Patent Grant
12002601
The present disclosure belongs to the field of polymer materials technology and science, and particularly relates to a stress-resistant, creep-resistant, high-temperature resistant and high-insulation sheath material for a 620 km/h maglev train, and a manufacturing method and use thereof.
The successful operation of a 620 km/h maglev train has greatly filled a speed gap between China's high-speed rail and air transportation, but it also puts forward higher requirements for structural size, electrical performance, mechanical and physical performance, and safety performance of cables. It is necessary to achieve long-term stable operation of materials under high temperature, high stress and strong twisting environments.
In Patent Application Publication CN108239322A, high-density polyethylene is used as a carrier to be mixed with carbon black and extruded together with different polyethylene resins so as to prepare high-hardness, wear-resistance high-toughness polyethylene sheaths, thereby improving the hardness and cracking resistance time of the material. In Patent Application Publication CN104774363A, a blended masterbatches is prepared from vinyl tris(2-methoxyethoxy) silane, tert-butyl benzoyl peroxide and polyethylene, and then blended with a low-density polyethylene matrix, and a silane crosslinked polyethylene cable material is prepared in a closed space with water under the sun so that the cable has a high crosslinking degree. However, the improvement of material performance in the above studies is relatively single, and has not been mentioned in terms of high temperature resistance, stress resistance, etc. The scope of application is relatively low, making it difficult to meet the application requirements in complex environments. At present, the technology related to maglev trains in China is mostly monopolized by foreign countries, so it is of great significance to develop sheath materials with independent intellectual property rights that are resistant to stress, creep, high temperature and high insulation.
The present disclosure provides a stress-resistant, creep-resistant, high-temperature resistant and high-insulation sheath material for a maglev train cable, and a manufacturing method and use thereof. The sheath material comprises the raw materials in parts by weight: 100-150 parts of ultra-high molecular weight polyethylene (UHMWPE); 50-80 parts of functional polyvinylsilicone grease; 50-80 parts of ceramicized silicone rubber; 120-200 parts of phosphorus nitrogen flame retardant; 30-50 parts of reinforcing fillers; 5-10 parts of vulcanizing agent; 1-5 parts of vulcanization accelerator; 1-5 parts of coupling agent; 5-10 parts of compatibilizer; 2-5 parts of lubricant; 1-3 parts of antioxidant; and 1-2 parts of antistatic agent. A multiple chemical crosslinking structure is constructed by blending of a polyvinylsilicone grease with UHMWPE and a ceramicized silicone rubber as a cable material matrix and using electron beam irradiation. In addition, organic/inorganic fillers in the matrix can form physical crosslinking points in the material. A physical-chemical dual crosslinking structure is constructed in the matrix, where the multiple chemical and physical crosslinking structure can limit the motion and relaxation of molecular chains and improve the interaction between the insulation layer and sheath layer and refractory layers such as fillers and mica tapes to avoid the relative shift during the laying and operation and improve the high-temperature resistance, creep resistance and stress relaxation resistance of a UHMWPE cable sheath material.
A specific solution is as follows.
A stress-resistant, creep-resistant, high-temperature resistant and high-insulation sheath material for a maglev train cable, comprising the raw materials in parts by weight:
where z, x, m and n are numbers of repeated units, and are independently integrals between 300 and 500; where the sheath material is prepared by performing melting blend on the UHMWPE, functional polyvinylsilicone grease, ceramicized silicone rubber, phosphorus nitrogen flame retardant, reinforcing filler, coupling agent, compatibilizer, lubricant, antioxidant and antistatic agent in ratios to obtain blended masterbatches and then performing melting blend on the blended masterbatches, vulcanizing agent and vulcanization accelerator to obtain pre-crosslinked masterbatches.
Further, the UHMWPE has a density of 0.92-1.08 g/cm3, a boiling point of 120-140° C., a melt flowing rate of 0.05-0.3 g/10 min under the condition of 190° C./2.16 kg, a molecular weight of 4×106 g/mol-107 g/mol, a shore hardness (D) of 60-65 and a notch impact strength of 50-65 kJ/m2;
A method of manufacturing the sheath material, comprising the following steps:
Further, the method also comprises preparing the functional polyvinylsilicone grease, and specific steps are as follows:
The above copolymer (1) together with hydrothermal reagents, namely 5% NaOH, KOH, NH3·H2O, 2.5% Na2CO3 solution and a 5% ethanol solution is placed in a hydrothermal reactor at the reaction temperature of 400° C. for 4 h to obtain a solid phase product (1) as the functional polyvinylsilicone grease.
where z, x, m and n are numbers of repeated units, which are independently integrals between 300 and 500.
Further, a method of applying the sheath material is as follows:
The present disclosure has the following beneficial effects.
