Thermoplastic low-density high-performance low-smoke halogen-free high-flame-retardant polyolefin material as well as preparation method and application thereof
By preparing a thermoplastic low-density, high-performance, low-smoke, halogen-free, and highly flame-retardant polyolefin material containing ethylene-vinyl acetate copolymer, flame retardant, and additives, the problems of low density, high performance, and high flame retardancy in cable materials have been solved, the overall performance and processability of the material have been improved, and illegal cost-cutting practices have been avoided.
Patent Information
- Application Number
- CN202411511962.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Priority Date
- 2024-09-02
- Filing Date
- 2024-10-28
- Publication Date
- 2025-01-10
AI Technical Summary
Existing wire and cable materials cannot simultaneously meet the requirements of low density, high performance, low smoke, and high flame retardancy, resulting in poor quality of finished cables. Furthermore, the illegal reduction of costs under cost pressure is rampant.
Thermoplastic low-density, high-performance, low-smoke, halogen-free, and highly flame-retardant polyolefin material is prepared by using ethylene-vinyl acetate copolymer, chemically produced magnesium hydroxide, aluminum hydroxide, and phosphorus-nitrogen flame retardants, combined with compatibilizers and additives, through a process of intensive mixing, twin-screw extrusion, and granulation.
This has resulted in low-density, high-performance, low-smoke, halogen-free, and highly flame-retardant cable materials, improving the mechanical and physical properties and processability of the materials, reducing cost pressures, and avoiding the phenomenon of cutting corners.
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Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of wire and cable materials, and in particular to a thermoplastic low-density, high-performance, low-smoke, halogen-free and highly flame-retardant polyolefin material, and a preparation method and application thereof. Background Art
[0002] With the continuous development of the plastics industry, the power industry and the construction industry, as well as people's close attention to the safety of electricity, the application of wire and cable materials is becoming more and more extensive. The research and development of new wire and cable materials is the top priority of the current materials industry.
[0003] In the current cable production, the labor cost and material price (especially copper and other core materials) are getting higher and higher, but the price of finished cables is getting lower and lower. Under the huge cost pressure, some people cut corners and use inferior products to reduce costs. It is precisely because of this pressure that various products are defective after the cable is completed, which reduces the quality of the product.
[0004] In order to reasonably reduce product costs, the existing formula must be improved without reducing product performance. Summary of the invention
[0005] The purpose of the present invention is to provide a thermoplastic low-density, high-performance, low-smoke, halogen-free and highly flame-retardant polyolefin material and its preparation method and application, which solves the problem that wire and cable materials in the prior art cannot simultaneously meet the requirements of low density, high performance, low smoke, halogen-free and highly flame-retardant.
[0006] In order to achieve the above object, the technical solution adopted by the present invention is:
[0007] The first aspect of the present invention provides a thermoplastic low-density, high-performance, low-smoke, halogen-free, and highly flame-retardant polyolefin material, comprising the following components in parts by weight:
[0008] 20-30 parts of ethylene-vinyl acetate copolymer;
[0009]
[0010] The vinyl acetate content of the ethylene-vinyl acetate copolymer is 16% to 20%, the melt index of the ethylene-vinyl acetate copolymer is 3 to 6 g / 10 min; and the melt index of the high-density polyethylene is 6 to 8 g / 10 min.
[0011] Furthermore, the grafted compatibilizer is a compatibilizer grafted with MLLDPE and maleic anhydride.
[0012] Furthermore, the flame retardant is a mixture of chemically produced magnesium hydroxide, aluminum hydroxide and a phosphorus-nitrogen flame retardant, wherein the mass ratio of the chemically produced magnesium hydroxide, the aluminum hydroxide and the phosphorus-nitrogen flame retardant is (15-18):(25-30):(2-4).
[0013] Furthermore, the auxiliary agent includes at least one of a lubricant, an antioxidant, an antioxidant and a coupling agent.
[0014] Furthermore, the lubricant comprises an internal lubricant and an external lubricant, the internal lubricant is PE wax, the external lubricant is silicone masterbatch, and the lubricant is preferably a combination of 0.3-0.5 parts by weight of PE wax and 0.8-1.2 parts by weight of silicone masterbatch.
[0015] Furthermore, the antioxidant is at least one selected from the group consisting of antioxidant MBZ and antioxidant 1035, and the antioxidant is preferably a combination of 0.3 to 0.5 parts by weight of antioxidant MBZ and 0.3 to 0.5 parts by weight of antioxidant 1035.
[0016] Furthermore, the antioxidant is antioxidant 1010, and the antioxidant is preferably antioxidant 1010 in an amount of 0.3 to 0.5 parts by mass.
