surface.
2. The mildew-resistant and high / low temperature resistant ethylene polymer material according to claim 1, characterized in that, The polypropylene melt index is 25-30 g / 10 min.
3. The mildew-resistant and high / low temperature resistant ethylene polymer material according to claim 1, characterized in that, The ethylene-propylene copolymer has a melt flow rate of 0.8-1.0 g / 10 min and an ethylene weight content of 16-22%.
4. The mildew-resistant and high / low temperature resistant ethylene polymer material according to claim 1, characterized in that, The melt index of the maleic anhydride-grafted polyethylene is 2-10 g / 10 min; more preferably 2 g / 10 min.
5. The mildew-resistant and high / low temperature resistant ethylene polymer material according to claim 1, characterized in that, The copper-manganese oxide composite material is prepared by heat treatment of copper acetate and manganese acetate.
6. The mildew-resistant and high / low temperature resistant ethylene polymer material according to claim 5, characterized in that, The molar ratio of copper acetate to manganese acetate is 1:1-2.
7. The mildew-resistant and high / low temperature resistant ethylene polymer material according to claim 5, characterized in that, The heat treatment temperature is 350-380℃, and the heat treatment time is 2-3 hours.
8. The mildew-resistant and high / low temperature resistant ethylene polymer material according to claim 1, characterized in that, The aminosilane coupling agent is one of γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, or N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane.
9. The mildew-resistant and high / low temperature resistant ethylene polymer material according to claim 1, characterized in that, The method for preparing the anti-mildew and high / low temperature resistant ethylene polymer material is as follows: Polypropylene and maleic anhydride-grafted polyethylene are mixed in equal proportions, thermoplastic starch is added, and after extrusion granulation, it is further blended with ethylene-propylene copolymer and modified copper-manganese oxide composite material and extruded granulation to obtain the final product.
10. The mildew-resistant and high / low temperature resistant ethylene polymer material according to claim 9, characterized in that, The first extrusion temperature is 160-180℃, and the second extrusion temperature is 160-210℃.