Anti-oxidation cable protection sleeve material and preparation method thereof
By using compound antioxidants and modified graphene microflakes in cable protective sleeve materials, the problem of strength loss after high-temperature aging of protective sleeve materials has been solved, achieving high aging resistance and wear resistance.
Patent Information
- Application Number
- CN202511306041.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-12
- Publication Date
- 2025-11-14
AI Technical Summary
Existing cable protective sleeve materials exhibit a high rate of loss in tensile strength and poor aging resistance after heat aging treatment at 135℃ for 240 hours.
By using a combination of antioxidants 1010 and 168, combined with modified graphene microsheets, and by grafting pre-monomers and carboxymethyl chitosan onto the surface of the graphene microsheets, the aging resistance and tensile strength of the material are improved.
The protective sleeve material achieved a tensile strength loss rate of less than 5% and a mass wear amount of less than 15mg after heat aging at 135℃ for 240h, exhibiting high tensile strength, aging resistance, and wear resistance.
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Abstract
Description
Technical Field
[0001] This application relates to the field of cable technology, and more specifically, to an antioxidant cable protective sheath material and its preparation method. Background Technology
[0002] Cables are carriers of electrical energy and communication, and are widely used in vehicle transportation, urban construction, aerospace, petrochemicals, subways, ships, and other fields. They are also an indispensable infrastructure in daily life. The outer surface of cables is often covered with a protective sheath, which protects the cable. The protective sheath is made by extrusion of a protective sheath material. The raw material for the protective sheath material is primarily polyethylene. Some researchers add antioxidant 1010 to the raw material to improve its aging resistance. However, in practical applications, the applicant found that the protective sheath material obtained by adding antioxidant 1010 exhibits a high loss rate of tensile strength after heat aging treatment at 135℃ for 240 hours, indicating poor aging resistance, which needs further improvement. Summary of the Invention
[0003] To improve the aging resistance of protective sleeve materials, this application provides an antioxidant cable protective sleeve material and its preparation method.
[0004] In a first aspect, this application provides an antioxidant cable protective sleeve material, which adopts the following technical solution: An antioxidant cable protective sleeve material is mainly made of the following raw materials in parts by weight: 85-95 parts linear low-density polyethylene, 5-15 parts high-density polyethylene, 4-6 parts maleic anhydride grafted polyethylene, 1-3 parts organic peroxide, 4-6 parts modified graphene microsheets, 1-3 parts compound antioxidant, 9-11 parts flame retardant, 2-4 parts silane coupling agent, and 0.5-1.5 parts lubricant; The compound antioxidants are antioxidant 1010 and antioxidant 168, and the weight ratio of antioxidant 1010 to antioxidant 168 is 1:(1-3). The modified graphene microsheets are obtained by treating graphene microsheets with pre-prepared monomers and carboxymethyl chitosan. The pre-prepared monomers are prepared by 4,4'-carbonyl phthalic anhydride and N-aminoethyl-3-aminopropyltriethoxysilane.
[0005] The antioxidant cable protective sleeve material of this application, through the synergistic effect of the raw materials, exhibits high tensile strength (>42MPa) and low tensile strength loss rate and mass wear after 135℃×240h heat aging (<5% tensile strength loss rate and <15mg mass wear). This antioxidant cable protective sleeve material demonstrates high tensile strength, good aging resistance, and high wear resistance, meeting market demands.
[0006] The antioxidant cable protective sleeve material of this application optimizes the compounded antioxidants and selects antioxidants 1010 and 168 for compounding. Antioxidant 1010 can terminate the oxidation chain, and antioxidant 168 can decompose hydroperoxides. By utilizing their synergistic effect, the aging resistance is improved. Modified graphene microflakes are added to the raw materials, and pre-made monomers and carboxymethyl chitosan are grafted onto the surface of the graphene microflakes. Carbonyl, benzene ring, carboxyl, amide, primary amine, hydroxyl, carboxymethyl, and glucosamine groups are introduced into the surface of the graphene microflakes, increasing the number of branches and groups. This allows the modified graphene microflakes to be uniformly dispersed in the protective sleeve material, and also increases compatibility, bonding force, and integrity, improves tensile strength, and reduces mass wear. At the same time, it can reduce voids and form a barrier, blocking gas and water vapor pathways, delaying oxygen penetration, improving barrier properties, and reducing the thermal aging tensile strength loss rate. As a result, the protective sleeve material has better tensile strength, aging resistance, and wear resistance.