[0017] Furthermore, the coupling agent is a mixture of one or more selected from coupling agent 172, coupling agent 171 and coupling agents 11-100, and the coupling agent is preferably 0.3 to 0.5 parts by mass of coupling agent 172.
[0018] The second aspect of the present invention provides a method for preparing a thermoplastic low-density, high-performance, low-smoke, halogen-free and highly flame-retardant polyolefin material, comprising the following steps:
[0019] S1: Put the above raw materials into a mixer according to the proportion and mix them to obtain a molten material block. The mixing temperature is 160-165°C;
[0020] S2: After the molten material block is subjected to double-stage cone feeding, it is sheared and discharged in a twin-screw extruder at a shear temperature of 120-145° C.;
[0021] S3: extruding the sheared material in step S2 into granules through a single screw, with the granulation temperature being 135-155° C.;
[0022] S4: air-cooling and pelletizing the granulated material in step S3, followed by collecting, cooling and packaging, to obtain the thermoplastic low-density, high-performance, low-smoke, halogen-free and highly flame-retardant polyolefin material.
[0023] The third aspect of the present invention provides an application of a thermoplastic low-density, high-performance, low-smoke, halogen-free, and highly flame-retardant polyolefin material, wherein the thermoplastic low-density, high-performance, low-smoke, halogen-free, and highly flame-retardant polyolefin material can be applied to cables and wires.
[0024] Due to the application of the above technical solution, the present invention has the following advantages compared with the prior art:
[0025] The present invention provides a thermoplastic low-density, high-performance, low-smoke, halogen-free, and highly flame-retardant polyolefin material, comprising the following components by mass: 20 to 30 parts of ethylene-vinyl acetate copolymer; 10 to 15 parts of high-density polyethylene; 5 to 10 parts of polyethylene elastomer; 5 to 10 parts of grafting compatibilizer; 43 to 52 parts of flame retardant; 3 to 5 parts of auxiliary agent; wherein the content of vinyl acetate in the ethylene-vinyl acetate copolymer is 16% to 20%, the melt index of the ethylene-vinyl acetate copolymer is 3 to 6 g / 10 min; and the melt index of the high-density polyethylene is 6 to 8 g / 10 min. This type of ethylene-vinyl acetate copolymer has strong processability and good radiation cross-linking performance; the high-density polyethylene has good fluidity; the use of polyolefin elastomer greatly improves the mechanical and physical properties of the material, and combined with the use of flame retardants and auxiliary agents, the prepared thermoplastic low-density, high-performance, low-smoke, halogen-free, and highly flame-retardant polyolefin material has excellent performance. DETAILED DESCRIPTION
[0026] The following examples are provided for a better understanding of the present invention, but are not intended to limit the best mode of implementation, nor to limit the content and protection scope of the present invention. Any product identical or similar to the present invention obtained by anyone under the inspiration of the present invention or by combining the features of the present invention with other prior arts shall fall within the protection scope of the present invention.
[0027] The thermoplastic low-density, high-performance, low-smoke, halogen-free and highly flame-retardant polyolefin material of the present invention comprises the following components in parts by weight: 20 to 30 parts of ethylene-vinyl acetate copolymer; 10 to 15 parts of high-density polyethylene; 5 to 10 parts of polyethylene elastomer; 5 to 10 parts of grafting compatibilizer; 43 to 52 parts of flame retardant; and 3 to 5 parts of auxiliary agent.
[0028] The VA content of the ethylene-vinyl acetate copolymer selected in the embodiment of the present invention is 16% to 20%, and the melt index is 3 to 6g / 10min, such as the brand 18j3 of Sinopec, 5110M of Sulbang, 420vs of LG, etc. This type of EVA has good mechanical and physical properties and good fluidity, and has strong processability among wire and cable materials.
[0029] The high-density polyethylene used in the present invention has a melt index of 6 to 8 g / 10 min (190°C*2.16 kg), such as 8008 from Yangzi Petrochemical and HMA025 from ExxonMobil. Such high-density polyethylene has excellent mechanical and physical properties and is used to increase the processing performance of the material.
[0030] The polyethylene elastomer used in the present invention is a 4C high tensile strength material with a melt index of 0.5-1.5 g / 10 min, such as DF810 from Mitsui and 7270 from DOW. Such materials have good mechanical and physical properties and moderate fluidity.
[0031] The grafted compatibilizer in the present invention is a compatibilizer grafted with MLLDPE and maleic anhydride. Such a material has excellent compatibility and mechanical and physical properties, can increase the tensile strength and filling dispersibility of the material, and also has good extrusion processing performance.
