Ultraviolet irradiation crosslinking color split-phase cable material and preparation method thereof
Through the combination of specific composite coatings and color masterbatches, the problems of long production cycles and uneven colors of traditional silane cross-linking polyethylene insulated low-voltage cables are solved, and the insulation thermal extension is achieved is achieved, and the production efficiency is improved.
Patent Information
- Application Number
- CN202510179468.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-19
- Publication Date
- 2025-07-04
AI Technical Summary
Traditional silane crosslinked polyethylene insulated low-voltage cables have a long production cycle, and warm water crosslinking can easily cause the conductor to oxidize and turn black, and the color of the ultraviolet irradiation crosslinking material is uneven when the color is separated, affecting the insulation performance.
Specific composite coatings and color masterbatches are used, and the insulating and crosslinking are performed simultaneously during the extrusion process through ultraviolet radiation crosslinking technology. Polyester acrylate is used as the matrix resin, combining acrylate monomers, silane coupling agents and tetraethyl orthosilicate and other additives to form a uniform color phase separation cable material.
It achieves stable insulation thermal extension, uniform insulation color, shortens production cycle and improves production efficiency.
Smart Images
Figure CN120248646A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of cable materials, and particularly relates to an ultraviolet radiation cross-linked color-phase separated cable material and a preparation method thereof. Background Art
[0002] Traditional cross-linked polyethylene insulated low-voltage power cables are applicable to distribution networks or industrial installations with a power frequency rated voltage of 0.6 / 1 kV and below. Usually, silane cross-linked polyethylene insulating materials are used. Silane cross-linking is also called warm water cross-linking. Its mechanism is to use organic peroxides as initiators, graft through silane coupling agents, and then undergo hydrolysis and condensation (cross-linking) to introduce them into polyethylene, increasing the strength, anti-aging properties, etc. of polyethylene. The material properties and process properties of the obtained cross-linked polyethylene cables are stable. The disadvantages are that the production cycle is long, and the warm water cross-linking process is still required after extrusion. If the front end of the warm water cross-linking process is not sealed properly, water is likely to enter, resulting in oxidation and blackening of the conductor. After cross-linking, the surface of the insulated wire core is relatively dirty and has scale. With the increasing delivery period requirements of low-voltage power cables in the market, the existing production process cannot meet the needs of a large number of orders.
[0003] Ultraviolet radiation cross-linking is to add an appropriate amount of photo-cross-linking sensitizer to a base resin mainly composed of polyethylene. Utilizing the characteristic that polyethylene material is in a transparent state when heated and extruded, the ultraviolet radiation is focused and transmitted into the material, so that high-energy ultraviolet light initiates the sensitizer to form free radicals, and further induces polyethylene units to generate macromolecular free radicals. The free radicals form cross-linked polyethylene materials through bonding, changing from a linear structure to a network structure. This technology only needs to add an ultraviolet cross-linking irradiator to the existing extruder, and insulation extrusion and cross-linking can be carried out simultaneously, reducing the warm water cross-linking process, greatly shortening the production cycle time, and improving production efficiency.
[0004] The insulation of low-voltage power cables is conventionally divided into 5 colors: yellow, green, red, blue, and black. In order to distinguish the colors, color masterbatches of different colors need to be added, and special color masterbatches need to be added to the ultraviolet cross-linked materials. Since different colors have different effects on ultraviolet radiation cross-linking, color masterbatches of different colors will hinder and attenuate the energy and beam penetration of ultraviolet light irradiation, reducing the irradiation effect. After being irradiated by high-energy ultraviolet light, the color depth and uniformity of the color masterbatch will change, affecting the insulation heat elongation. The ultraviolet radiation cross-linking technology is particularly sensitive to colors. For example, if color-phase separation is used for insulation and the color masterbatch mixing ratio of the silane cross-linked material is still used for proportioning, the heat elongation after irradiation cross-linking will be unqualified. Based on this, domestic cable factories use color tape phase separation (the insulation is the natural color) for ultraviolet cross-linked insulation, but most customers cannot accept it and still require color-phase separation. How to solve this problem has become the key to realizing this technology. Summary of the Invention
[0005] The object of the present invention is to address the above technical problems and provide an ultraviolet radiation cross-linked color-separated cable compound and a preparation method thereof. By combining a specific composite coating with a color masterbatch and applying the ultraviolet radiation cross-linking technology, the object of qualified and stable insulation heat elongation, uniform insulation color, and improved production efficiency is achieved.
