Waterproof aluminum plastic composite tape for cable and preparation method thereof
By anodizing the aluminum strip with phosphoric acid solution and optimizing the polyolefin material, the problems of poor interfacial adhesion and insufficient water resistance of the aluminum-plastic composite tape were solved, achieving improved high strength and water resistance, making it suitable for cable materials.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-25
- Publication Date
- 2026-03-20
AI Technical Summary
Existing aluminum-plastic composite tapes have poor interfacial adhesion due to polarity differences, which affects the cable strength and water resistance. Furthermore, the introduction of polar groups leads to a decrease in insulation, posing a safety hazard to the cable in high-temperature and high-humidity environments.
By subjecting aluminum strips to phosphoric acid solution anodizing and coupling agent treatment, interfacial properties are improved. Furthermore, by optimizing the polyolefin material composition, including the use of ethylene-acrylic acid copolymer, GMA-EMA copolymer, isocyanate-modified low-density polyethylene, and modified hexagonal boron nitride, a multi-functional cross-linked network is formed, thereby enhancing interfacial bonding strength and water resistance.
It effectively improves the interfacial bonding strength and water resistance of aluminum-plastic composite tape, enhances the overall strength and service life of cables, especially the water resistance in high temperature and high humidity environments.
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Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of aluminum-plastic composite tape, in particular to a water-resistant aluminum-plastic composite tape for cables and a preparation method thereof. BACKGROUND
[0002] The aluminum-plastic composite tape is generally a composite material obtained by compounding an aluminum tape and a plastic such as polyolefin; has the advantages of light weight, moisture resistance, etc., and is widely used in the cable industry.
[0003] At present, due to the existence of polarity difference between the aluminum tape and the polyolefin and other materials, the bonding property of the composite interface is poor, which affects the overall strength of the cable and has limitations for use in some environments. In the prior art, a substance containing a polar group is usually introduced into the polyolefin material to enhance the bonding property of the interface; since the introduction of the substance containing a polar group will cause a decrease in insulation, boron nitride and other substances are introduced to ensure the electrical insulation performance; however, there are the following problems: first, the substance containing a polar group, boron nitride and other components have compatibility problems, which affect the mechanical properties; second, the polar group has hygroscopicity, so that the water resistance of the aluminum-plastic composite tape is insufficient, and the plastic layer is prone to peeling in a humid environment for a long time; and the polyolefin material also has poor heat resistance, and if it is used in a high temperature and high humidity environment, the risk of the cable will be increased and the service life of the cable will be affected.
[0004] In summary, it is of great significance to solve the above problems and prepare a water-resistant aluminum-plastic composite tape for cables. SUMMARY
[0005] The present application aims to provide a water-resistant aluminum-plastic composite tape for cables and a preparation method thereof to solve the problems raised in the background.
[0006] In order to solve the above technical problems, the present application provides the following technical scheme:
[0007] A preparation method of a water-resistant aluminum-plastic composite tape for cables, comprising the following steps:
[0008] Step 1: (1) oil removal and electrolysis of the surface of the aluminum tape, anodic oxidation treatment in a phosphoric acid solution to obtain a pretreated aluminum tape; (2) pretreatment of the pretreated aluminum tape in a coupling agent solution to obtain an interface-modified aluminum tape;
[0009] Step 2: mixing ethylene-acrylic acid copolymer, GMA-EMA copolymer, low-density polyethylene, isocyanate-modified low-density polyethylene, modified hexagonal boron nitride, peroxide initiator, lubricant and antioxidant, and reserving after opening the mill to obtain a polyolefin material;
[0010] Step 3: preheating the interface-modified aluminum tape, setting the polyolefin material on the surface, hot pressing and vulcanization, cooling, trimming to obtain a water-resistant aluminum-plastic composite tape.
[0011] More preferably, the preparation method of the pretreated aluminum strip is: the surface of the aluminum strip is wiped with acetone, then placed in a 10-20wt% perchloric acid-ethanol solution, with a platinum foil as the counter electrode, setting the current to 2.5-3A at room temperature, electrolytic treatment for 120-150 seconds, washing, drying; transferred to a 5-6wt% phosphoric acid-water solution, setting the voltage to 40-60V at room temperature, anodic oxidation for 60-120 minutes, washing, drying, to obtain the pretreated aluminum strip.