[0032] As for the flame retardant, the flame retardant selected in the embodiment of the present invention is a combination of chemical magnesium hydroxide, aluminum hydroxide and phosphorus nitrogen flame retardant. Among them, the chemical magnesium hydroxide uses imported materials, such as S-6 from Japan's Kamishima, H5 from Albemarle, etc. Such materials have good flame retardant properties as filling flame retardants, and have good dispersion properties in the material, which is beneficial to improving the extrusion processing performance of the material. Aluminum hydroxide uses imported aluminum hydroxide, such as Albemarle 104 aluminum, etc. Such materials have environmental protection properties and good flame retardant properties in polyolefin materials, and the use of compound magnesium hydroxide can increase the flame retardant effect of the material. Phosphorus nitrogen flame retardant uses MCA (melamine), which can improve the self-extinguishing properties of polyolefin materials and increase the flame retardant properties of polyolefin materials when used in polyolefin materials.
[0033] In addition to the above-mentioned preparations, a certain amount of auxiliary agents are added in the present invention for material compounding. Specifically, the auxiliary agents include at least one of lubricants, antioxidants, antioxidants and coupling agents.
[0034] In the embodiment of the present invention, an internal lubricant and an external lubricant are compounded and used together. PE wax (such as Honeywell's AC-6A) is selected as the internal lubricant, and silicone masterbatch is selected as the external lubricant. This type of mixed lubricant has a good surface lubrication effect, which helps to increase the surface finish of the material and avoid over-temperature decomposition of the material during processing. The antioxidant is selected from at least one of the antioxidant MBZ and the antioxidant 1035. The role of the antioxidant MBZ and the antioxidant 1035 is to improve the stability of the material under high temperature conditions and reduce the oxidation effect of the material under high temperature conditions. The antioxidant is selected from the antioxidant 1010 to reduce the oxidation effect of the material under high temperature conditions. The coupling agent is selected from the coupling agent 172, the coupling agent 171 and the coupling agent 11-100, etc., because the aforementioned coupling agent has a good surface treatment effect when the material is filled, it helps to promote the dispersion of the flame retardant in the material, increase the effective flame retardant effect of the flame retardant in the material, and can also increase the water resistance of the material.
[0035] The present invention also provides a method for preparing the thermoplastic low-density, high-performance, low-smoke, halogen-free and highly flame-retardant polyolefin material as described above, comprising the following steps:
[0036] S1: Put the raw materials into a mixer according to the proportion and mix them to obtain a molten material block. The mixing temperature is 160-165°C;
[0037] S2: After the molten material block is subjected to double-stage cone feeding, it is sheared and discharged in a twin-screw extruder at a shear temperature of 120-145° C.;
[0038] S3: extruding the sheared material in step S2 into granules through a single screw, with the granulation temperature being 135-155° C.;
[0039] S4: air-cooling and pelletizing the granulated material in step S3, followed by collecting, cooling and packaging, to obtain the thermoplastic low-density, high-performance, low-smoke, halogen-free and highly flame-retardant polyolefin material.
[0040] Certain embodiments are selected below to further describe the present invention.
[0041] Examples 1 to 3 and Comparative Examples 1 to 11 respectively provide a thermoplastic low-density, high-performance, low-smoke, halogen-free and highly flame-retardant polyolefin material. The amounts of components in each example and comparative example are shown in Table 1.
[0042] Note: In Examples 1 to 3, ethylene-vinyl acetate copolymer is 18j3 from Sinopec, high-density polyethylene is 8008 from Yangzi Petrochemical, polyethylene elastomer is DF810 from Mitsui, compatibilizer is MLLDPE3518 and maleic anhydride grafted compatibilizer, the brand of which is ExxonMobil's 3518 grafted compatibilizer; chemical magnesium hydroxide is S-6 from Japan's Kamishima, aluminum hydroxide is 104 aluminum from Albemarle, and phosphorus-nitrogen flame retardant is MCA from Tianyi.
[0043] The lubricant used is MaiTai's silicone masterbatch with 50% PE carrier and Honeywell's PE wax AC-6A (wherein the mass ratio of silicone masterbatch to PE wax AC-6A is 8-12:3-5); the antioxidant used is Shanghai Dirui's antioxidant MBZ, Shanghai Dirui's antioxidant 1035 and Jiyi's antioxidant 1010 (wherein the mass ratio of antioxidant MBZ, antioxidant 1035 and antioxidant 1010 is 1:1:1); the coupling agent used is Shanghai Chunguang's FA-9003).