[0006] In the technical solution of the present invention, the ultraviolet radiation cross-linked color-separated cable compound comprises the following raw material components in parts by weight: 1 to 10 parts of a composite coating, 10 to 30 parts of an ultraviolet light insulating material, and a color masterbatch accounting for 0.2 to 2.0% of the mass of the composite coating.
[0007] Further, the composite coating comprises the following raw material components in parts by weight: 40 to 60 parts of polyester acrylate, 10 to 20 parts of inorganic filler, 1.0 to 2.5 parts of acrylate monomer, 5 to 10 parts of silane coupling agent, 1.0 to 5.0 parts of tetraethyl orthosilicate, 1.0 to 2.5 parts of photoinitiator, 0.5 to 1.0 part of ultraviolet absorber, and 0.1 to 0.5 part of antioxidant.
[0008] Using polyester acrylate as the matrix resin, combining specific acrylate monomers, silane coupling agents, and tetraethyl orthosilicate, as well as other additives, a composite coating with appropriate viscosity is obtained. Co-extruding with the ultraviolet light insulating material and the color masterbatch yields a cable compound with excellent performance; among them, tetraethyl orthosilicate can form a dense film when encountering moisture, thereby improving the moisture-proof ability of the cable compound in different environments.
[0009] Further, the color of the color masterbatch is one or more of yellow, green, red, blue, and black.
[0010] Preferably, the particle size of the inorganic filler is 10 to 100 nm, including but not limited to any one of calcium carbonate, silicon dioxide, aluminum oxide, titanium dioxide, and zirconium oxide.
[0011] Further, the acrylate monomer is a chain compound with no more than 20 carbon atoms and a carbon-carbon double bond in its molecular structure; including but not limited to one or more of tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, 4-hydroxybutyl acrylate, 2-propylheptyl acrylate, 2,5-dimethyl-2,5-hexanediol dimethacrylate, dipropylene glycol diacrylate, 3,5,5-trimethylhexyl acrylate, dipropylene glycol triacrylate, and 2,3,3-trimethylisobutyl alcohol acrylate.
[0012] The chain structure with an appropriate number of carbon atoms in the acrylate monomer enables the acrylate monomer to be better mixed evenly with other components. Under the action of the photoinitiator, the carbon-carbon double bond undergoes cross-linking and is further evenly distributed in the cable compound system.
[0013] Further, the number of carbon atoms in the acrylate monomer is 5 to 15.
[0014] Furthermore, the silane coupling agent is a chain silane compound containing a carbon-carbon double bond in its molecular structure; including but not limited to one or more of vinylmethylsilane, 2-allyltrimethylsilane, vinyl(chloromethyl)dimethoxysilane, dimethyl(dimethylamino)vinylsilane, 3-chloropropyldimethylvinylsilane, and vinyldimethylethoxysilane.
[0015] Preferably, the photoinitiator is any one of benzoyl derivatives, dialkoxyacetophenones, α-hydroxyalkylphenones, and acylphosphine oxides; including but not limited to any one of 2,4,6(trimethylbenzoyl)diphenylphosphine oxide (TPO), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (photoinitiator 819), α,α-dimethoxy-α-phenylacetophenone (photoinitiator 651), α,α-ethoxyacetophenone (photoinitiator DEAP), and 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMPP).
[0016] Furthermore, the ultraviolet absorber is any one of benzophenones and benzotriazoles; including but not limited to any one of 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-(2ˊ-hydroxy-5ˊ-methylphenyl)benzotriazole, and 2-(2’-hydroxy-3’,5’-diphenyl)-5-chlorobenzotriazole.
[0017] Preferably, the antioxidant includes but not limited to one or more of antioxidant 1010, antioxidant 1076, antioxidant CA, antioxidant 168, antioxidant DNP, and antioxidant DLTP.
