Wear-resistant, oil-resistant and flame-retardant polyolefin cable material and preparation method thereof

Abstract

The present invention relates to the technical field of cable materials, and discloses a wear-resistant, oil-resistant and flame-retardant polyolefin cable material and a preparation method thereof; the raw material components, by weight, include 90 to 100 parts of polyolefin resin, 0.5 to 5 parts of antioxidant, 0.5 to 5 parts of dispersant, 2 to 6 parts of lubricant, 15 to 30 parts of reinforcing agent, and 30 to 50 parts of modified compound; the modified compound is obtained by modifying flame-retardant filler and wear-resistant filler. The present invention uses EVA in combination with other polyolefin resins to make the cable material have the purposes of oil resistance, good material compatibility, and improved repeated bending performance. By grafting whiskers with HNTs, not only can the breakage of whiskers be avoided, but also the whiskers and HNTs are connected by covalent bonds, which can further improve their wear resistance; the cable material provided by the present invention has the effects of oil resistance, wear resistance, and flame retardancy.

Description

Technical Field

[0001] The invention relates to the technical field of cable materials, in particular to a wear-resistant, oil-resistant and flame-retardant polyolefin cable material and a preparation method thereof. Background Art

[0002] Polyolefin cable material is a commonly used cable insulation material. The raw material polyolefin material has excellent insulation performance, heat resistance and chemical corrosion resistance, and is widely used in power cables, communication cables and optical cables. Halogen-containing flame-retardant cable materials have always dominated the cable materials due to their high flame-retardant efficiency, good processing performance and low price. However, cables containing halogens will produce toxic and harmful gases when burned, which can easily cause suffocation of people in the event of a fire. Based on this, low-smoke halogen-free flame-retardant cables have gradually become the main force in the cable market.

[0003] Low-smoke halogen-free base materials usually include EVA, polyethylene (PE), polypropylene (PP), ethylene-propylene rubber (EPR), etc. However, PE, PP, and EPR have poor compatibility with halogen-free flame retardants with strong polarity. The addition of halogen-free flame retardants will cause the mechanical properties of the materials to deteriorate. At the same time, these materials have poor oil resistance and it is difficult to meet the application of cables in complex environments. In addition, wear-resistant agents are added to low-smoke halogen-free cable materials to improve the wear resistance of cable materials to prevent damage to wires when dragging wires. Wear-resistant agents are also inorganic fillers, and their compatibility with cable material base materials is poor, which will also lead to the problem of limited improvement in wear resistance. Summary of the invention

[0004] Technical problems solved by the present invention:

[0005] Aiming at the deficiencies of the prior art, a wear-resistant, oil-resistant and flame-retardant polyolefin cable material is provided.

[0006] The technical solution adopted by the present invention is:

[0007] In view of the above technical problems, the object of the present invention is to provide a wear-resistant, oil-resistant and flame-retardant polyolefin cable material and a preparation method thereof.

[0008] Based on this, the specific implementation plan is:

[0009] A wear-resistant, oil-resistant and flame-retardant polyolefin cable material, wherein the raw material components, by weight, include 90-100 parts of polyolefin resin, 0.5-5 parts of antioxidant, 0.5-5 parts of dispersant, 2-6 parts of lubricant, 15-30 parts of reinforcing agent, and 30-50 parts of modified compound; the modified compound is obtained by modifying flame-retardant filler and wear-resistant filler. In the present invention, the polyolefin resin includes ethylene-vinyl acetate copolymer, ethylene-butene copolymer and high-density polyethylene, and the ratio of the three is 4-6:0.8-1.8:2-4.

[0010] In the present invention, the antioxidant includes at least one of antioxidant 2246 , antioxidant 1010 , antioxidant 1024 , antioxidant 1036 , and antioxidant 300 .

[0011] In the present invention, vinyltriethoxysilane is selected as the dispersant.

[0012] In the present invention, the reinforcing agent is carbon black or white carbon black.

[0013] In the present invention, the lubricant includes at least one of zinc stearate, silicone masterbatch, polyethylene wax, paraffin wax and calcium stearate.