[0044] Table 1 Composition of thermoplastic low-density, high-performance, low-smoke, halogen-free, highly flame-retardant polyolefin materials in Examples 1 to 3 and Comparative Examples 1 to 11
[0045]
[0046]
[0047] Note: The vinyl acetate content of the ethylene-vinyl acetate copolymer used in Comparative Example 1 is 28%, the melt index is 3.5 g / min, and its brand is 7470M of Formosa Plastics; the vinyl acetate content of the ethylene-vinyl acetate copolymer used in Comparative Example 2 is 14%, the melt index is 3.5 g / min, and its brand is 560VA of Mitsui; the high-density polyethylene used in Comparative Example 3 has a melt index of 3.1 g / min, and its brand is 3300J of Maoyanshan Petrochemical; the high-density polyethylene used in Comparative Example 4 has a melt index of 10 g / min, and its brand is 2480 of Qilu Petrochemical.
[0048] The polyethylene elastomer used in Comparative Example 5 has a tensile strength of 8C and a melt index of 1.5, and its brand is DOW 8440; the polyethylene elastomer used in Comparative Example 6 has a tensile strength of 4C and a melt index of 3.5 g / min, and its brand is Mitsui's DF740; the grafting compatibilizer used in Comparative Example 7 is LDPE grafting, and its brand is Yanshan Petrochemical 7042; the grafting compatibilizer used in Comparative Example 8 is POE grafting, and its brand is DOW 8150.
[0049] In Comparative Example 9, physical magnesium is used; in Comparative Example 10, domestically produced chemical magnesium hydroxide is used, with a brand of Kemet PM5SL; and in Comparative Example 11, domestically produced aluminum is used, with a brand of Zhongchao 01DG.
[0050] The performance of the thermoplastic low-density, high-performance, low-smoke, halogen-free and highly flame-retardant polyolefin materials in Examples 1 to 3 and Comparative Examples 1 to 11 was tested, and the test results are shown in Table 2.
[0051] Table 2 Performance test table of thermoplastic low-density high-performance low-smoke halogen-free high-flame-retardant polyolefin materials in Examples 1 to 3 and Comparative Examples 1 to 11
[0052]
[0053]
[0054]
[0055]
[0056] Note: Specific gravity ≤ 1.35g*cm 3 , oxygen index ≥ 28; when testing tensile strength, GB / T32129, test speed 250mm / s, required value ≥ 12.5Mpa; when testing elongation at break, GB / T32129, test speed 250mm / s, required value ≥ 300%; when testing flame retardant properties, insulation 5*35mm 2 , wrapped with two layers of glass fiber tape, the sheath wall thickness is 2.5mm, and the flame retardant requirements must pass: GB / T19666.6.2ZC bundle combustion, and the combustion performance must pass GB / T19666,6.3,6.4,6.5.
[0057] When testing aging performance, natural ventilation aging box 110℃*240h, GB / T32129, requires strength retention rate ≥75%, elongation retention rate ≥75%. When testing temperature resistance, 110℃*6h, pressure coefficient K=0.7, requires indentation <50%. Thermal shock: 3mm sheet, 130℃*1h*2kg hanging weight, requires winding test without cracking.
[0058] When testing high temperature mass loss, 100℃*168h, the weight loss is required to be less than 0.5%. When testing water absorption, 85℃*336h, the square test plate size is 8cm long*8cm wide*1mm thick, and the water absorption weight is required to be less than 5g. When testing water immersion, 0℃*168h, the mechanical and physical properties change rate is required to be ≥30%.
[0059] From the data changes in Table 2, it can be concluded that the appropriate material ratios in Examples 1 to 3 meet the test performance of the materials, and the performance of a polyolefin material provided in Example 2 is the best.
[0060] Comparative Examples 1 to 8: The influence of ethylene-vinyl acetate copolymer on the material lies in the mechanical and physical properties; high-density polyethylene affects the mechanical and physical properties and temperature resistance, as well as high temperature pressure resistance of the material; polyethylene elastomer has a greater influence on the aging properties of the material; the grafting compatibilizer mainly affects the mechanical properties and aging properties of the material.
[0061] Comparative Examples 9 to 11: In view of the influence of flame retardant materials, magnesium hydroxide must be prepared by chemical method, and quantitative addition can ensure the flame retardant properties and mechanical and physical properties of the material; replacing the basic properties of the flame retardant has a greater impact on the material.