[0018] The present invention also provides a method for preparing the above ultraviolet light irradiated crosslinked color phase separated cable material, comprising the following steps: (1) Mix polyester acrylate, inorganic filler, acrylate monomer, silane coupling agent, tetraethyl orthosilicate, photoinitiator, ultraviolet absorber, and antioxidant evenly to obtain a composite coating; (2) Mix the composite coating, ultraviolet light insulating material, and color masterbatch evenly, and perform ultraviolet light crosslinking during the extrusion process.
[0019] Furthermore, in step (2), the ultraviolet light crosslinking during the extrusion process is achieved by setting an ultraviolet light crosslinking irradiator on the extruder.
[0020] Furthermore, in step (2), the ultraviolet light wavelength during ultraviolet light crosslinking is 200~400nm.
[0021] Preferably, after the composite coating, the UV light insulating material and the color masterbatch are uniformly mixed, they are extruded through an extruder, and a UV light crosslinking irradiator is arranged on the extruder so that extrusion and crosslinking are carried out simultaneously.
[0022] Preferably, the temperature from the barrel to the head of the extruder is 150-260 °C, and a filter screen with 40-60 meshes is arranged.
[0023] Compared with the prior art, the technical solution of the present invention has the following beneficial effects: (1) The present invention combines a specific composite coating with a color masterbatch, and uses the UV light irradiation crosslinking technology during the extrusion process to obtain a color-phase separated cable material with qualified and stable insulation heat elongation and uniform insulation color. (2) The present invention uses polyester acrylate as the matrix resin, combines specific acrylate monomers, silane coupling agents and tetraethyl orthosilicate, as well as other additives, to obtain a composite coating with appropriate viscosity, and co-extrudes it with the UV light insulating material and the color masterbatch to obtain a cable material with excellent performance. (3) The chain structure with a suitable number of carbon atoms in the acrylate monomer enables the acrylate monomer to be mixed well with other components. The carbon-carbon double bonds in it and the carbon-carbon double bonds in the silane coupling agent crosslink under the action of a photoinitiator and are further uniformly distributed in the cable material system. (4) A UV light crosslinking irradiator is arranged on the extruder so that extrusion and crosslinking are carried out simultaneously, reducing a production process, improving the production turnover cycle, and greatly improving the production efficiency. BRIEF DESCRIPTION OF THE DRAWINGS
[0024] Figure 1 It is a picture of the UV light irradiated crosslinked color-phase separated cable material of the present invention. DETAILED DESCRIPTION OF THE INVENTION
[0025] The technical solution of the present invention will be further described and illustrated below through specific examples and drawings. It should be understood that the specific examples described here are only for helping to understand the present invention and are not used for specific limitations of the present invention. And the drawings used in this article are only for better explaining the content disclosed by the present invention and do not have a limiting effect on the protection scope. If there is no special description, the raw materials used in the embodiments of the present invention are all commonly used raw materials in the art, and the methods used in the embodiments are all conventional methods in the art.