[0012] More preferably, the solid content of the coupling agent solution is 10-12wt% ethanol solution; the silane coupling agent includes methyl methacrylate silane coupling agent and mercapto silane coupling agent in a mass ratio of 4-5:1; the volume ratio of the pretreated aluminum strip to the coupling agent solution is 1:4-6.
[0013] More preferably, the raw material of the polyolefin material includes the following components: 43-48 parts by weight of ethylene-acrylic acid copolymer, 8-12 parts by weight of GMA-EMA copolymer, 25-30 parts by weight of low-density polyethylene, 15-20 parts by weight of isocyanate modified low-density polyethylene, 9-12 parts by weight of modified hexagonal boron nitride, 0.05-0.1 parts by weight of peroxide initiator, 0.2-0.3 parts by weight of lubricant, and 0.2-0.3 parts by weight of antioxidant.
[0014] More preferably, the preparation method of the isocyanate modified low-density polyethylene is: low-density polyethylene is added to xylene, isocyanatoethyl methacrylate and peroxide initiator are added, under a nitrogen atmosphere, setting the temperature to 120-125℃ for 4-5 hours of reaction, cooling, washing, and drying to obtain isocyanate group low-density polyethylene; the mass ratio of low-density polyethylene to isocyanatoethyl methacrylate is 1:0.1-0.2.
[0015] More preferably, the preparation method of the modified hexagonal boron nitride is:
[0016] (1) hexagonal boron nitride and epoxy silane coupling agent are sequentially added to 40-50% ethanol aqueous solution, stirring at 60-70℃ for 24 hours, washing, and drying to obtain epoxidized boron nitride; the epoxidized boron nitride is added to tetrahydrofuran, 4-aminobiphenyl and 3-amino-1-propanol are added, stirring at 60-70℃ for 4-6 hours, washing, and drying to obtain intercalated boron nitride; the intercalated boron nitride is uniformly dispersed in toluene, triethylamine is added and stirred uniformly; under ice bath, bromoisobutyryl bromide-toluene solution is added dropwise, stirring at room temperature overnight, centrifugation, washing, and drying to obtain bromine-based boron nitride;
[0017] (2) ethylene-acrylic acid copolymer, triethylamine, hydroquinone are added into DMF, under nitrogen atmosphere, temperature is raised to 50~60 DEG C, perilla aldehyde-DMF solution is added dropwise, temperature is set to 65~80 DEG C, reaction is carried out for 4~8 hours, and then washing and drying are carried out to obtain modified ethylene-acrylic acid copolymer;
[0018] (3) bromine-based boron nitride is added into methanol aqueous solution, under nitrogen atmosphere, modified ethylene-acrylic acid copolymer and copper bromide are added, and then reaction is carried out for 48 hours in dark, and then washing and drying are carried out to obtain modified hexagonal boron nitride.
[0019] More preferably, in the raw material of the epoxidized boron nitride, the mass ratio of boron nitride and epoxy silane coupling agent is 1:0.2~0.5; in the raw material of the intercalated boron nitride, the mass ratio of epoxidized boron nitride, 4-amino diphenyl and 3-amino-1-propanol is 1:0.2~0.3:0.2~0.3; in the raw material of the bromine-based boron nitride, the mass ratio of intercalated boron nitride and bromo isobutyryl bromide is 1:0.1~0.2;
[0020] In the raw material of the modified ethylene-acrylic acid copolymer, the mass ratio of ethylene-acrylic acid copolymer and perilla aldehyde is 1:0.2~0.3;
[0021] In the raw material of the modified hexagonal boron nitride, the mass ratio of bromine-based boron nitride and modified ethylene-acrylic acid copolymer is 1:2.
[0022] More preferably, the temperature of the open mill is 135~145 DEG C; the preheating temperature is 120~130 DEG C; the hot pressing vulcanization temperature is 160~180 DEG C, the pressure is 8~12 Mpa, and the time is 5~15 minutes;
[0023] More preferably, the thickness of the aluminum strip is 0.1~0.2 mm; and the thickness of the polyolefin material is set to 0.05~0.15 mm.
[0024] A preparation method of a water-resistant aluminum plastic composite strip for cable.
[0025] Compared with the prior art, the present application has the following beneficial effects: first, the aluminum strip is treated in a specific manner, which effectively improves the surface properties of the aluminum strip and promotes the interfacial adhesion between the aluminum strip and the polyolefin material; second, the components of the polyolefin material are optimized and modified, which effectively improves the interfacial adhesion between the aluminum strip and the polyolefin material and improves the water resistance and mechanical properties.
