CN110862601A - High-oil-resistance long-service-life irradiation crosslinking halogen-free low-smoke flame-retardant elastomer cable material for locomotive cable and preparation method thereof - Google Patents
High-oil-resistance long-service-life irradiation crosslinking halogen-free low-smoke flame-retardant elastomer cable material for locomotive cable and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-oil-resistance long-service-life irradiation crosslinking halogen-free low-smoke flame-retardant elastomer cable material for locomotive cables and a preparation method thereof, wherein the cable material comprises the following raw material components of 30-60 parts of ethylene-vinyl acetate copolymer, 10-30 parts of ethylene-butyl acrylate, 15-30 parts of polyethylene, 5-10 parts of ethylene propylene terpolymer, 5-15 parts of grafting material, 140-170 parts of inorganic flame retardant, 5-10 parts of nano montmorillonite, 1-3 parts of lubricant, 3-8 parts of antioxidant, 1-3 parts of vinyl tris (β -methoxyethoxy) silane and 1-3 parts of triallyl isocyanurate.
Description
Technical Field
The invention relates to a high-oil-resistance long-service-life irradiation crosslinking halogen-free low-smoke flame-retardant elastomer cable material for locomotive cables and a preparation method thereof, belonging to the field of cables.
Background
With the acceleration of the pace of track traffic construction in China and the increase of mileage of railway operation, the wire and cable used by matching track traffic vehicles is also developed and widely applied. At present, the domestic rail transit cable not only needs to meet ROHS and REACH environmental protection regulations of European Union, but also meets the cable standard requirements of TJ/CL 254-. Because the locomotive cable is mainly used in places with relatively dense personnel, such as subway vehicles, locomotive vehicles and the like, the requirements on the flame retardance and the light transmittance of the cable are higher in consideration of the problems of dredging of the personnel and casualties caused by suffocation of toxic gas and smoke under the condition of fire. Under the influence of the use environment, the locomotive cable is required to have excellent mineral oil resistance, fuel oil resistance, low temperature resistance, wear resistance and good electrical performance, and the service life of the cable is correspondingly regulated (the service life is not less than 30 years under the environment of 90 ℃). In addition, there is a certain requirement for flexibility of the material in view of convenience of the cable during the laying process.
In published Chinese patent documents, there are also reports on radiation-crosslinked flame-retardant cable materials for locomotive cables, but none of the reports on the polyolefin materials have improved the service life of the materials, and the reports on the polyolefin materials which have oil resistance, scratch resistance, low temperature resistance, high flame retardance, low smoke and flexibility are few. As CN 105061872A: an irradiation crosslinking type low-smoke halogen-free flame-retardant locomotive oil-resistant cable material and a preparation method thereof, only EVA and acrylic acid grafted EVA are adopted as base materials, the mechanical properties of the cable material are low in tensile strength, low-temperature performance and poor in scratch and abrasion resistance, and meanwhile, the melting temperature of the base materials is low, so that the product is high in viscosity during processing, the processing plasticizing time is limited, the die casting phenomenon is easy to occur during extrusion processing, and the production efficiency and the extrusion appearance are influenced; as CN 105504480B: an oil-resistant irradiation crosslinking low-smoke halogen-free flame-retardant polyolefin material for locomotive cables is prepared by compounding a large amount of (25-40%) VA-containing EVA with a small amount of MLLDPE, and because the VA content is low and the high-melting-point resin is few, the material cannot play a fundamental role in high-temperature long-term mineral oil and fuel oil resistance tests, gradually expands, melts and decays, and meanwhile, the low-temperature resistance and the extrusion processability are poor.
In conclusion, the irradiation crosslinking flame-retardant cable material for the locomotive cable in the prior art has no improvement on the service life, and simultaneously has the defects of mineral oil resistance, fuel oil resistance, low temperature resistance, scratch and abrasion resistance, flame retardance, low smoke performance and the like, and the extrusion processing performance cannot meet the requirement of high-efficiency extrusion, so that how to overcome the technical problems is the direction of research and development personnel to be careful.
Disclosure of Invention
The invention aims to provide a high-oil-resistance long-service-life irradiation crosslinking halogen-free low-smoke flame-retardant elastomer cable material for locomotive cables, which overcomes the defects of flame retardance, low smoke, mineral oil resistance, fuel oil resistance, low temperature resistance, scratch and abrasion resistance, low production efficiency and the like, and has the service life of not less than 32 years at the temperature of 90 ℃.