[0026] In the following examples and comparative examples, the polyester acrylate is M-8060 purchased from Dong-A Synthetic (Zhuhai) Co., Ltd.; the UV light insulating material is CUV-9018J purchased from Shanghai Kaibo High Polymer Materials Co., Ltd.; the yellow color masterbatch, red color masterbatch, blue color masterbatch, and green color masterbatch are purchased from Tianjin Mingkun New Material Technology Co., Ltd. Example 1
[0027] The preparation method of the ultraviolet radiation cross-linked color phase-separated cable material in this embodiment includes the following steps: (1) Mix 45 parts of polyester acrylate, 15 parts of silicon dioxide, 1.5 parts of tripropylene glycol diacrylate, 6.0 parts of vinyl methyl silane, 2.0 parts of tetraethyl orthosilicate, 1.0 part of photoinitiator 651, 0.6 part of 2,4-dihydroxybenzophenone, and 0.2 part of antioxidant 1010 evenly to obtain a composite coating; (2) Pour 5 kg of the composite coating obtained in the above step, 20 kg of ultraviolet insulating material, and 50 g of yellow color masterbatch into a mixer and stir and mix evenly. Then, extrude using a single-screw extruder. The temperature from the barrel to the head of the extruder is 170 - 220 °C. Set a 40-mesh filter screen, and use a tube extrusion die for the extrusion die; and set an ultraviolet cross-linking irradiator on the extruder to perform ultraviolet cross-linking during the extrusion of the mixture. The wavelength of the ultraviolet light is 300 nm. Example 2
[0028] The preparation method of the ultraviolet radiation cross-linked color phase-separated cable material in this embodiment includes the following steps: (1) Mix 50 parts of polyester acrylate, 12 parts of silicon dioxide, 1.8 parts of 4-hydroxybutyl acrylate, 8.0 parts of vinyl methyl silane, 3.0 parts of tetraethyl orthosilicate, 1.5 parts of TPO, 0.8 part of 2-hydroxy-4-methoxybenzophenone, and 0.2 part of antioxidant 1010 evenly to obtain a composite coating; (2) Pour 6 kg of the composite coating obtained in the above step, 23 kg of ultraviolet insulating material, and 50 g of yellow color masterbatch into a mixer and stir and mix evenly. Then, extrude using a single-screw extruder. The temperature from the barrel to the head of the extruder is 170 - 220 °C. Set a 40-mesh filter screen, and use a tube extrusion die for the extrusion die; and set an ultraviolet cross-linking irradiator on the extruder to perform ultraviolet cross-linking during the extrusion of the mixture. The wavelength of the ultraviolet light is 300 nm. Example 3
[0029] The preparation method of the ultraviolet radiation cross-linked color phase-separated cable material in this embodiment includes the following steps: (1) Mix 55 parts of polyester acrylate, 16 parts of silicon dioxide, 2.0 parts of dipropylene glycol triacrylate, 8.0 parts of 2-allyltrimethylsilane, 4.0 parts of tetraethyl orthosilicate, 1.6 part of photoinitiator 651, 0.6 part of 2,4-dihydroxybenzophenone, and 0.4 part of antioxidant DLTP evenly to obtain a composite coating; (2) Pour 8 kg of the composite coating obtained in the above step, 26 kg of the UV insulating material, and 50 g of the yellow color masterbatch into a blender and stir and mix evenly. Then, extrude using a single-screw extruder. The temperature from the barrel to the head of the extruder is 170 - 220 °C. Set a 40-mesh filter screen, and use a tube extrusion die for the extrusion die; and set a UV cross-linking irradiator on the extruder to perform UV cross-linking during the extrusion of the mixture. The UV wavelength is 300 nm. Example 4
[0030] The difference between this example and Example 1 is only that in step (2), 5 kg of the composite coating obtained in the above step, 20 kg of the UV insulating material, and 50 g of the red color masterbatch are poured into a blender and stir and mix evenly. Then, extrude using a single-screw extruder. The temperature from the barrel to the head of the extruder is 170 - 220 °C. Set a 40-mesh filter screen, and use a tube extrusion die for the extrusion die; and set a UV cross-linking irradiator on the extruder to perform UV cross-linking during the extrusion of the mixture. The UV wavelength is 300 nm. Example 5
[0031] The difference between this example and Example 1 is only that in step (2), 5 kg of the composite coating obtained in the above step, 20 kg of the UV insulating material, and 60 g of the blue color masterbatch are poured into a blender and stir and mix evenly. Then, extrude using a single-screw extruder. The temperature from the barrel to the head of the extruder is 170 - 220 °C. Set a 40-mesh filter screen, and use a tube extrusion die for the extrusion die; and set a UV cross-linking irradiator on the extruder to perform UV cross-linking during the extrusion of the mixture. The UV wavelength is 300 nm. Example 6