[0007] Optionally, the modified graphene microsheets are prepared using the following method: S1. Mix organic solvent and 4,4'-carbonyl phthalic anhydride, and add N-aminoethyl-3-aminopropyltriethoxysilane dropwise. The addition time of N-aminoethyl-3-aminopropyltriethoxysilane is 40-80 min. After the addition is completed, continue stirring for 2-4 h, and then distill under reduced pressure to obtain the pre-prepared monomer for later use. S2. At a temperature of 80-90℃, water and graphene microsheets are mixed. The pre-prepared monomer is added for the first time and stirred for 1-3 hours. The pre-prepared monomer is added for the second time and stirred for 1-3 hours. The pre-prepared monomer is added for the third time and stirred for 1-3 hours. The pH value is adjusted to 9-12. Then, carboxymethyl chitosan and sodium trimetaphosphate are added and stirred for 2-4 hours. The mixture is filtered, washed, and dried to obtain modified graphene microsheets.
[0008] Optionally, the weight ratio of the graphene microsheets, the first addition of pre-prepared monomer, the second addition of pre-prepared monomer, the third addition of pre-prepared monomer, and carboxymethyl chitosan is 10:(0.4-0.6):(0.4-0.6):(0.8-1.2):(0.7-1.1).
[0009] By adopting the above technical solution, 4,4'-carbonyl phthalic anhydride contains one carbonyl group, two benzene rings, and two anhydride groups, while N-aminoethyl-3-aminopropyltriethoxysilane contains three siloxy groups, one primary amine group, and one secondary amine group. In the organic system, 4,4'-carbonyl phthalic anhydride and N-aminoethyl-3-aminopropyltriethoxysilane are contacted, and the anhydride group and secondary amine group react to form one carboxyl group and one amide group, i.e., the molar ratio of 4,4'-carbonyl phthalic anhydride to N-aminoethyl-3-aminopropyltriethoxysilane is 1:2, and a pre-prepared monomer is obtained. At this time, the pre-prepared monomer contains one carbonyl group, two benzene rings, six siloxy groups, two primary amine groups, two carboxyl groups, and two amide groups.
[0010] In an aqueous system, graphene microsheets are mixed with a pre-prepared monomer added initially. Using siloxy groups, the pre-prepared monomer is grafted onto the surface of the graphene microsheets, introducing primary amine and carboxyl groups. A second addition of the pre-prepared monomer causes the primary amine groups on the graphene microsheet surface to react with the carboxyl groups of the pre-prepared monomer, introducing more primary amine groups. Simultaneously, the carboxyl groups on the graphene microsheet surface react with the primary amine groups of the pre-prepared monomer, introducing more carboxyl groups. Similarly, a third addition of the pre-prepared monomer causes a reaction between carboxyl and primary amine groups, achieving grafting and increasing the number of branches and functional groups on the graphene microsheet surface. Then, carboxymethyl chitosan and sodium trimetaphosphate are added. Using sodium trimetaphosphate, the primary amine groups on the graphene microsheet surface and the primary amine and hydroxyl groups in carboxymethyl chitosan crosslink, achieving grafting and thus obtaining modified graphene microsheets.
[0011] Using the preparation method of this application, a pre-prepared monomer is prepared in advance, and then the pre-prepared monomer is grafted onto the surface of graphene microsheets in three steps, followed by grafting carboxymethyl chitosan. That is, grafting is carried out on the surface of graphene microsheets in steps, which facilitates the preparation of modified graphene microsheets and improves the use effect of modified graphene microsheets, thereby enhancing the tensile strength, aging resistance and wear resistance of the protective sleeve material.