The second purpose of the invention is to provide a preparation method of the high-oil-resistance long-service-life irradiation crosslinking halogen-free low-smoke flame-retardant elastomer cable material for the locomotive cable, which has the advantages of simple process and low production cost.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a high-oil-resistance long-service-life irradiation crosslinking halogen-free low-smoke flame-retardant elastomer cable material for locomotive cables is composed of the following raw materials in parts by weight:
the applicant finds through research and practice that the flame retardance of the cable material can be remarkably improved and the effect of the flame retardance can be enhanced by adding the nano-montmorillonite into the polyolefin cable material, the temperature resistance of the cable material is improved by adding the ethylene-butyl acrylate, the processability of the material is improved by the cooperation with other materials, the extrusion appearance is good, the effective efficiency is high, the mechanical performance of the cable material is remarkably improved by compounding the polyethylene and other materials, the low temperature resistance and the scratch and abrasion resistance of the cable material are remarkably improved by compounding the ethylene-propylene-diene copolymer and other materials, the cross-linking degree among molecules is enhanced by adding the grafting material, the flame retardance, the oil resistance, the scratch and abrasion resistance and the mechanical performance are remarkably improved, the mechanical performance of the cable material is remarkably improved by adding the vinyl tri (β -methoxyethoxy) silane and the triallyl isocyanurate, the service life is prolonged to more than 33 years, and the comprehensive performance of the cable material is remarkably improved by compounding the specific components and the specific dosage components, and the service life is remarkably prolonged.
In order to further improve the mechanical property of the cable material, the mass content of vinyl acetate in the ethylene-vinyl acetate copolymer is 20-70%, more preferably the mass ratio of the ethylene-vinyl acetate copolymer with the mass content of 25-40% of vinyl acetate to the ethylene-vinyl acetate copolymer with the mass content of 65-70% of vinyl acetate is (3-8): (3-13).
In order to further improve the temperature resistance of the cable material, the mass content of butyl acrylate in the ethylene-butyl acrylate is 10-30%.
In order to further improve the mechanical property of the cable material, the polyethylene is at least one of linear low density polyethylene, bimodal polyethylene or high density polyethylene. Further preferably, the polyethylene is linear low density polyethylene and the bimodal polyethylene in a mass ratio of (1-1): (3-4).
In order to further improve the low temperature property and the scratch and abrasion resistance of the cable material, the ethylene propylene diene copolymer is at least one of ethylene propylene diene monomer with high ethylene content or ethylene propylene diene monomer with low ethylene content.
In order to further improve the comprehensive performance of the cable material, the grafting material is at least one of maleic anhydride grafted linear low-density polyethylene, maleic anhydride grafted ethylene-vinyl acetate copolymer or maleic anhydride grafted ethylene-octene copolymer. .
In order to further improve the flame retardance of the cable material and reduce the using amount of the flame retardant, the inorganic flame retardant is at least one of magnesium hydroxide or aluminum hydroxide. More preferably, the inorganic flame retardant is prepared by mixing chemical magnesium hydroxide and aluminum hydroxide in a mass ratio of (2.5-3.5): 1, and the particle sizes are all 0.8-1.2 microns.
In order to further improve the processability and the extrusion appearance of the cable material, the lubricant is at least one of polyethylene wax, stearic acid or zinc stearate, and further preferably, the mass ratio of the polyethylene wax to the stearic acid is (0.8-1.2): 1.
In order to further improve the weather resistance of the cable material, the antioxidant is at least one of pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], dilauryl thiodiacrylate, 4 '-thiobis (6-tert-butyl-3-methylphenol), distearyl thiodipropionate, pentaerythritol dodecadithiophosphate or 1,2- [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine, the antioxidant is pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], dilauryl thiodiacrylate, 4' -thiobis (6-tert-butyl-3-methylphenol), distearyl thiodipropionate, pentaerythritol dodecathiopropionate and 1, 2-bis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine in a mass ratio of 1 (1-1.5): 0.5: 0.8: 0.5: 1.5: 0.5.
The preparation method of the high-oil-resistance long-service-life irradiation crosslinking halogen-free low-smoke flame-retardant elastomer cable material for the locomotive cable comprises the steps of putting ethylene-vinyl acetate copolymer, ethylene-butyl acrylate, polyethylene, a grafting material, an inorganic flame retardant, nano montmorillonite, a lubricant, an antioxidant, vinyl tris (β -methoxyethoxy) silane and triallyl isocyanurate into an internal mixer for mixing, discharging when the temperature of the mixed material reaches 160-165 ℃, passing the mixed material through a double-cone feeding system to a double-screw extruder, and finally entering single-screw extrusion granulation and air cooling packaging to obtain a finished product material, wherein the temperature of one area to seven areas of the double-screw extruder is set to be 100-105 ℃ from one area to two areas, and the temperature of three areas to 95-100 ℃ from three areas, the temperature of the single-screw extruder is set to be 105-110 ℃ from one area to 115-120 ℃ from three areas, 125-130 ℃, the temperature of the head is 135-140 ℃ and the hot cutting die surface.