[0026] In this scheme, the interface-modified aluminum strip is anodized in a phosphoric acid solution to form a porous oxide layer, giving the surface a certain roughness to promote interfacial bonding of the polyolefin material and improve interfacial strength. Simultaneously, a silane coupling agent containing methacrylate and mercapto groups is used to react and crosslink with the groups contained in the polyolefin material, further improving interfacial strength. Compared to using a sulfuric acid solution, using a phosphoric acid solution results in better interfacial adhesion because the micropores formed by the phosphoric acid oxide layer have a larger diameter and more uniform distribution, which facilitates the penetration of the polyolefin melt, enhances mechanical interlocking (anchoring effect), and increases the effective contact area, thereby improving physical bonding.
[0027] In this design, the polyolefin material primarily consists of ethylene-acrylic acid copolymer and low-density polyethylene, compounded with GMA-EMA copolymer and isocyanate-modified low-density polyethylene to form a multi-functional cross-linked network. This improves material compatibility, enhances interfacial adhesion, effectively promotes cross-linked network formation, reduces polar groups, and enhances water resistance. Furthermore, the introduction of modified hexagonal boron nitride effectively ensures insulation while improving mechanical properties, heat resistance, and water resistance under hot and humid conditions; thus enhancing the overall performance and service life of the water-resistant aluminum-plastic composite tape.
[0028] The inclusion of GMA-EMA copolymer can partially replace ethylene-acrylic acid copolymer. Its epoxy groups can crosslink with the thiol groups on the interface-modified aluminum tape and also with the carboxyl groups of the ethylene-acrylic acid copolymer, improving the crosslinking network and enhancing water resistance. However, since the crosslinking of epoxy groups and carboxyl groups produces hydroxyl groups, water-absorbing groups remain. Therefore, isocyanate-modified low-density polyethylene is introduced to effectively consume hydroxyl groups, improving water resistance while strengthening the crosslinking network and enhancing mechanical properties. Simultaneously, the sequential crosslinking of the multi-functional crosslinking network effectively buffers crosslinking stress, effectively improving the overall strength of the water-resistant aluminum-plastic composite tape.
[0029] Hexagonal boron nitride, due to its dispersibility and interfacial compatibility, is first epoxidized and then intercalated with epoxy groups or surface-grafted with 4-aminobiphenyl and 3-amino-1-propanol to obtain intercalated boron nitride. The introduction of biphenyl structure and propane chain effectively increases the interlayer spacing, improves the dispersibility of boron nitride, and enhances heat resistance. Simultaneously, the hydroxyl groups on the intercalated boron nitride react with bromoisobutyryl bromide to form bromoboron nitride, allowing it to react with unsaturated groups. Thus, the modified ethylene-acrylic acid copolymer grafted with perillaldehyde contains vinyl groups that react with bromoboron nitride. Utilizing the compatibility of the modified ethylene-acrylic acid copolymer, the modified hexagonal boron nitride is effectively and uniformly dispersed in the matrix material, improving both mechanical strength and heat resistance, as well as heat resistance under hot and humid conditions. Detailed Implementation
[0030] The technical solutions in the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all the other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the present application.
[0031] It should be noted that the following parts are by weight, and there is no special restriction on the purchase manufacturer of all the raw materials involved in the present application, which exemplarily includes: in the following embodiments, the trade name of ethylene-acrylic acid copolymer is CS-1, the trade name of low-density polyethylene is 0220KJ, GMA-EMA copolymer is glycidyl methacrylate grafted ethylene-methyl acrylate copolymer, the trade name is SH022, the article number of hexagonal boron nitride is hexagonal boron nitride, the brand is Xi'an Qiyue; the above-mentioned and the raw materials involved are all commercially available.