[0012] Optionally, the weight ratio of the graphene microsheets to sodium trimetaphosphate is 10:(0.5-1.5).
[0013] By adopting the above technical solution, the amount of sodium trimetaphosphate added is optimized, reducing the impact of insufficient addition on the grafting effect and the increase in cost due to excessive addition. Furthermore, when the weight ratio of sodium trimetaphosphate to graphene microsheets is selected within the above range, the expected results can be achieved.
[0014] Optionally, the weight ratio of the graphene microsheets to water is 1:(7-13). In several embodiments, the weight ratio of 4,4'-carbonyl phthalic anhydride to organic solvent is 1:10, but it can also be set to 1:7, 1:8, 1:9, 1:11, 1:12, 1:13, etc., as needed, but is not limited to the listed values; other unlisted values within this range are also applicable.
[0015] Optionally, the weight ratio of 4,4'-carbonyl phthalic anhydride to N-aminoethyl-3-aminopropyltriethoxysilane is (9-11):(14-18).
[0016] By adopting the above technical solution, the weight ratio of 4,4'-carbonyl phthalic anhydride and N-aminoethyl-3-aminopropyltriethoxysilane is optimized, facilitating the preparation of the pre-prepared monomer. In several embodiments, the weight ratio of 4,4'-carbonyl phthalic anhydride and N-aminoethyl-3-aminopropyltriethoxysilane is 10:16.4. This ratio can also be set to 9:14, 9:16, 9:18, 10:14, 10:16, 10:18, 11:14, 11:16, 11:18, etc., as needed, but is not limited to the listed values; other unlisted values within this range are also applicable.
[0017] Optionally, the weight ratio of the 4,4'-carbonyl phthalic anhydride to the organic solvent is (9-11):(70-130). In several embodiments, the weight ratio of the 4,4'-carbonyl phthalic anhydride to the organic solvent is 10:100. It can also be set to 9:70, 9:100, 9:130, 10:70, 10:130, 11:70, 11:100, 11:130, etc., as needed, but is not limited to the listed values; other unlisted values within this range are also applicable.
[0018] Optionally, the organic solvent is one or more of tetrahydrofuran, dimethyl sulfoxide, cyclohexanone, xylene, toluene, ethanol, and isopropanol.
[0019] By adopting the above technical solution, the organic solvent is optimized to ensure that 4,4'-carbonyl phthalic anhydride and N-aminoethyl-3-aminopropyltriethoxysilane can fully contact and react, which facilitates the preparation of pre-prepared monomers.
[0020] Preferably, the organic solvent is either tetrahydrofuran or xylene, and the weight ratio of tetrahydrofuran to xylene is 1:(1-10). In several embodiments, the weight ratio of tetrahydrofuran to xylene is 1:4, but it can also be set to 1:1, 1:2, 1:3, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, etc., as needed, but it is not limited to the listed values; other unlisted values within this range are also applicable.
[0021] Optionally, the organic peroxide is one or more of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, dicumyl peroxide, tert-butyl peroxide, and cumyl peroxide neodecanoate.
[0022] By adopting the above technical solution, the organic peroxide is optimized, making it easier to select the appropriate organic peroxide. Moreover, organic peroxides can release free radicals, which helps to stimulate cross-linking reactions, improve the integrity of the protective sleeve material, and enable the protective sleeve material to exhibit better mechanical properties, aging resistance, and wear resistance.
[0023] Optionally, the silane coupling agent is one or more of vinyltris(2-methoxyethoxy)silane, 3-allyloxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and anilinemethyltrimethoxysilane.
[0024] By adopting the above technical solution, the silane coupling agent is optimized, which facilitates the selection of the silane coupling agent, and also effectively increases the interfacial bonding force, improves the integrity of the protective sleeve material, and makes the protective sleeve material exhibit better mechanical properties.