The prior art is referred to in the art for techniques not mentioned in the present invention.
The high-oil-resistance long-service-life irradiation crosslinking halogen-free low-smoke flame-retardant elastomer cable material for the locomotive cable has the advantages of flame retardance, low smoke, mineral oil resistance, fuel oil resistance, low temperature resistance, scrape abrasion resistance, softness, high production efficiency and the like, and the service life of the material is not less than 32 years at 90 ℃; the process is simple and the production cost is low.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
In each example, the compositions of the high oil-resistant long-life irradiation crosslinking halogen-free low-smoke flame-retardant elastomer cable material for locomotive cables are shown in table 1, wherein parts represent parts by weight.
TABLE 1 raw material composition of each example
| Components | Example 1 | Example 2 | Example 3 | Example 4 |
| Ethylene-vinyl acetate copolymer (EVA) | 35 | 42 | 35 | 30 |
| Ethylene-butyl acrylate (EBA) | 30 | 15 | 18 | 25 |
| Polyethylene | 17 | 25 | 25 | 25 |
| Ethylene propylene diene monomer copolymer | 8 | 8 | 10 | 10 |
| Grafting material | 10 | 10 | 12 | 15 |
| Inorganic flame retardant | 155 | 160 | 155 | 155 |
| Nano montmorillonite | 5 | 5 | 8 | 8 |
| Lubricant agent | 2 | 2 | 2 | 2 |
| Antioxidant agent | 5.5 | 5.5 | 5.5 | 5.5 |
| Vinyl tris (β -methoxyethoxy) silane | 2 | 2 | 2 | 2 |
| Triallylisocyanurate | 2 | 2 | 2 | 2 |
In each case, the ethylene-butyl acrylate (EBA) is E2770(REPSOL, BA content 27%, melt index 7g/10min), the nano-montmorillonite is I.44PT (NONONOCOR, 20nm), the lubricant is a mixture of polyethylene wax (Tiaohao chemical Co., Ltd.) and stearic acid (Tiaohao chemical science Co., Ltd.) in a mass ratio of 1: 1, and the antioxidant is a mixture of pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], dilauryl thiodiacrylate, 4' -thiobis (6-tert-butyl-3-methylphenol), distearyl thiodipropionate, dodecylthiopropionate pentaerythrityl and 1, 2-bis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine in a mass ratio of 1: 1.2: 1.3: 0.8: 1.1: 0.3.
In example 1, the mass ratio of EVA 6110MC (yangbasff, VA content 26%) to 700XL (arnerzone, VA content 70%) is 4: 3; the polyethylene is high density polyethylene 6098 (medium petrochemical, melt index 10g/10 min); the ethylene-propylene-diene copolymer was 4725P (DOW, ethylene content 73%, third monomer content 5%); the grafting material is maleic anhydride grafted linear low density polyethylene MC226 (Ningbo optical New Material science and technology Co., Ltd., grafting rate 0.8%, melt index 1.1g/10 min); the inorganic flame retardant is chemical magnesium hydroxide A10(KAUSTIK, particle size 1.0 micron).
In example 2, the mass ratio of EVA 40L-03 (DuPont, 40% VA) to 700XL (Arnetaceae, 70% VA) is 8: 13; the polyethylene is linear low density polyethylene 2520 (China petrochemical, melting index is 20g/10min) and bimodal polyethylene B5822(Sabic, melting index is 0.2g/10min) in a mass ratio of 2: 3; the ethylene-propylene-diene monomer copolymer is high-ethylene-propylene-diene monomer 4725P (DOW, the ethylene content is 73 percent, and the third monomer content is 5 percent); the grafting material is maleic anhydride grafted linear low density polyethylene MC226 (Ningbo optical New Material science and technology Co., Ltd., grafting rate 0.8%, melt index 1.1g/10 min); the inorganic flame retardant is prepared by mixing chemical magnesium hydroxide A7(KAUSTIK, particle size of 1.2 microns) and aluminum hydroxide AH-01M (Luoyang super nonmetal material Co., Ltd., particle size of 0.7 microns) at a mass ratio of 3: 1.