[0032] The preparation method of the isocyanate-modified low-density polyethylene is as follows: 10 parts of low-density polyethylene is added to 70 parts of xylene, 2 parts of isocyanatoethyl methacrylate and 0.2 parts of peroxide initiator DCP are added, the temperature is set to 120℃ under nitrogen atmosphere, and the reaction is carried out for 5 hours, then cooling, washing and drying are carried out to obtain isocyanate-modified low-density polyethylene;
[0033] The preparation method of the modified hexagonal boron nitride is as follows: (1) 10 parts of hexagonal boron nitride and 4 parts of epoxy silane coupling agent KH560 are sequentially added to 50 parts of 50% ethanol aqueous solution, stirring is carried out at 60℃ for 24 hours, then washing and drying are carried out to obtain epoxidized boron nitride; 10 parts of epoxidized boron nitride is added to 50 parts of tetrahydrofuran, 0.2 parts of 4-aminobiphenyl and 0.3 parts of 3-amino-1-propanol are added, stirring is carried out at 70℃ for 4 hours, then washing and drying are carried out to obtain intercalated boron nitride; 10 parts of intercalated boron nitride is uniformly dispersed in 60 parts of toluene, 1 part of triethylamine is added and uniformly stirred; under ice bath, 15wt% toluene solution containing 0.15 parts of bromoisobutyryl bromide is added dropwise, stirring is carried out at room temperature overnight, then centrifugation, washing and drying are carried out to obtain bromine-based boron nitride; (2) 10 parts of ethylene-acrylic acid copolymer, 1 part of triethylamine and 0.5 parts of hydroquinone are added to 50 parts of DMF, the temperature is raised to 50℃ under nitrogen atmosphere, 30wt% DMF solution containing 3 parts of perilla aldehyde is added dropwise, the temperature is set to 70℃, and the reaction is carried out for 6 hours, then washing and drying are carried out to obtain modified ethylene-acrylic acid copolymer; (3) 5 parts of bromine-based boron nitride is added to 50 parts of methanol aqueous solution, 10 parts of modified ethylene-acrylic acid copolymer and copper bromide are added under nitrogen atmosphere; the reaction is carried out for 48 hours in the dark, then washing and drying are carried out to obtain modified hexagonal boron nitride.
[0034] Embodiment 1: A preparation method of a water-resistant aluminum plastic composite tape for cables, comprising the following steps:
[0035] Step 1: (1) The surface of the aluminum strip with a thickness of 0.15 mm was wiped with acetone, then placed in a 10wt% perchloric acid-ethanol solution, with a platinum foil as the counter electrode, set the current to 3A at room temperature, electrolytic treatment for 120 seconds, washed, dried; transferred to a 5wt% phosphoric acid-water solution, set the voltage to 50V at room temperature, anodized for 100 minutes, washed, dried, to obtain a pretreated aluminum strip; (2) The pretreated aluminum strip was placed in an ethanol solution with a solid content of 10wt% (50wt% ethanol aqueous solution), the volume ratio of the two was 1:5, and the pretreatment time was 4 hours, to obtain an interface modified aluminum strip; the silane coupling agent was composed of methyl methacrylate silane coupling agent KH570 and mercapto silane coupling agent KH590 with a mass ratio of 5:1;
[0036] Step 2: 45 parts of ethylene-acrylic acid copolymer, 10 parts of GMA-EMA copolymer, 26 parts of low density polyethylene, 19 parts of isocyanate modified low density polyethylene, 10 parts of modified hexagonal boron nitride, 0.1 part of peroxide initiator DCP, 0.2 part of lubricant liquid paraffin, 0.2 part of antioxidant 1178 were mixed and prepared by opening at 140°C, to obtain a polyolefin material;
[0037] Step 3: The interface modified aluminum strip was preheated to 120°C, the surface was provided with 0.1mm polyolefin material, and hot pressing vulcanization was carried out at a temperature of 160°C and a pressure of 10Mpa for 10 minutes, then cooled, trimmed, to obtain a water-resistant aluminum plastic composite strip.
[0038] Example 2: A method for preparing a water-resistant aluminum plastic composite strip for cables, comprising the following steps:
[0039] Step 1: (1) The surface of the aluminum strip with a thickness of 0.15 mm was wiped with acetone, then placed in a 10wt% perchloric acid-ethanol solution, with a platinum foil as the counter electrode, set the current to 3A at room temperature, electrolytic treatment for 120 seconds, washed, dried; transferred to a 5wt% phosphoric acid-water solution, set the voltage to 50V at room temperature, anodized for 100 minutes, washed, dried, to obtain a pretreated aluminum strip; (2) The pretreated aluminum strip was placed in an ethanol solution with a solid content of 10wt% (50wt% ethanol aqueous solution), the volume ratio of the two was 1:5, and the pretreatment time was 4 hours, to obtain an interface modified aluminum strip; the silane coupling agent was composed of methyl methacrylate silane coupling agent KH570 and mercapto silane coupling agent KH590 with a mass ratio of 4:1;
[0040] Step 2: 43 parts of ethylene-acrylic acid copolymer, 12 parts of GMA-EMA copolymer, 30 parts of low density polyethylene, 15 parts of isocyanate modified low density polyethylene, 10 parts of modified hexagonal boron nitride, 0.1 part of peroxide initiator DCP, 0.2 part of lubricant liquid paraffin, 0.2 part of antioxidant 1178 were mixed and prepared by opening at 140°C, to obtain a polyolefin material;
[0041] Step 3: The interfacial modification aluminum strip is preheated to 120℃, and a 0.1mm polyolefin material is arranged on the surface. Hot pressing vulcanization is performed at a temperature of 160℃ and a pressure of 10Mpa for 10 minutes, and then cooling, trimming, and obtaining a water-resistant aluminum-plastic composite strip.