[0025] Optionally, the flame retardant is one or more of magnesium hydroxide, aluminum hydroxide, zinc borate, and ammonium tripolyphosphate; the lubricant is one or more of calcium stearate, zinc stearate, oleamide, and erucamide.
[0026] By adopting the above technical solutions, the flame retardants and lubricants are optimized, facilitating their selection. Furthermore, the flame retardants increase the flame retardancy of the protective sleeve material, while the lubricants improve processing fluidity, reduce friction during processing, and facilitate molding.
[0027] Secondly, this application provides a method for preparing the aforementioned antioxidant cable protective sleeve material, employing the following technical solution: A method for preparing the aforementioned antioxidant cable protective sleeve material includes the following steps: Linear low-density polyethylene, high-density polyethylene, maleic anhydride-grafted polyethylene, organic peroxide, modified graphene microsheets, compound antioxidants, flame retardants, silane coupling agents, and lubricants are mixed and then extruded at a temperature of 160-180℃ to obtain the protective sleeve material.
[0028] By adopting the above technical solution, it is easier to prepare protective sleeve materials.
[0029] In summary, this application has at least the following beneficial effects: 1. The anti-oxidation cable protective sleeve material of this application, through the mutual combination of raw materials, has a tensile strength >42MPa, a tensile strength loss rate of <5% after 135℃×240h heat aging, and a mass wear amount <15mg. It has the characteristics of high tensile strength, good aging resistance, and high wear resistance, which meets market demand.
[0030] 2. The antioxidant cable protective sleeve material of this application utilizes a compound of antioxidant 1010 and antioxidant 168 to improve aging resistance. Modified graphene microflakes are also added to the raw materials, and a large number of branches and groups are introduced onto the surface of the graphene microflakes, allowing the modified graphene microflakes to be uniformly dispersed in the protective sleeve material. This also increases compatibility, bonding strength, integrity, and barrier properties, improves tensile strength, reduces mass wear, and lowers the thermal aging tensile strength loss rate, giving the protective sleeve material superior tensile strength, aging resistance, and wear resistance. Detailed Implementation
[0031] To make this application easier to understand, the following detailed description will be provided with reference to embodiments. These embodiments are for illustrative purposes only and are not intended to limit the scope of application of this application. Unless otherwise specified, the raw materials or components used in this application can be obtained commercially or by conventional methods.
[0032] Preparation Example Preparation Example 1 A modified graphene microsheet is prepared by the following method: S1. Add 10 kg of 4,4'-carbonyl phthalic anhydride to 100 kg of organic solvent and stir for 3 min. Add 16.4 kg of N-aminoethyl-3-aminopropyltriethoxysilane dropwise over 60 min. After the addition is complete, continue stirring for 3 h. Then perform vacuum distillation to remove the organic solvent, obtaining the pre-prepared monomer for later use.
[0033] The organic solvents are tetrahydrofuran and xylene, and the weight ratio of tetrahydrofuran to xylene is 1:4.
[0034] S2. At 85℃, add 10kg of graphene microsheets to 100kg of water and stir for 10min. First, add 0.5kg of the pre-prepared monomer obtained in step S1 and stir for 2h. Second, add 0.5kg of the pre-prepared monomer obtained in step S1 and stir for 2h. Third, add 1kg of the pre-prepared monomer obtained in step S1 and stir for 2h. Adjust the pH to 10 using a saturated sodium hydroxide aqueous solution, then add 0.9kg of carboxymethyl chitosan and 1kg of sodium trimetaphosphate, and stir for 3h. Then filter and wash three times with water, using 30kg of water each time. Finally, dry to obtain modified graphene microsheets.
[0035] Among them, the graphene microplate is graphene microplate KNG-C162, and is selected from Xiamen Kaina Graphene Technology Co., Ltd.; the carboxymethyl chitosan is carboxymethyl chitosan V30064, and is selected from Shanghai Yuanye Biotechnology Co., Ltd.
[0036] Preparation Example 2 A modified graphene microsheet differs from preparation example 1 in that the amounts of the pre-prepared monomer added in the first, second, and third steps of step S2 are different.