[0014] In the present invention, the flame retardant filler mentioned in the modified composite may be halloysite nanotubes (HNTs), and the wear-resistant filler mentioned in the modified composite may be at least one of barium sulfate whiskers, calcium carbonate whiskers, and calcium sulfate whiskers.

[0015] In the present invention, the preparation method of the modified composite is as follows: (1) HNTs are placed in a H2O2 solution, boiled for 2 hours, separated, washed to obtain HNTs-1, HNTs-1 is dispersed in toluene, treated with n-octyltriethoxysilane, and then washed and dried to obtain HNTs-2. HNTs-2 is dispersed in a ferric chloride / ferrous chloride solution and ultrasonically treated at 30W for 10 to 30 minutes. HNTs-2 and Fe 2+ / Fe 3+ The mass ratio of ammonia to Fe is 1:0.1-0.2, and then ammonia water is added to deposit Fe, and the mixture is placed at 85℃ for 8h. The concentration of ammonia water is 8mol / L. 2+ / Fe 3+ The molar ratio is 1:10. Then, HNTs-3 is obtained by washing and drying. (2) After adjusting the pH value of HNTs-3 to 7.2-7.6, HNTs-3 is placed in a dopamine aqueous solution, ultrasonically dispersed at 80W for 30-60min, centrifuged, washed, and HNTs-4 is obtained; wherein, the mass ratio of HNTs-3 to dopamine is 1:0.1-0.5; HNTs-4 is placed in a PEI aqueous solution, ultrasonically treated at 60W for 4-8h, filtered, and dried to obtain HNTs-4@PEI. The whiskers are placed in an acid solution for a period of time (65℃, 5h), then washed and dried to obtain whiskers-1. The acid solution is a mixture of concentrated sulfuric acid and concentrated nitric acid, with a volume ratio of 1:1. HNTs-4@PEI and whisker-1 were placed in Tris buffer and ultrasonicated at 40W for 4h, filtered and dried to obtain HNTs-4@PEI@whisker-1, wherein the mass ratio of HNTs-4:PEI:whisker-1 was 1 to 2:2:1, and a modified composite was obtained.

[0016] Second, the present invention provides a method for preparing the aforementioned wear-resistant, oil-resistant and flame-retardant polyolefin cable material, comprising the following steps:

[0017] After the polyolefin resin is mixed, an antioxidant, a dispersant, a lubricant, a modified compound, and a reinforcing agent are added, mixed, extruded, and granulated to obtain a cable material; the preparation process is carried out in a mixer. Mixing: 150-170°C, 10-30min; blending: 300-600r / min, 5-20min.

[0018] The technical mechanism and beneficial effects adopted by the present invention are as follows:

[0019] By combining EVA with other polyolefin resins, the cable material can be made oil-resistant, have good material compatibility, and improve repeated bending performance. The modified composites of flame-retardant fillers and wear-resistant fillers can improve the compatibility of fillers with matrix resins, thereby avoiding the problem of uneven dispersion; iron oxides are loaded in HNTs to achieve the purpose of synergistic flame retardancy; the traditional method of adding whiskers to improve wear resistance has a poor effect of improving wear resistance due to the easy breakage of whiskers during the mixing process. By grafting whiskers with HNTs, not only can the breakage of whiskers be avoided, but also the whiskers and HNTs are connected by covalent bonds, which can further improve their wear resistance. In addition, due to the use of a variety of matrix resins, it is inevitable that the compatibility of additives with matrix resins will be caused. By using PEI to graft whiskers with HNTs, the compatibility with the matrix resin can also be improved. PEI can also improve the thermal decomposition problem of cable materials, thereby improving the purpose of flame retardancy. DETAILED DESCRIPTION

[0020] In order to make the purpose, technical scheme and advantages of the embodiments of the present invention clearer, the technical scheme in the embodiments of the present invention will be described clearly and completely below. If the specific conditions are not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially.