[0042] Example 3: A preparation method of a water-resistant aluminum-plastic composite strip for a cable, comprising the following steps:
[0043] Step 1: (1) The aluminum strip with a thickness of 0.15mm is wiped with acetone, and then placed in a 10wt% perchloric acid-ethanol solution. A platinum foil is used as a counter electrode, and an electric current of 3A is set at room temperature. The electrolytic treatment is performed for 120 seconds, and then washed, dried, and transferred to a 5wt% phosphoric acid-water solution. A voltage of 50V is set at room temperature, and anodic oxidation is performed for 100 minutes. Then, the aluminum strip is washed, dried, and obtained as a pretreated aluminum strip; (2) The pretreated aluminum strip is placed in an ethanol solution with a solid content of 10wt% (50wt% ethanol aqueous solution), and the volume ratio of the two is 1:5. The pretreatment is performed for 4 hours, and an interfacial modification aluminum strip is obtained. The silane coupling agent is composed of methyl methacrylate silane coupling agent KH570 and mercapto silane coupling agent KH590 with a mass ratio of 5:1;
[0044] Step 2: 48 parts of ethylene-acrylic acid copolymer, 8 parts of GMA-EMA copolymer, 25 parts of low-density polyethylene, 18 parts of isocyanate-modified low-density polyethylene, 12 parts of modified hexagonal boron nitride, 0.1 parts of peroxide initiator DCP, 0.2 parts of lubricant liquid paraffin, and 0.2 parts of antioxidant 1178 are mixed and prepared by opening the mill at 140℃, and a polyolefin material is obtained;
[0045] Step 3: The interfacial modification aluminum strip is preheated to 120℃, and a 0.1mm polyolefin material is arranged on the surface. Hot pressing vulcanization is performed at a temperature of 160℃ and a pressure of 10Mpa for 10 minutes, and then cooling, trimming, and obtaining a water-resistant aluminum-plastic composite strip.
[0046] Comparative Example 1: An anodic oxidation treatment is performed using a 5wt% sulfuric acid-water solution; the rest is the same as Example 1; and the specific process is as follows:
[0047] Step 1: (1) The surface of the aluminum tape with a thickness of 0.15 mm was wiped with acetone and then placed in a 10wt% perchloric acid-ethanol solution with a platinum foil as the counter electrode. The current was set to 3A at room temperature, and the electrolytic treatment was performed for 120 seconds. After washing and drying, it was transferred to a 5wt% sulfuric acid-water solution, and the voltage was set to 50V at room temperature. Anodic oxidation was performed for 100 minutes, followed by washing, drying, and obtaining a pretreated aluminum tape; (2) The pretreated aluminum tape was placed in an ethanol solution with a solid content of 10wt% (50wt% ethanol aqueous solution) at a volume ratio of 1:5 for pretreatment for 4 hours, obtaining an interface-modified aluminum tape; the silane coupling agent was composed of methyl methacrylate silane coupling agent KH570 and mercapto silane coupling agent KH590 at a mass ratio of 5:1;
[0048] Step 2: 45 parts of ethylene-acrylic acid copolymer, 10 parts of GMA-EMA copolymer, 26 parts of low-density polyethylene, 19 parts of isocyanate-modified low-density polyethylene, 10 parts of modified hexagonal boron nitride, 0.1 part of peroxide initiator DCP, 0.2 parts of lubricant liquid paraffin, and 0.2 parts of antioxidant 1178 were mixed and prepared for use after opening and kneading at 140°C, obtaining a polyolefin material;
[0049] Step 3: The interface-modified aluminum tape was preheated to 120°C, and a 0.1mm polyolefin material was placed on the surface. Hot pressing vulcanization was performed at a temperature of 160°C and a pressure of 10Mpa for 10 minutes, followed by cooling, trimming, and obtaining a water-resistant aluminum plastic composite tape.