1) The functional polyvinylsiloxane grease is a polymer containing a large number of unsaturated bonds and having an eight-membered cyclic structure. The eight-membered ring structure can effectively prevent the slipping of molecular chains, plays a role in resisting creep and stress relaxation, and a large number of double bonds can be used for chemical crosslinking to improve the crosslinking degree.
2) The fillers are introduced to construct physical crosslinking points, while initiating chemical crosslinking of double bonds through irradiation, further limiting the relaxation of molecular chains and improving the strength and toughness of the material. After irradiation crosslinking, the functional polyvinylsilicone grease can interact strongly with the ceramicized silicone rubber refractory layer, thereby reducing the relative displacement between the refractory layer and the insulation layer, achieving long-term stable operation of cables in high temperature, high stress and strong twisting environments, and improving the high-temperature, creep and stress relaxation resistance of the UHMWPE cable sheath material.
3) The following steps are further described, i.e., the above blended masterbatches, the vulcanizing agent and the vulcanization accelerator are added into a high-speed mixer for 15 min of blending at 3500 r/min, the blending is stopped, and then the mixture is placed in a twin screw extruder for melting blend and extrusion, the processing temperatures are respectively 100° C., 110° C., 120° C., 130° C., 135° C. and 140° C. from the material mouth to the mold mouth, after cooling and drying, pre-crosslinked masterbatches are obtained, the fillers are evenly dispersed in the matrix, at the same time, the generation efficiency of free radicals of the vulcanizing agent and the vulcanization accelerator is increased, and then the crosslinking degree is improved.
Next, the present disclosure will be described in detail through specific examples, however, the scope of protection of the present disclosure is not limited to these examples.
The raw materials used in the following examples are as follows:
UHMWPE: ultra-high molecular weight polyethylene, with a density of 1.03 g/cm3, a Rockwell hardness (R) of 58, a tensile strength of 46 MPa, elongation at break of 7%, a bending modulus of 2210 MPa, a bending strength of 43 MPa, a Vicat softening temperature of 130° C., a dielectric strength of 60 kV/mm and a dielectric constant of 2.5, which is L4420 from Mitsui Chemical L4420, Japan.
Functional polyvinylsiloxane grease: a four-arm eight-membered cyclic star-shaped polymer containing a large number of unsaturated bonds, which is prepared by the following steps: weighing a metallocene catalyst (nBuCp)2ZrCl2 in a nitrogen glove box and completely dissolving the catalyst into toluene; sequentially adding 100 ml of n-heptane, 60 ml of 6-chloro-1-hexene, 0.126 g of trimethylaluminum (MAO) and 0.18 g of metallocene catalyst that are accurately weighed into a vacuum reactor in a nitrogen environment, stirring, and heating to 85° C.; after the system temperature rises to the reaction temperature, adding 15 ml of 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane and stopping the introduction after 8 h of reaction, pouring the copolymer into a glass container after the temperature drops to a room temperature, and slowly adding an excessive 5% hydrochloric acid ethanol solution into the container to stop the reaction, filtering, and drying in vacuum at 80° C. for 12 h to obtain a solid copolymer; and placing the above copolymer (1) together with hydrothermal reagents (5% NaOH, KOH, NH3·H2O, 2.5% Na2CO3 solution and 5% ethanol solution) in a hydrothermal reactor in a ratio of the copolymer to the hydrothermal reagents of 1:20 at the reaction temperature 400° C. for 4 h to obtain a solid phase product (I) as the functional polyvinylsilicone grease.
Ceramicized silicone rubber: a Shore hardness (A) of 70, a density of 1.46 g/cm3, an elongation at break of 447%, a tensile strength of 10.7 MPa, a dielectric constant of 28, an oxygen index of 38, which is TCHS-0001S from Guangdong Antop Polymer Technology Co., Ltd.
Phosphorus nitrogen flame retardant: a mixture of triethyl phosphate (TEP), 9,10-dihydro-9-oxyphenanthrene-10 oxide (DOPO) and melamine cyanurate (MCA) in a mass ratio of 1:1:1, which are from Shanghai Aladdin Biochemical Technology Co., Ltd.
Reinforcing filler: a mixture of mica and talc powder in a mass ratio of 1:1. Mica is from Anhui Gerui New Material Technology Co., Ltd. GM-3; talcum powder is from Quanzhou Xufeng Powder Raw Materials Co., Ltd. BHS-8860.
Vulcanizing agent: 2,5-dimethyl-2,5-bis(peroxy-tert-butyl) hexane (AD), which is from Shanghai Aladdin Biochemical Technology Co., Ltd.
Vulcanization accelerator: tetramethylthiuram disulfide (TMTD), which is from Shanghai Aladdin Biochemical Technology Co., Ltd.