[0062] In summary, in the present invention, by selecting ethylene-vinyl acetate copolymer with a specific VA content, combining high-density polyethylene material and polyethylene elastomer, adding a certain amount of flame retardant and additives with the support of MLLDPE and maleic anhydride grafted compatibilizer, a thermoplastic low-density, high-performance, low-smoke, halogen-free and highly flame-retardant polyolefin material is prepared, which has excellent anti-aging and oxidation properties and mechanical and physical properties.
[0063] The above embodiments are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with this technology to understand the contents of the present invention and implement them accordingly. They cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.
Claims
1. A thermoplastic low-density, high-performance, low-smoke, halogen-free, highly flame-retardant polyolefin material, characterized in that: The composition includes the following components in parts by weight: 20-30 parts of ethylene-vinyl acetate copolymer; High-density polyethylene 10-15 parts; Polyethylene elastomer 5-10 parts; 5-10 parts of grafting compatibilizer; 43~52 parts of flame retardant; 3~5 parts of additives; The vinyl acetate content of the ethylene-vinyl acetate copolymer is 16% to 20%, the melt index of the ethylene-vinyl acetate copolymer is 3 to 6 g / 10 min; and the melt index of the high-density polyethylene is 6 to 8 g / 10 min.
2. A thermoplastic low-density, high-performance, low-smoke, halogen-free, highly flame-retardant polyolefin material according to claim 1, characterized in that: The grafted compatibilizer is a compatibilizer grafted with MLLDPE and maleic anhydride.
3. The thermoplastic low-density, high-performance, low-smoke, halogen-free, and highly flame-retardant polyolefin material according to claim 1, characterized in that: The flame retardant is a mixture of chemically produced magnesium hydroxide, aluminum hydroxide and a phosphorus-nitrogen flame retardant, wherein the mass ratio of the chemically produced magnesium hydroxide, the aluminum hydroxide and the phosphorus-nitrogen flame retardant is (15-18): (25-30): (2-4).
4. The thermoplastic low-density, high-performance, low-smoke, halogen-free, and highly flame-retardant polyolefin material according to claim 1, characterized in that: The auxiliary agent includes at least one of a lubricant, an antioxidant, an antioxidant and a coupling agent.
5. The thermoplastic low-density, high-performance, low-smoke, halogen-free, and highly flame-retardant polyolefin material according to claim 4, characterized in that: The lubricant comprises an internal lubricant and an external lubricant, the internal lubricant is PE wax, the external lubricant is silicone masterbatch, and the lubricant is preferably a combination of 0.3-0.5 parts by weight of PE wax and 0.8-1.2 parts by weight of silicone masterbatch.
6. The thermoplastic low-density, high-performance, low-smoke, halogen-free, and highly flame-retardant polyolefin material according to claim 4, characterized in that: The antioxidant is at least one selected from the group consisting of antioxidant MBZ and antioxidant 1035. The antioxidant is preferably a combination of 0.3-0.5 parts by weight of antioxidant MBZ and 0.3-0.5 parts by weight of antioxidant 1035.
7. The thermoplastic low-density, high-performance, low-smoke, halogen-free, and highly flame-retardant polyolefin material according to claim 4, characterized in that: The antioxidant is antioxidant 1010, and the antioxidant is preferably antioxidant 1010 in an amount of 0.3 to 0.5 parts by weight.
8. The thermoplastic low-density, high-performance, low-smoke, halogen-free, and highly flame-retardant polyolefin material according to claim 4, characterized in that: The coupling agent is a mixture of one or more selected from coupling agent 172, coupling agent 171 and coupling agents 11-100, and the coupling agent is preferably 0.3-0.5 parts by weight of coupling agent 172.
9. A method for preparing a thermoplastic low-density, high-performance, low-smoke, halogen-free, highly flame-retardant polyolefin material as claimed in any one of claims 1 to 8, characterized in that: The following steps are involved: S1: Put the raw materials in claims 1-8 into an internal mixer in proportion and mix them to obtain a molten material block. The mixing temperature is 160-165° C.; S2: After the molten material block is subjected to double-stage cone feeding, it is sheared and discharged in a twin-screw extruder at a shear temperature of 120-145° C.; S3: extruding the sheared material in step S2 into granules through a single screw extruder at a granulation temperature of 135-155° C.; S4: air-cooling and pelletizing the granulated material in step S3, followed by collecting, cooling and packaging, to obtain the thermoplastic low-density, high-performance, low-smoke, halogen-free and highly flame-retardant polyolefin material.
10. Use of the thermoplastic low-density, high-performance, low-smoke, halogen-free and highly flame-retardant polyolefin material according to any one of claims 1 to 8 in cables and wires.