[0050] Comparative Example 2: The GMA-EMA copolymer was replaced with ethylene-acrylic acid copolymer, and the isocyanate-modified low-density polyethylene was replaced with low-density polyethylene; the rest was the same as Example 1; the specific process was as follows:
[0051] Step 1: (1) The surface of the aluminum tape with a thickness of 0.15 mm was wiped with acetone and then placed in a 10wt% perchloric acid-ethanol solution with a platinum foil as the counter electrode. The current was set to 3A at room temperature, and the electrolytic treatment was performed for 120 seconds. After washing and drying, it was transferred to a 5wt% sulfuric acid-water solution, and the voltage was set to 50V at room temperature. Anodic oxidation was performed for 100 minutes, followed by washing, drying, and obtaining a pretreated aluminum tape; (2) The pretreated aluminum tape was placed in an ethanol solution with a solid content of 10wt% (50wt% ethanol aqueous solution) at a volume ratio of 1:5 for pretreatment for 4 hours, obtaining an interface-modified aluminum tape; the silane coupling agent was composed of methyl methacrylate silane coupling agent KH570 and mercapto silane coupling agent KH590 at a mass ratio of 5:1;
[0052] Step 2: 55 parts of ethylene-acrylic acid copolymer, 45 parts of low-density polyethylene, 10 parts of modified hexagonal boron nitride, 0.1 part of peroxide initiator DCP, 0.2 parts of lubricant liquid paraffin, and 0.2 parts of antioxidant 1178 were mixed and prepared for use after opening and kneading at 140°C, obtaining a polyolefin material;
[0053] Step 3: The interface modified aluminum strip is preheated to 120℃, and the surface is provided with 0.1mm polyolefin material. Hot vulcanization is performed at a temperature of 160℃ and a pressure of 10Mpa for 10 minutes. After cooling, trimming is performed to obtain a water-resistant aluminum-plastic composite strip.
[0054] Comparative Example 3: The isocyanate modified low-density polyethylene is replaced with low-density polyethylene; the rest is the same as Example 1; and the specific process is as follows:
[0055] Step 1: (1) The surface of the aluminum strip with a thickness of 0.15mm is wiped with acetone, and then placed in a 10wt% perchloric acid-ethanol solution. A platinum foil is used as a counter electrode, and an electric current of 3A is set at room temperature. The electrolytic treatment is performed for 120 seconds, and then the aluminum strip is cleaned and dried. The pretreated aluminum strip is then transferred to a 5wt% phosphoric acid-water solution, and a voltage of 50V is set at room temperature. Anodic oxidation is performed for 100 minutes, and then the aluminum strip is cleaned and dried to obtain a pretreated aluminum strip; (2) The pretreated aluminum strip is placed in an ethanol solution with a solid content of 10wt% (50wt% ethanol aqueous solution) at a volume ratio of 1:5. The pretreated aluminum strip is pretreated for 4 hours to obtain an interface modified aluminum strip. The silane coupling agent is composed of methacrylate silane coupling agent KH570 and mercapto silane coupling agent KH590 at a mass ratio of 5:1;
[0056] Step 2: 45 parts of ethylene-acrylic acid copolymer, 10 parts of GMA-EMA copolymer, 45 parts of low-density polyethylene, 10 parts of modified hexagonal boron nitride, 0.1 parts of peroxide initiator DCP, 0.2 parts of lubricant liquid paraffin, and 0.2 parts of antioxidant 1178 are mixed and prepared by opening the mill at 140℃. The polyolefin material is obtained.
[0057] Step 3: The interface modified aluminum strip is preheated to 120℃, and the surface is provided with 0.1mm polyolefin material. Hot vulcanization is performed at a temperature of 160℃ and a pressure of 10Mpa for 10 minutes. After cooling, trimming is performed to obtain a water-resistant aluminum-plastic composite strip.