[0032] The difference between this example and Example 1 is only that in step (2), 5 kg of the composite coating obtained in the above step, 20 kg of the UV insulating material, 30 g of the yellow color masterbatch, and 70 g of the green color masterbatch are poured into a blender and stir and mix evenly. Then, extrude using a single-screw extruder. The temperature from the barrel to the head of the extruder is 170 - 220 °C. Set a 40-mesh filter screen, and use a tube extrusion die for the extrusion die; and set a UV cross-linking irradiator on the extruder to perform UV cross-linking during the extrusion of the mixture. The UV wavelength is 300 nm. Example 7
[0033] The difference between this example and Example 1 is only that in step (1), 45 parts of polyester acrylate, 15 parts of silicon dioxide, 1.5 parts of 3,5-dihydroxyphenyl methacrylate, 6.0 parts of vinyl methyl silane, 2.0 parts of tetraethyl orthosilicate, 1.0 part of photoinitiator 651, 0.6 part of 2,4-dihydroxybenzophenone, and 0.2 part of antioxidant 1010 are mixed evenly to obtain the composite coating. Example 8
[0034] The difference between this example and Example 1 is only that in step (1), 45 parts of polyester acrylate, 15 parts of silicon dioxide, 1.5 parts of octadecyl methacrylate, 6.0 parts of vinylmethylsilane, 2.0 parts of tetraethyl orthosilicate, 1.0 part of photoinitiator 651, 0.6 part of 2,4-dihydroxybenzophenone, and 0.2 part of antioxidant 1010 are mixed evenly to obtain a composite coating. Example 9
[0035] The difference between this example and Example 1 is only that in step (1), 45 parts of polyester acrylate, 15 parts of silicon dioxide, 1.5 parts of tripropylene glycol diacrylate, 6.0 parts of vinylmethylsilane, 1.0 part of photoinitiator 651, 0.6 part of 2,4-dihydroxybenzophenone, and 0.2 part of antioxidant 1010 are mixed evenly to obtain a composite coating. Comparative Example 1
[0036] The difference between this comparative example and Example 1 is only that in step (2), 5 kg of the composite coating obtained in the above step, 20 kg of ultraviolet light insulating material, and 5 g of yellow color masterbatch are poured into a blender and stirred and mixed evenly, and then extruded using a single-screw extruder. The temperature from the barrel to the head of the extruder is 170 - 220 °C, a 40-mesh filter screen is set, and the extrusion die uses a tube extrusion type; and an ultraviolet light cross-linking irradiator is set on the extruder to perform ultraviolet light cross-linking during the extrusion of the mixture, and the ultraviolet light wavelength is 300 nm. Comparative Example 2
[0037] The difference between this comparative example and Example 1 is only that in step (2), 5 kg of the composite coating obtained in the above step, 20 kg of ultraviolet light insulating material, and 110 g of yellow color masterbatch are poured into a blender and stirred and mixed evenly, and then extruded using a single-screw extruder. The temperature from the barrel to the head of the extruder is 170 - 220 °C, a 40-mesh filter screen is set, and the extrusion die uses a tube extrusion type; and an ultraviolet light cross-linking irradiator is set on the extruder to perform ultraviolet light cross-linking during the extrusion of the mixture, and the ultraviolet light wavelength is 300 nm.
[0038] The present invention combines a specific composite coating with a color masterbatch and applies ultraviolet light irradiation cross-linking technology during extrusion to obtain a color-phase-separated cable material with uniform insulating color as shown in Figure 1 The mechanical properties and oxygen index (LOI) of the obtained color-phase-separated cable material are tested to characterize its performance, and the test results are shown in Table 1.
[0039] Table 1 Performance data table of ultraviolet light irradiation cross-linked color-phase-separated cable material Tensile strength Mpa Elongation at break % Degree of crosslinking Example 1 14.8 223% 82.3% Example 2 14.3 221% 82.0% Example 3 14.5 222% 82.1% Example 4 14.2 219% 82.2% Example 5 14.3 220% 81.8% Example 6 13.9 218% 82.0% Example 7 13.2 213% 80.6% Example 8 13.0 214% 80.1% Example 9 13.4 208% 81.2% Comparative example 1 14.3 216% 82.0% Comparative example 2 14.2 201% 80.3% .