Coupling agent: y-mercaptopropyl triethoxysilane, which is from Shanghai Aladdin Biochemical Technology Co., Ltd.
Compatibilizer: a mixture of glycidyl methacrylate grafted ethylene-vinyl acetate (EVA-g-GMA), maleic anhydride grafted ethylene-vinyl acetate (EVA-g-MAH) and glycidyl methacrylate grafted ethylene-octene copolymer (POE-g-GMA) in a mass ratio of 1:1:3. EVA-g-GMA is from Sumitomo BF-7M, Japan, EVA-g-MAH is from Akoma T9318, France, and POE-g-GMA is from DuPont N493, the United States.
Lubricant: paraffin wax, which is from Emilsogen P from Klein, Switzerland.
Antioxidant: a mixture of 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline and N-phenyl-N′-cyclohexyl-phenylenediamine in a mass ratio of 2:1, which is from Shanghai Aladdin Biochemical Technology Co., Ltd.
Antistatic agent: 1-allyl-3-vinylimidazole tetrafluoroborate, which is from Shanghai Chengjie Chemical Co., Ltd.
EVA: ethylene-vinyl acetate, with a melt index of 20 g/10 min, a density of 0.95 g/cm3, a VA content of 28 wt % and a melting point of 69° C., which is from Korean Lotte Chemical VA800.
The mass fractions of various raw materials in the following examples are seen in Table 1.
Table 1 Raw materials and amounts of stress-resistant, creep-resistant, high-temperature resistant and high-insulation sheath material for maglev train cable (based mass fraction)
Raw materials and formulas in this example are seen in Table 1. The preparation method was carried out according to the following steps:
UHMWPE, a functional polyvinylsilicone grease, a ceramicized silicone rubber, a phosphorus nitrogen flame retardant, a reinforcing filler, a coupling agent, a compatibilizer, a lubricant, an antioxidant and an antistatic agent were added into an internal mixer in ratios for 10 min of melting blend under the conditions of 180° C. and 50 rpm, then the above mixture was cooled, dried and then placed in a twin-screw extruder at 130-180° C. for melting blend and extrusion, and then cooled and dried to obtain blended masterbatches.
The above masterbatches together with a vulcanizing agent and a vulcanization accelerator were added into a high-speed mixer for 15 min of blending at 3500 r/min, then the blending was stopped, then the obtained product was placed in a twin-screw extruder for melting blend and extrusion, the processing temperatures were respectively 100° C., 110° C., 120° C., 130° C., 135° C. and 140° C. from the material mouth to the mold mouth, and then the above mixture was cooled and dried to obtained pre-crosslinked masterbatches.
The pre-crosslinked masterbatches were placed in a wire and cable extruder for melting and extrusion on a cable conductor core, the temperature of an inlet was 130° C., the temperature of a first zone was 130-140° C., the temperature of a second zone was 140-150° C., the temperature of a third zone was 150-160° C., the temperature of a fourth zone was 160-170° C., the temperature of a fifth zone was 170-180° C., and the temperature of an outlet was 175° C., the surface of a core of a cable conductor was wrapped with a sheath; and finally the wrapped core was irradiated for 8 min under the conditions that a beam pressure was 1.5-2 MeV, a beam current was 20 mA, and an irradiation dose was 400 kGy to obtain the sheath material.
Raw materials and formulas in this example are seen in Table 1, and the preparation process is the same as that in example 1.
Raw materials and formulas in this example are seen in Table 1, and the preparation process is the same as that in example 1.
Raw materials and formulas in this comparative example are seen in Table 1, and the preparation process is the same as that in example 1
Raw materials and formulas in this comparative example are seen in Table 1, and the preparation process is the same as that in example 1
Raw materials and formulas in this comparative example are seen in Table 1, and the preparation process is the same as that in example 1
Raw materials and formulas in this example are seen in Table 1. The preparation process was carried out according to the following steps:
The pre-blended masterbatches were placed in a wire and cable extruder for melting and extrusion on a cable conductor core, the temperature of an inlet was 130° C., the temperature of a first zone was 130-140° C., the temperature of a second zone was 140-150° C., the temperature of a third zone was 150-160° C., the temperature of a fourth zone was 160-170° C., the temperature of a fifth zone was 170-180° C., and the temperature of an outlet was 175° C., and finally the wrapped core was irradiated for 8 min under the conditions that a beam pressure was 1.5-2 MeV, a beam current was 20 mA, and an irradiation dose was 400 kGy to obtain the material
The main performance indexes of the cable materials obtained in examples 1-3 and comparative examples 1-4 are seen in Table 2.