[0021] <Example>

[0022] Example 1

[0023] This embodiment provides a method for preparing a wear-resistant, oil-resistant and flame-retardant polyolefin cable material, which is characterized by comprising the following steps:

[0024] Preparation of multi-scale micro-nano bodies: (1) HNTs were placed in a H2O2 solution, boiled for 2 h, separated, washed, and HNTs-1 was obtained. HNTs-1 was dispersed in toluene, treated with n-octyltriethoxysilane, and then washed and dried to obtain HNTs-2; the ratio of HNTs-1: toluene: n-octyltriethoxysilane was 6 g: 50 mL: 1 mL. HNTs-2 was dispersed in a ferric chloride solution and ultrasonically treated at 30 W for 20 min. HNTs-2 and Fe 3+ The mass ratio of ammonia water is 1:0.2, and then ammonia water is added for precipitation, and the mixture is placed at 85℃ for 8h. The concentration of ammonia water is 8mol / L. 2+ / Fe 3+ The molar ratio of HNTs-3 is 1:10. Finally, HNTs-3 is obtained by washing and drying. (2) The pH value of HNTs-3 is adjusted to 7.2-7.6, HNTs-3 is placed in a dopamine aqueous solution, ultrasonically dispersed at 80W for 30-60min, centrifuged, washed, and HNTs-4 is obtained; wherein, the mass ratio of HNTs-3 to dopamine is 1:0.2; HNTs-4 is placed in a PEI aqueous solution, ultrasonically treated at 60W for 4-8h, filtered, and dried to obtain HNTs-4@PEI. Barium sulfate whiskers are placed in an acid solution (V 浓硫酸 :V 浓硝酸 =1:1) at 65°C for 5h, then washed and dried to obtain barium sulfate whisker-1. HNTs-4@PEI and barium sulfate whisker-1 were ultrasonically treated in Tris buffer at 40W for 4h, filtered and dried to obtain HNTs-4@PEI@barium sulfate whisker-1, wherein the mass ratio of HNTs-4:PEI:barium sulfate whisker-1 was 2:2:1, and HNTs-4@PEI@barium sulfate whisker-1 was the modified composite.

[0025] Weigh 50 parts of ethylene-vinyl acetate copolymer, 10 parts of ethylene-butene copolymer, 40 parts of high-density polyethylene, 1.5 parts of antioxidant 224, 1.5 parts of antioxidant 1036, 3 parts of vinyl triethoxysilane, 2 parts of zinc stearate, 2 parts of silicone masterbatch, 2 parts of paraffin, 20 parts of white carbon black, and 45 parts of modified compound. After treating 50 parts of ethylene-vinyl acetate copolymer, 10 parts of ethylene-butene copolymer, and 40 parts of high-density polyethylene in an internal mixer at 170°C for 20 minutes, put the remaining raw materials into a high-speed mixer, treat at 500r / min for 15 minutes, and then extrude and granulate to obtain cable material.

[0026] Example 2

[0027] The difference between this embodiment and embodiment 1 is that the components of the cable material include: weigh 45 parts of ethylene-vinyl acetate copolymer, 15 parts of ethylene-butene copolymer, 40 parts of high-density polyethylene, 1.5 parts of antioxidant 224, 1.5 parts of antioxidant 1036, 3 parts of vinyl triethoxy silane, 2 parts of zinc stearate, 2 parts of silicone masterbatch, 2 parts of paraffin, 20 parts of white carbon black, and 42 parts of modified compound.

[0028] Example 3

[0029] The difference between this embodiment and embodiment 1 is that the mass ratio of HNTs-4:PEI:barium sulfate whisker-1 is 1:2:1.

[0030] Example 4

[0031] The difference between this embodiment and embodiment 1 is that the barium sulfate whiskers are replaced by calcium sulfate whiskers.

[0032] <Comparative Example>

[0033] Comparative Example 1

[0034] The difference between this comparative example and Example 1 is that the modified composite is replaced by HNTs and barium sulfate whiskers.

[0035] Comparative Example 2

[0036] The difference between this comparative example and Example 1 is that HNTs-3 is replaced by HNTs.