In example 3, the mass ratio of EVA 40L-03 (DuPont, 40% VA) to 700XL (Arnetaceae, 70% VA) was 3: 4; the polyethylene is linear low density polyethylene 2520 (China petrochemical, melting index is 20g/10min) and bimodal polyethylene B5822(Sabic, melting index is 0.2g/10min) in a mass ratio of 1: 4; the ethylene-propylene-diene monomer copolymer is ethylene-propylene-diene monomer J-4045 (Jilin petrochemical, ethylene content 51.5%, third monomer content 7.9%) with low ethylene content; the grafting material is maleic anhydride grafted ethylene-octene copolymer MC509 (Ningbo optical New Material science and technology Co., Ltd., grafting ratio of 0.8%, melt index of 1.1g/10 min); the inorganic flame retardant is chemical magnesium hydroxide A10(KAUSTIK, particle size 1.0 micron).
In example 4, EVA was 500HV (alanyl-neotame, VA content 50%); the polyethylene is high density polyethylene 6098 (medium petrochemical, melt index 10g/10 min); the ethylene-propylene-diene monomer copolymer is ethylene-propylene-diene monomer J-4045 (Jilin petrochemical, ethylene content 51.5%, third monomer content 7.9%) with low ethylene content; the grafting material is MC509 (Ningbo energy optical new materials science and technology Limited, grafting ratio is 0.8%, melt index is 1.1g/10 min); the inorganic flame retardant is chemical magnesium hydroxide A10(KAUSTIK, particle size 1.0 micron).
The preparation method of the high-oil-resistance long-service-life irradiation crosslinking halogen-free low-smoke flame-retardant elastomer cable material for locomotive cables comprises the following steps of weighing ethylene-vinyl acetate copolymer, ethylene-butyl acrylate, polyethylene, a grafting material, an inorganic flame retardant, nano montmorillonite, a lubricant, an antioxidant, vinyl tris (β -methoxyethoxy) silane and triallyl isocyanurate according to parts by weight, putting the mixture into an internal mixer for mixing, discharging the mixture when the temperature of the mixture reaches 160-165 ℃, passing the mixture through a double-cone feeding system to a double-screw extruder, finally feeding the mixture into a single-screw extruder for extrusion granulation, performing air cooling and packaging to obtain a finished product, setting the temperatures of one zone to seven zones of the double-screw extruder to be 100-105 ℃ from the first zone to the second zone and 95-100 ℃ from the third zone to the seventh zone, setting the temperature of the single-screw extruder to be 105-110 ℃ from the first zone, 115-120 ℃ and 125-130 ℃ and 135-140 ℃ at a machine head, and setting the.
The performance test data of the high oil resistance long-life irradiation crosslinking halogen-free low-smoke flame-retardant elastomer cable material for the locomotive cable obtained in each example are shown in table 2.
TABLE 2 Property Table of the Cable materials obtained in the examples
Example 3 was selected for a 90 ℃ heat aging evaluation test using IEC 60216-1: 2013, selecting 4 temperature points (180 ℃, 165 ℃, 150 ℃ and 135 ℃) to carry out an aging test, taking the aging time of 50% of the retention rate of elongation at break after aging as the termination time, and calculating the service life of the material to be 32.2 years in the environment of 90 ℃ according to the Allen nius equation, wherein the aging termination time corresponding to the 4 temperature points is 12 days, 32 days, 87 days and 257 days respectively. The life of example 1/2/4 tested in the same manner was 32.2 years or more.
From the example performance test data: the high-oil-resistance long-service-life irradiation crosslinking halogen-free low-smoke flame-retardant elastomer cable material for the locomotive cable, provided by the invention, has excellent mechanical properties, electrical properties and oil resistance, and also has excellent flame-retardant properties and light transmittance, can be used for producing the locomotive cable meeting the requirements of national standards and European standards, and has the service life of more than 33.2 years.
Claims (10)
1. The utility model provides a high resistant oily high life irradiation crosslinking halogen-free low smoke flame retardant elastomer cable material for locomotive cable which characterized in that: the composition comprises the following raw materials in parts by weight:
2. the high oil-resistant long-life irradiation crosslinking halogen-free low-smoke flame-retardant elastomer cable material for the locomotive cable according to claim 1, characterized in that: the mass content of vinyl acetate in the ethylene-vinyl acetate copolymer is 20-70%; the mass content of butyl acrylate in the ethylene-butyl acrylate is 10-30%.
3. The high oil resistance long-life irradiation crosslinking halogen-free low-smoke flame-retardant elastomer cable material for the locomotive cable according to claim 2, characterized in that: the ethylene-vinyl acetate copolymer is an ethylene-vinyl acetate copolymer with the mass content of vinyl acetate of 25-40% and an ethylene-vinyl acetate copolymer with the mass content of vinyl acetate of 65-70%, and the mass ratio of the ethylene-vinyl acetate copolymer to the vinyl acetate copolymer is (3-8): (3-13).