[0037] Furthermore, the amount of pre-prepared monomer added for the first time was 0.4g, the amount of pre-prepared monomer added for the second time was 0.6g, the amount of pre-prepared monomer added for the third time was 1.2g, the amount of carboxymethyl chitosan added was 0.7g, and the amount of sodium trimetaphosphate added was 0.5g.
[0038] Preparation Example 3 A modified graphene microsheet differs from preparation example 1 in that the amounts of the pre-prepared monomer added in the first, second, and third steps of step S2 are different.
[0039] Furthermore, the amount of pre-prepared monomer added in the first addition was 0.6g, the amount of pre-prepared monomer added in the second addition was 0.4g, the amount of pre-prepared monomer added in the third addition was 0.8g, the amount of carboxymethyl chitosan added was 1.1g, and the amount of sodium trimetaphosphate added was 1.5g.
[0040] Preparation Example 4 A modified graphene microsheet differs from preparation example 1 in that step S2 is different.
[0041] Step S2 specifically involves adding 10 kg of graphene microsheets to 100 kg of water at 85°C and stirring for 10 min. Then, 2 kg of the pre-prepared monomer obtained in step S1 is added, and the mixture is stirred for 6 h. The pH is adjusted to 10 using a saturated sodium hydroxide aqueous solution, followed by the addition of 0.9 kg of carboxymethyl chitosan and 1 kg of sodium trimetaphosphate, and the mixture is stirred for 3 h. The mixture is then filtered and washed three times with 30 kg of water each time. Finally, it is dried to obtain the modified graphene microsheets.
[0042] Among them, the graphene microplate is graphene microplate KNG-C162, and is selected from Xiamen Kaina Graphene Technology Co., Ltd.; the carboxymethyl chitosan is carboxymethyl chitosan V30064, and is selected from Shanghai Yuanye Biotechnology Co., Ltd. Example
[0043] Table 1. Content of each raw material in the protective sleeve material (unit: kg) Example Example 1 Example 2 Example 3 Linear low-density polyethylene 90 85 95 High-density polyethylene 10 15 5 Maleic anhydride-grafted polyethylene 5 6 4 Organic peroxides 2 1 3 Modified graphene microplates 5 4 6 Compound antioxidants 2 3 1 Flame retardant 10 9 11 Silane coupling agents 3 4 2 lubricant 1 0.5 1.5 Example 1 An antioxidant cable protective sleeve material, the raw materials and their proportions are shown in Table 1.
[0044] The density of linear low-density polyethylene is 0.934 g / cm³. 3 The density of high-density polyethylene is 0.962 g / cm³. 3 The melt index of maleic anhydride-grafted polyethylene at 190℃ / 2.16kg is 2g / 10min, and the grafting rate is 0.6%; the organic peroxide is 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane; the flame retardant is magnesium hydroxide; the silane coupling agent is vinyltris(2-methoxyethoxy)silane; and the lubricant is oleic acid amide.
[0045] The modified graphene microsheets were prepared using the method described in Preparation Example 1; the compounded antioxidants were antioxidant 1010 and antioxidant 168, and the weight ratio of antioxidant 1010 to antioxidant 168 was 1:2.
[0046] A method for preparing an antioxidant cable protective sleeve material includes the following steps: High-density polyethylene, maleic anhydride-grafted polyethylene, organic peroxide, modified graphene microsheets, compound antioxidants, flame retardants, silane coupling agents, and lubricants are added to linear low-density polyethylene and stirred for 10 minutes to obtain a mixture.
[0047] The mixture is fed into a twin-screw extruder and extruded at a temperature of 170℃ and a screw speed of 350r / min to obtain the protective sleeve material.
[0048] Example 2 An antioxidant cable protective sleeve material is different from that in Example 1 in that the raw material ratio of the protective sleeve material is different, and the raw material ratio of the protective sleeve material is shown in Table 1.
[0049] Example 3 An antioxidant cable protective sleeve material is different from that in Example 1 in that the raw material ratio of the protective sleeve material is different, and the raw material ratio of the protective sleeve material is shown in Table 1.