[0037] <Test example>

[0038] The cable materials prepared in Examples 1-4 and Comparative Examples 1-2 were used as samples to measure performance, and the results are shown in Table 1. (The example is represented by E, and the comparative example is represented by D)

[0039] Table 1 Measurement results

[0040]

[0041] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A wear-resistant, oil-resistant and flame-retardant polyolefin cable material, characterized in that: The raw material components are calculated by weight, including 90-100 parts of polyolefin resin, 0.5-5 parts of antioxidant, 0.5-5 parts of dispersant, 2-6 parts of lubricant, 15-30 parts of reinforcing agent, and 30-50 parts of modified compound; The modified composite is obtained by modifying a flame retardant filler and a wear resistant filler; the flame retardant filler is HNTs; the wear resistant filler includes at least one of barium sulfate whiskers, calcium carbonate whiskers and calcium sulfate whiskers; The preparation method of the modified composite is: (1) HNTs were placed in a H2O2 solution, boiled for 2 h, separated and washed to obtain HNTs-1, HNTs-1 was dispersed in toluene, treated with n-octyltriethoxysilane, washed and dried to obtain HNTs-2; HNTs-2 was dispersed in a ferric chloride / ferrous chloride solution and ultrasonically treated at 30W for 10-30min. 2+ / Fe 3+ The mass ratio of ammonia to Fe is 1:0.1~0.2, and then ammonia water is added to deposit Fe, and the mixture is placed at 85℃ for 8h. The concentration of ammonia water is 8mol / L. 2+ / Fe 3+ The molar ratio is 1:10; and then HNTs-3 is obtained by washing and drying; (2) After adjusting the pH value of HNTs-3 to 7.2-7.6, HNTs-3 was placed in a dopamine aqueous solution, ultrasonically dispersed at 80W for 30-60min, centrifuged, washed, and HNTs-4 was obtained; wherein the mass ratio of HNTs-3 to dopamine was 1:0.1-0.5; HNTs-4 was placed in a PEI aqueous solution, ultrasonically treated at 60W for 4-8h, filtered, and dried to obtain HNTs-4@PEI; the whiskers were placed in an acid solution at 65°C for 5h, washed, and dried to obtain whiskers-1; the acid solution was a mixture of concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 1:1; HNTs-4@PEI and whiskers-1 were placed in a Tris buffer solution ultrasonically treated at 40W for 4h, filtered, and dried to obtain HNTs-4@PEI@whisker-1, wherein the mass ratio of HNTs-4:PEI:whisker-1 was 1-2:2:1, and a modified composite was obtained.

2. The wear-resistant, oil-resistant and flame-retardant polyolefin cable material according to claim 1, characterized in that: The polyolefin resin includes at least one of ethylene-vinyl acetate copolymer, ethylene-butene copolymer, and high-density polyethylene.

3. The wear-resistant, oil-resistant and flame-retardant polyolefin cable material according to claim 1, characterized in that: The antioxidant includes at least one of antioxidant 2246 , antioxidant 1010 , antioxidant 1024 , antioxidant 1036 , and antioxidant 300 .

4. The wear-resistant, oil-resistant and flame-retardant polyolefin cable material according to claim 1, characterized in that: The dispersant is vinyl triethoxysilane; and / or the reinforcing agent is carbon black or white carbon black.

5. The wear-resistant, oil-resistant and flame-retardant polyolefin cable material according to claim 1, characterized in that: The lubricant includes at least one of zinc stearate, silicone masterbatch, polyethylene wax, paraffin wax and calcium stearate.

6. A method for preparing the wear-resistant, oil-resistant and flame-retardant polyolefin cable material according to any one of claims 1 to 5, characterized in that: The steps include: After the polyolefin resin is internally kneaded, an antioxidant, a dispersant, a lubricant, a modified compound and a reinforcing agent are added, and then the polyolefin resin is blended, extruded and granulated to obtain a cable material; the preparation process is carried out in an internal mixer.

7. The method for preparing the wear-resistant, oil-resistant and flame-retardant polyolefin cable material according to claim 6, characterized in that: Internal mixing: 150~170℃, 10~30min; blending: 300~600r / min, 5~20min.

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