[0040] The UV-irradiation crosslinked color-phase separated cable materials obtained in Examples 1-6 exhibited excellent mechanical properties and flame retardancy. In Example 7, the use of acrylate monomers with benzene ring structures in the composite coating and in Example 8, the use of acrylate monomers with long straight-chain structures having a relatively large number of carbon atoms in the composite coating both had relatively large steric hindrances, which affected the crosslinking effect and caused a decrease in the mechanical properties of the obtained UV-irradiation crosslinked color-phase separated cable materials. In Example 9, tetraethyl orthosilicate was not used in the composite coating, and a protective film could not be formed in a humid environment, resulting in a decrease in the moisture resistance of the obtained UV-irradiation crosslinked color-phase separated cable materials. In Comparative Example 1, a relatively small amount of yellow color masterbatch was used, and the obtained UV-irradiation crosslinked color-phase separated cable materials had a lighter and uneven color. In Comparative Example 2, an excessive amount of yellow color masterbatch was used, increasing the difficulty of dispersion, resulting in an increase in the crosslinking difficulty of the UV-irradiation crosslinked color-phase separated cable materials, a decrease in the crosslinking degree, and a decrease in the mechanical properties.
[0041] Finally, it should be noted that the specific embodiments described herein are merely illustrative of the spirit of the present invention and not a limitation on the embodiments of the present invention. Those skilled in the art of the present invention can make various modifications or supplements to the described embodiments or use similar methods for substitution. It is not necessary and impossible to list all embodiments here. And these obvious changes or variations derived from the essence of the present invention still fall within the protection scope of the present invention. Interpreting them as any additional limitation is contrary to the spirit of the present invention.
Claims
1. An ultraviolet radiation cross-linked color phase-separated cable compound, characterized in that, It includes the following raw material components in parts by weight: 1 - 10 parts of composite coating, 10 - 30 parts of ultraviolet light insulating material, and 0.2 - 2.0% of color masterbatch based on the mass of the composite coating.
2. The ultraviolet radiation cross-linked color-phase separated cable compound according to claim 1, wherein The composite coating includes the following raw material components in parts by weight: 40 - 60 parts of polyester acrylate, 10 - 20 parts of inorganic filler, 1.0 - 2.5 parts of acrylate monomer, 5 - 10 parts of silane coupling agent, 1.0 - 5.0 parts of tetraethyl orthosilicate, 1.0 - 2.5 parts of photoinitiator, 0.5 - 1.0 part of ultraviolet absorber, 0.1 - 0.5 part of antioxidant.
3. The ultraviolet light irradiation cross-linked color phase-separated cable material according to claim 1, wherein The color of the color masterbatch is one or more of yellow, green, red, blue, and black.
4. The ultraviolet radiation crosslinked color-phase separated cable compound according to claim 2, characterized in that The acrylate monomer is a chain compound with no more than 20 carbon atoms and a carbon - carbon double bond in its molecular structure.
5. The ultraviolet light irradiation crosslinked color phase-separated cable material according to claim 4, wherein The number of carbon atoms in the acrylate monomer is 5 - 15.
6. The ultraviolet radiation cross-linked color phase-separated cable material according to claim 2, characterized in that, The silane coupling agent is a chain silane compound with a carbon - carbon double bond in its molecular structure.
7. The ultraviolet light irradiation crosslinked color phase-separated cable material according to claim 2, characterized in that, The photoinitiator is any one of benzil derivatives, dialkoxyacetophenone, α - hydroxyalkylphenone, and acylphosphine oxides.
8. A method for preparing an ultraviolet irradiation crosslinked color phase-separated cable material as described in claim 1 or 2, characterized in that, It includes the following steps: (1) Mix polyester acrylate, inorganic filler, acrylate monomer, silane coupling agent, tetraethyl orthosilicate, photoinitiator, ultraviolet absorber, and antioxidant evenly to obtain the composite coating; (2) Mix the composite coating, ultraviolet light insulating material, and color masterbatch evenly, and perform ultraviolet cross - linking during the extrusion process.
9. The preparation method according to claim 8, characterized in that, In step (2), the ultraviolet cross - linking during the extrusion process is achieved by setting an ultraviolet cross - linking irradiator on the extruder.
10. The preparation method according to claim 8, characterized in that, In step (2), the wavelength of the ultraviolet light during ultraviolet cross - linking is 200 - 400 nm.