[0050] Example 4 An antioxidant cable protective sleeve material is different from that in Example 1. The raw materials of the protective sleeve material contain different compound antioxidants. The compound antioxidants are antioxidant 1010 and antioxidant 168, and the weight ratio of antioxidant 1010 and antioxidant 168 is 1:1.
[0051] Example 5 An antioxidant cable protective sleeve material differs from that in Example 1 in that the raw materials of the protective sleeve material contain different compound antioxidants, and the compound antioxidants are antioxidant 1010 and antioxidant 168, and the weight ratio of antioxidant 1010 and antioxidant 168 is 1:3.
[0052] Example 6 An antioxidant cable protective sleeve material differs from Example 1 in that the modified graphene microsheets in the raw materials of the protective sleeve material are from a different source, and the modified graphene microsheets are prepared using the method of Preparation Example 2.
[0053] Example 7 An antioxidant cable protective sleeve material differs from Example 1 in that the modified graphene microsheets in the raw materials of the protective sleeve material have a different source, and the modified graphene microsheets are prepared using the method of Preparation Example 3.
[0054] Example 8 An antioxidant cable protective sleeve material differs from Example 1 in that the modified graphene microsheets in the raw materials of the protective sleeve material are from a different source, and the modified graphene microsheets are prepared using the method of Preparation Example 4.
[0055] Comparative Example Comparative Example 1 An antioxidant cable protective sleeve material is different from that in Example 1 in that the raw materials of the protective sleeve material contain different compound antioxidants, and the compound antioxidant is antioxidant 1010.
[0056] Comparative Example 2 An antioxidant cable protective sleeve material is different from that in Example 1 in that the raw materials of the protective sleeve material contain different compound antioxidants, and the compound antioxidant is antioxidant 168.
[0057] Comparative Example 3 An antioxidant cable protective sleeve material differs from Example 1 in that, in the raw materials of the protective sleeve material, an equal amount of graphene micro-silicon flakes replaces the modified graphene micro-flakes.
[0058] Comparative Example 4 An antioxidant cable protective sleeve material differs from Example 1 in that, in the preparation method of modified graphene microsheets, an equal amount of 3-aminopropyltriethoxysilane replaces the pre-prepared monomer and carboxymethyl chitosan in the raw materials of the protective sleeve material.
[0059] Comparative Example 5 An antioxidant cable protective sleeve material differs from Example 1 in that, in the preparation method of modified graphene microsheets, an equal amount of 3-aminopropyltriethoxysilane is used to replace the pre-prepared monomer in the raw materials of the protective sleeve material.
[0060] Comparative Example 6 An antioxidant cable protective sleeve material differs from Example 1 in that, in the preparation method of modified graphene microsheets, an equal amount of pre-prepared monomers are used to replace carboxymethyl chitosan in the raw materials of the protective sleeve material.
[0061] Comparative Example 7 An antioxidant cable protective sleeve material differs from Example 1 in that, in the preparation method of modified graphene microsheets in the raw materials of the protective sleeve material, an equal amount of carboxymethyl chitosan is used to replace the pre-prepared monomer.
[0062] Performance testing (1) Take the protective sleeve materials obtained in Examples 1-8 and Comparative Examples 1-7 respectively, and perform the following performance tests on the protective sleeve materials. The test results are shown in Table 2.
[0063] In particular, the tensile strength of the protective sheath material was tested in accordance with GB / T 2951.11-2008 "General Test Methods for Insulation and Sheath Materials of Cables and Optical Cables - Part 11: General Test Methods for Thickness and Dimensional Measurement and Mechanical Properties".
[0064] According to GB / T2951.12-2008 "General Test Methods for Insulation and Sheath Materials of Cables and Optical Fibers - Part 12: General Test Methods - Thermal Aging Test Method", the protective sheath material was thermally aged for 240 hours at a temperature of 135℃, and the retention rate of thermal aging tensile strength and the loss rate of thermal aging tensile strength were calculated.