[0058] Comparative Example 4: 10 parts of modified hexagonal boron nitride are replaced with 3 parts of modified hexagonal boron nitride; the rest is the same as Example 1; and the specific process is as follows:
[0059] Step 1: (1) The surface of the aluminum tape with a thickness of 0.15 mm was wiped with acetone and then placed in a 10 wt% perchloric acid-ethanol solution, using a platinum foil as the counter electrode, and electrolytic treatment was performed at room temperature with a current of 3 A for 120 seconds, followed by washing, drying, and transferring to a 5 wt% phosphoric acid-water solution, and anodic oxidation was performed at room temperature with a voltage of 50 V for 100 minutes, followed by washing, drying, and obtaining a pretreated aluminum tape; (2) The pretreated aluminum tape was placed in an ethanol solution with a solid content of 10 wt% (50 wt% ethanol aqueous solution) at a volume ratio of 1:5 for 4 hours, and an interface-modified aluminum tape was obtained; the silane coupling agent was composed of methyl methacrylate silane coupling agent KH570 and mercapto silane coupling agent KH590 at a mass ratio of 5:1;
[0060] Step 2: 45 parts of ethylene-acrylic acid copolymer, 10 parts of GMA-EMA copolymer, 26 parts of low-density polyethylene, 19 parts of isocyanate-modified low-density polyethylene, 3 parts of modified hexagonal boron nitride, 0.1 parts of peroxide initiator DCP, 0.2 parts of lubricant liquid paraffin, and 0.2 parts of antioxidant 1178 were mixed and prepared by opening the mill at 140°C, and a polyolefin material was obtained;
[0061] Step 3: The interface-modified aluminum tape was preheated to 120°C, and a 0.1 mm polyolefin material was arranged on the surface, and hot pressing vulcanization was performed at a temperature of 160°C and a pressure of 10 Mpa for 10 minutes, followed by cooling, trimming, and obtaining a water-resistant aluminum-plastic composite tape.
[0062] Performance Test 1: The water-resistant aluminum-plastic composite tapes prepared in the examples and comparative examples were tested for related properties; according to the standard method of GB / T8808, the water-resistant aluminum-plastic composite tapes were subjected to 180° peeling test at a tensile rate of 300 mm / min, and the peeling strength A was obtained; then they were placed in 68°C water for 168 hours, and the peeling strength B was further detected; the data are shown in the following table:
[0063]
[0064] Conclusion: From the data in the above table, it can be seen that by treating the aluminum tape in a specific manner and optimizing and modifying the components of the polyolefin material, the interfacial strength and water resistance of the water-resistant aluminum-plastic composite tape are effectively improved. In Comparative Example 1, the use of sulfuric acid-water solution anodic oxidation treatment caused the interface to have decreased interlocking properties, resulting in decreased peeling strength; in Comparative Example 2, the absence of GMA-EMA copolymer and isocyanate-modified low-density polyethylene resulted in decreased crosslinking degree and increased polar groups, leading to decreased water resistance; in Comparative Example 3, the absence of isocyanate-modified low-density polyethylene resulted in decreased peeling strength and water resistance; and in Comparative Example 4, the absence of modification of hexagonal boron nitride resulted in decreased interfacial properties, affecting the peeling strength and water resistance.
[0065] Finally, it should be noted that the above only describes the preferred embodiments of the present application and is not intended to limit the present application. Although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art will appreciate that the technical solutions described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalent ones. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims
1. A method for preparing a water-resistant aluminum-plastic composite tape for cables, characterized in that: Includes the following steps: Step 1: (1) Degrease and electrolyze the surface of the aluminum strip, and anodize it in phosphoric acid solution to obtain a pretreated aluminum strip; (2) The pretreated aluminum strip is pretreated in a coupling agent solution to obtain an interface-modified aluminum strip; Step 2: Mix ethylene-acrylic acid copolymer, GMA-EMA copolymer, low-density polyethylene, isocyanate-modified low-density polyethylene, modified hexagonal boron nitride, peroxide initiator, lubricant, and antioxidant, and then grind them for later use to obtain polyolefin material; Step 3: Preheat the interface-modified aluminum strip, apply polyolefin material to the surface, hot press vulcanize, cool, and trim to obtain a water-resistant aluminum-plastic composite strip; The raw materials of the polyolefin material include the following components by weight: 43-48 parts