The test results are as shown in Table 2. The comprehensive performance of example 2 is optimal. Due to a high crosslinking degree in the system and the presence of a rigid structure, the breakage of the molecular chain can be effectively prevented, and the strength and elongation at break of the material are improved. The functional polyvinylsilicone grease can interact strongly with the ceramicized silicone rubber refractory layer to reduce the relative displacement between the refractory layer and the insulation layer, and improve the insulation and fire resistance performance of the material. During the oil resistance test, the movement of molecular chains is limited and difficult to swell, thereby leading to an improvement in oil resistance performance. By comparing example 2 with example 1, it shows that the contents of the functional polyvinylsilicone grease and the ceramicized silicone rubber are proportionally increased, and the crosslinking degree of the materials is increased, thereby resulting in less deformation of the material when being subjected to external forces; the deformation can rapidly restore when the external forces are removed so as to enhance the interaction between the functional polyvinylsilicone grease and the ceramicized silicone rubber refractory layer, leading to an improvement in the overall performance of the material. By comparing example 2 with example 3, it shows that due to the excess of UHMWPE and the ceramicized silicone rubber in example 3, the crosslinking degree of the material is decreased, and an interaction between the functional polyvinylsilicone grease and the refractory layer is weakened, thereby resulting in a decrease in comprehensive performance. By comparing example 2 to comparative example 1, it shows that in comparative example 1, the traditional EVA is used as a matrix, without the addition of the functional polyvinylsilicone grease and the ceramicized silicone rubber, thereby resulting in poor overall performance. By comparing example 2 with comparative examples 2 and 3, it shows that the combination of the functional polyvinylsilicone grease and the ceramicized silicone rubber is not used in formulations of comparative examples, thereby resulting in performance defects existing in the material. In conclusion, it exhibits the superiority of the formula designed in example 2.
Example 1 has the same formula as comparative example 4, but the preparation processes are different. In comparative example 4, due to one-step mixing, the dispersion effect of the filler is poor, and the generation efficiency of free radical during irradiation crosslinking is poor, thereby resulting in a decrease in crosslinking degree, and reflecting the superiority of the preparation process.
Based on the analysis of test data, it can be seen that the performance of the sheath material with stress resistance, creep resistance, high temperature resistance and high insulation for the maglev train cable has been significantly improved due to the following reasons.
Firstly, specific processing techniques result in uniform dispersion of fillers, enhancing the generation efficiency of free radicals during irradiation, and improving the crosslinking degree compared to traditional one-step methods.
Secondly, the circular structure in the functional polyvinylsiloxane can improve the strength of the material.
Thirdly, due to the unique star-shaped structure and a large number of unsaturated bonds of the functional polyvinylsilicone grease, a highly crosslinked body structure is formed after irradiation, this chemical crosslinking inhibits the slip of different molecular chains, while forming physical crosslinking points between fillers and limiting the movement of chain segments, however, the ring structure in the single molecular chain can also effectively prevent the breakage. This will reduce the deformation of the material when subjected to external forces, providing creep resistance. At the same time, when the external force is removed, the deformation will quickly recover and store energy.
Fourthly, after irradiation crosslinking, the functional polyvinylsilicone grease can interact strongly with the ceramicized silicone rubber refractory layer, reduces the relative displacement between the refractory layer and the insulation layer, and leads to an improvement in high-temperature resistance and other properties.
Lastly, the cross-linked structure can effectively prevent material swelling in oil and improve oil resistance. In addition, excessive double bonds in polyvinylsilicone grease can effectively prevent material aging and improve the performance of the material after aging testing.
In the present disclosure, the functional polyvinylsilicone grease with a specific structure is synthesized and the UHMWPE matrix is introduced by compounding functional polyvinylsilicone grease with the ceramicized silicone rubber. Through irradiation crosslinking, the comprehensive performance of the material is improved, thereby overcoming the problem of stress relaxation and creep that occur in traditional materials under high stress conditions, leading to a rapid decline in the performance of cables under actual operating conditions, and achieving long-term stable operation of cables under high temperature, high stress and strong twisting environments. The materials and related technologies can be applied to cables for 620 km/h maglev trains and related intelligent equipment.
Although the content of the present disclosure has been described in detail through the above preferred embodiments, it should be recognized that the above description should not be considered a limitation to the present disclosure. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present disclosure should be included within the scope of protection of the present disclosure.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202210775361.8 | Jul 2022 | CN | national |
This application is a continuation of International Application No. PCT/CN2023/095747, filed on May 23, 2023, which claims priority to Chinese Patent Application No. 202210775361.8, filed on Jul. 1, 2022. All of the aforementioned applications are incorporated herein by reference in their entireties.
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| Number | Date | Country | |
|---|---|---|---|
| 20240062935 A1 | Feb 2024 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/CN2023/095747 | May 2023 | US |
| Child | 18496779 | US |