4. The high oil-resistant long-life irradiation crosslinking halogen-free low-smoke flame-retardant elastomer cable material for the locomotive cable according to any one of claims 1 to 3, characterized in that: the polyethylene is at least one of linear low density polyethylene, bimodal polyethylene or high density polyethylene; the grafting material is at least one of maleic anhydride grafted linear low-density polyethylene, maleic anhydride grafted ethylene-vinyl acetate copolymer or maleic anhydride grafted ethylene-octene copolymer.
5. The high oil resistance long-life irradiation crosslinking halogen-free low-smoke flame-retardant elastomer cable material for the locomotive cable according to claim 4, characterized in that: the polyethylene is linear low-density polyethylene and the bimodal polyethylene in a mass ratio of (1-2): (3-4).
6. The high oil-resistant long-life irradiation crosslinking halogen-free low-smoke flame-retardant elastomer cable material for the locomotive cable according to any one of claims 1 to 3, characterized in that: the inorganic flame retardant is at least one of magnesium hydroxide or aluminum hydroxide; the lubricant is at least one of polyethylene wax, stearic acid or zinc stearate.
7. The high oil resistance long-life irradiation crosslinking halogen-free low-smoke flame-retardant elastomer cable material for the locomotive cable according to claim 6, characterized in that: the inorganic flame retardant is magnesium hydroxide and aluminum hydroxide with the mass ratio of (2.5-3.5): 1; the lubricant is polyethylene wax and stearic acid in a mass ratio of (0.8-1.2): 1.
8. The high oil resistance long-life irradiation crosslinking halogen-free low smoke flame retardant elastomer cable material for the locomotive cable according to claim 1 or 2, characterized in that the antioxidant is at least one of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, dilauryl thiodiacrylate, 4' -thiobis (6-tert-butyl-3-methylphenol), distearyl thiodipropionate, pentaerythritol-type dodecyl disulfide or 1,2- [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine.
9. The high oil resistance long-life irradiation crosslinking halogen-free low-smoke flame retardant elastomer cable material for the locomotive cable as claimed in claim 8, wherein the antioxidant is a mixture of pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], dilauryl thiodiacrylate, 4' -thiobis (6-tert-butyl-3-methylphenol), distearyl thiodipropionate, pentaerythrityl dodecylthiopropyl ester and 1, 2-bis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine in a mass ratio of 1 (1-1.5): 0.5-1.5): 0.8-1.5): 0.1-0.5.
10. The preparation method of the high-oil-resistance long-life irradiation crosslinking halogen-free low-smoke flame-retardant elastomer cable material for the locomotive cable according to any one of claims 1 to 9 is characterized in that an ethylene-vinyl acetate copolymer, ethylene-butyl acrylate, polyethylene, a grafting material, an inorganic flame retardant, nano montmorillonite, a lubricant, an antioxidant, vinyl tris (β -methoxyethoxy) silane and triallyl isocyanurate are put into an internal mixer for mixing, when the material temperature reaches 160-165 ℃, the material is discharged and enters a double-screw extruder through a double-cone feeding system, and finally enters a single-screw extruder for extrusion granulation and air cooling packaging to obtain a finished product material, wherein the temperature of one zone to seven zones of the extruder is set to be 100-105 ℃ from one zone to two zones and 95-100 ℃ from three zones to seven zones, the temperature of the single-screw extruder is set to be 105-110 ℃ from one zone, 115-120 ℃ from two zones, 125-130 ℃ from three zones and 135-140 ℃ from a head, and the hot cutting die surface is 145-150 ℃.
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| CN201911194353.9A CN110862601A (en) | 2019-11-28 | 2019-11-28 | High-oil-resistance long-service-life irradiation crosslinking halogen-free low-smoke flame-retardant elastomer cable material for locomotive cable and preparation method thereof |
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| CN113817246A (en) * | 2021-05-28 | 2021-12-21 | 江苏上上电缆集团新材料有限公司 | Halogen-free flame-retardant polyolefin radiation material for high-electric-property weather-resistant thin-wall locomotive cable and preparation method thereof |
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| CN114773719A (en) * | 2022-03-28 | 2022-07-22 | 金发科技股份有限公司 | Polyolefin material and preparation method and application thereof |
| CN115873332A (en) * | 2022-08-16 | 2023-03-31 | 江苏上上电缆集团新材料有限公司 | Long-life environment-friendly polyolefin insulating material, preparation method and application in flexible energy storage cable |
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