ethylene-acrylic acid copolymer, 8-12 parts GMA-EMA copolymer, 25-30 parts low-density polyethylene, 15-20 parts isocyanate-modified low-density polyethylene, 9-12 parts modified hexagonal boron nitride, 0.05-0.1 parts peroxide initiator, 0.2-0.3 parts lubricant, and 0.2-0.3 parts antioxidant; The method for preparing isocyanate-modified low-density polyethylene is as follows: low-density polyethylene is added to xylene, followed by the addition of isocyanate ethyl methacrylate and a peroxide initiator. The reaction is carried out under a nitrogen atmosphere at a temperature of 120-125°C for 4-5 hours. The mixture is then cooled, washed, and dried to obtain isocyanate-based low-density polyethylene. The modified hexagonal boron nitride is prepared as follows: (1) Hexagonal boron nitride and epoxy silane coupling agent are added sequentially to a 40-50% ethanol aqueous solution, stirred at 60-70°C for 24 hours, washed and dried to obtain epoxide boron nitride; epoxide boron nitride is added to tetrahydrofuran, 4-aminobiphenyl and 3-amino-1-propanol are added, stirred at 60-70°C for 4-6 hours, washed and dried to obtain intercalated boron nitride; intercalated boron nitride is uniformly dispersed in toluene, triethylamine is added and stirred evenly; under ice bath, bromoisobutyryl bromide-toluene solution is added dropwise. (1) Stir at room temperature overnight, centrifuge, wash and dry to obtain bromoboron nitride; (2) Add ethylene-acrylic acid copolymer, triethylamine and hydroquinone to DMF, heat to 50~60℃ under nitrogen atmosphere, add perillaldehyde-DMF solution, set the temperature to 65~80℃, react for 4~8 hours, wash and dry to obtain modified ethylene-acrylic acid copolymer; (3) Add bromoboron nitride to methanol aqueous solution, add modified ethylene-acrylic acid copolymer and copper bromide under nitrogen atmosphere; react in the dark for 48 hours, wash and dry to obtain modified hexagonal boron nitride.
2. The method for preparing a water-resistant aluminum-plastic composite tape for cables according to claim 1, characterized in that: The method for preparing the pretreated aluminum strip is as follows: wipe the surface of the aluminum strip with acetone, then place it in a 10-20 wt% perchloric acid-ethanol solution, use platinum foil as the counter electrode, set the current to 2.5-3A at room temperature, electrolyze for 120-150 seconds, clean and dry; transfer it to a 5-6 wt% phosphoric acid-water solution, set the voltage to 40-60V at room temperature, anodize for 60-120 minutes, clean and dry to obtain the pretreated aluminum strip.
3. The method for preparing a water-resistant aluminum-plastic composite tape for cables according to claim 1, characterized in that: The coupling agent solution has a solid content of 10-12 wt% ethanol solution; the silane coupling agent includes methacrylate silane coupling agent and mercaptosilane coupling agent with a mass ratio of 4-5:1; the volume ratio of pretreated aluminum strip to coupling agent solution is 1:4-6.
4. The method for preparing a water-resistant aluminum-plastic composite tape for cables according to claim 1, characterized in that: The mass ratio of low-density polyethylene to isocyanate methacrylate is 1:0.1~0.
2.
5. The method for preparing a water-resistant aluminum-plastic composite tape for cables according to claim 1, characterized in that: In the raw materials for boron nitride epoxide, the mass ratio of boron nitride to epoxy silane coupling agent is 1:0.2~0.5; in the raw materials for intercalated boron nitride, the mass ratio of boron nitride epoxide to 4-aminobiphenyl and 3-amino-1-propanol is 1:0.2~0.3:0.2~0.3; in the raw materials for bromoboron nitride, the mass ratio of intercalated boron nitride to bromoisobutyryl bromide is 1:0.1~0.
2. In the raw materials of the modified ethylene-acrylic acid copolymer, the mass ratio of ethylene-acrylic acid copolymer to perillaldehyde is 1:0.2~0.3; In the raw materials for the modified hexagonal boron nitride, the mass ratio of bromo-boron nitride to the modified ethylene-acrylic acid copolymer is 1:
2.
6. The method for preparing a water-resistant aluminum-plastic composite tape for cables according to claim 1, characterized in that: The initial mixing temperature is 135~145℃; the preheating temperature is 120~130℃; the hot pressing vulcanization temperature is 160~180℃, the pressure is 8~12Mpa, and the time is 5~15 minutes.
7. The method for preparing a water-resistant aluminum-plastic composite tape for cables according to claim 1, characterized in that: The aluminum strip has a thickness of 0.1~0.2mm; the polyolefin material has a thickness of 0.05~0.15mm.
8. The water-resistant aluminum-plastic composite tape prepared by the method for preparing a water-resistant aluminum-plastic composite tape for cables according to any one of claims 1 to 7.
Citation Information
Patent Citations
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