[0065] Heat aging tensile strength retention rate (%) = (Tensile strength of protective sleeve material after heat aging / Tensile strength of protective sleeve material before heat aging) × 100%. Heat aging tensile strength loss rate (%) = 100% - Heat aging tensile strength retention rate.
[0066] According to GB / T 3960-2016 "Test Method for Sliding Friction and Wear of Plastics", the mass wear of the protective sleeve material was tested.
[0067] Table 2 Detection Results As shown in Table 2, the protective sleeve material of this application exhibits high tensile strength, ranging from 42.3 to 47.6 MPa, demonstrating its advantage of high tensile strength. Furthermore, after heat aging treatment at 135℃ for 240 hours, it maintains high heat-aged tensile strength and a high heat-aged tensile strength retention rate, with a heat-aged tensile strength of 41.6-47.2 MPa and a heat-aged tensile strength retention rate of 95.6-99.2%. At this point, the heat-aged tensile strength loss rate is 0.8-4.4%, demonstrating its advantage of high aging resistance. Moreover, it exhibits low mass wear, with a mass wear of 11.3-14.6 mg, demonstrating its advantage of high abrasion resistance. The protective sleeve material of this application, through the synergistic effect of the raw materials, possesses the characteristics of high tensile strength, good aging resistance, and high abrasion resistance, meeting market demands.
[0068] Example 1 and Comparative Examples 1-2 were compared. Antioxidant 1010 was added to the protective sleeve material of Comparative Example 1; antioxidant 168 was added to the protective sleeve material of Comparative Example 2; and both antioxidants 1010 and 168 were added to the protective sleeve material of Example 1. This shows that simultaneously adding antioxidants 1010 and 168 to the protective sleeve material, and utilizing their synergistic effect, significantly reduces the loss rate of thermal aging tensile strength and improves the aging resistance of the protective sleeve material.
[0069] Example 1 and Comparative Example 3 were compared. Graphene microflakes were added to the protective sleeve material of Comparative Example 3; modified graphene microflakes were added to the protective sleeve material of Example 1. This shows that modifying the graphene microflakes improves its performance and enhances the properties of the protective sleeve material.
[0070] Example 1 and Comparative Examples 4-7 were compared. The modified graphene microsheets of Comparative Example 4 were obtained by treating graphene microsheets with 3-aminopropyltriethoxysilane; the modified graphene microsheets of Comparative Example 5 were obtained by treating graphene microsheets with 3-aminopropyltriethoxysilane and carboxymethyl chitosan; the modified graphene microsheets of Comparative Example 6 were obtained by treating graphene microsheets with a pre-prepared monomer; the modified graphene microsheets of Comparative Example 7 were obtained by treating graphene microsheets with carboxymethyl chitosan; and the modified graphene microsheets of Example 1 were obtained by treating graphene microsheets with a pre-prepared monomer and carboxymethyl chitosan. This demonstrates that grafting pre-prepared monomers and carboxymethyl chitosan onto the surface of graphene microflakes during the modification process increases the amount of branches and functional groups. This not only improves the dispersibility of the modified graphene microflakes but also enhances their bonding strength and overall integrity, increases tensile strength, reduces mass wear, reduces voids, blocks gas and moisture pathways, and lowers the thermal aging tensile strength loss rate. Consequently, the protective sleeve material exhibits superior tensile strength, aging resistance, and wear resistance.
[0071] It should be noted that the embodiments described above are only for explaining this application and do not constitute any limitation on this application. This application has been described with reference to typical embodiments, but it should be understood that the terms used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to this application within the scope of the claims, and amendments can be made without departing from the scope and spirit of this application. Although the application described herein relates to specific methods, materials, and embodiments, it does not mean that this application is limited to the specific examples disclosed herein; on the contrary, this application can be extended to all other methods and applications with the same function.
Claims
1. An antioxidant cable protective sleeve material, characterized in that: The protective sleeve material is mainly made of the following raw materials in parts by weight: 85-95 parts linear low-density polyethylene, 5-15 parts high-density polyethylene, 4-6 parts maleic anhydride grafted polyethylene, 1-3 parts organic peroxide, 4-6 parts modified graphene microsheets, 1-3 parts compound antioxidant, 9-11 parts flame retardant, 2-4 parts silane coupling agent, and 0.5-1.5 parts lubricant; The compound antioxidants are antioxidant 1010 and antioxidant 168, and the weight ratio of antioxidant 1010 to antioxidant 168 is 1:(1-3). The modified graphene microsheets are obtained by treating graphene microsheets with pre-prepared monomers and carboxymethyl chitosan. The pre-prepared monomers are prepared by 4,4'-carbonyl phthalic anhydride and N-aminoethyl-3-aminopropyltriethoxysilane.
2. The anti-oxidation cable protective sleeve material according to claim 1, characterized in that: The modified graphene microsheets were prepared using the following method: S1. Mix organic solvent and 4,4'-carbonyl phthalic anhydride, and add N-aminoethyl-3-aminopropyltriethoxysilane dropwise. The addition time of N-aminoethyl-3-aminopropyltriethoxysilane is 40-80 min. After the addition is completed, continue stirring for 2-4 h, and then distill under reduced pressure to obtain the pre-prepared monomer for later use. S2. At a temperature of 80-90℃, water and graphene microsheets are mixed. The pre-prepared monomer is added for the first time and stirred for 1-3 hours. The pre-prepared monomer is added for the second time and stirred for 1-3 hours. The pre-prepared monomer is added for the third time and stirred for 1-3 hours. The pH value is adjusted to 9-12. Then, carboxymethyl chitosan and sodium trimetaphosphate are added and stirred for 2-4 hours. The mixture is filtered, washed, and dried to obtain modified graphene microsheets.
3. The anti-oxidation cable protective sleeve material according to claim 2, characterized in that: The weight ratio of the graphene microsheets, the first addition of pre-prepared monomers, the second addition of pre-prepared monomers, the third addition of pre-prepared monomers, and carboxymethyl chitosan is 10:(0.4-0.6):(0.4-0.6):(0.8-1.2):(0.7-1.1).
4. The anti-oxidation cable protective sleeve material according to claim 2, characterized in that: The weight ratio of the graphene microplates to sodium trimetaphosphate is 10:(0.5-1.5).
5. The anti-oxidation cable protective sleeve material according to claim 2, characterized in that: The weight ratio of 4,4'-carbonyl phthalic anhydride to N-aminoethyl-3-aminopropyltriethoxysilane is (9-11):(14-18).
6. The anti-oxidation cable protective sleeve material according to claim 2, characterized in that: The organic solvent is one or more of tetrahydrofuran, dimethyl sulfoxide, cyclohexanone, xylene, toluene, ethanol, and isopropanol.
7. The anti-oxidation cable protective sleeve material according to claim 1, characterized in that: The organic peroxide is one or more of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, dicumyl peroxide, tert-butyl peroxide, and cumyl peroxide neodecanoate.
8. The anti-oxidation cable protective sleeve material according to claim 1, characterized in that: The silane coupling agent is one or more of vinyltris(2-methoxyethoxy)silane, 3-allyloxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and anilinemethyltrimethoxysilane.
9. The anti-oxidation cable protective sleeve material according to claim 1, characterized in that: The flame retardant is one or more of magnesium hydroxide, aluminum hydroxide, zinc borate, and ammonium tripolyphosphate; The lubricant is one or more of calcium stearate, zinc stearate, oleamide, and erucamide.
10. A method for preparing an antioxidant cable protective sleeve material as described in any one of claims 1-9, characterized in that: Includes the following steps: Linear low-density polyethylene, high-density polyethylene, maleic anhydride-grafted polyethylene, organic peroxide, modified graphene microsheets, compound antioxidants, flame retardants, silane coupling agents, and lubricants are mixed and then extruded at a temperature of 160-180℃ to obtain the protective sleeve material.