CN110092968B - High-stability waterproof cable - Google Patents
High-stability waterproof cable Download PDFInfo
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- CN110092968B CN110092968B CN201910372728.XA CN201910372728A CN110092968B CN 110092968 B CN110092968 B CN 110092968B CN 201910372728 A CN201910372728 A CN 201910372728A CN 110092968 B CN110092968 B CN 110092968B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/28—Protection against damage caused by moisture, corrosion, chemical attack or weather
- H01B7/282—Preventing penetration of fluid, e.g. water or humidity, into conductor or cable
- H01B7/2825—Preventing penetration of fluid, e.g. water or humidity, into conductor or cable using a water impermeable sheath
Abstract
The invention relates to a high-stability waterproof cable which comprises a conductor, a semi-conductive shielding layer, an insulating layer, a waterproof layer, an armor layer and a sheath from inside to outside, wherein the semi-conductive shielding layer is made of a semi-conductive shielding material, and the semi-conductive shielding material comprises the following raw materials in percentage by weight: 50% of polyethylene, 20% of ethylene-vinyl acetate copolymer, 19% of modified carbon black, 10% of diethyl carbonate, 0.5% of cross-linking agent and 0.5% of antioxidant. The high-stability waterproof cable prepared by the invention has the advantages of simple structure, light weight, good shielding effect, high tensile strength, durability, corrosion resistance and long service life.
Description
Technical Field
The invention relates to a high-stability waterproof cable.
Background
With the acceleration of urbanization and modernization in China, domestic electric systems are also continuously improved. Various large hydroelectric power stations, large intensive coal-based power stations, hydroelectric power stations, nuclear power stations, renewable new energy power stations and the like are under construction in disputes. This has led to an increasing demand for crosslinked polyethylene insulated medium and high voltage power cables year after year.
In recent years, China is always striving to improve the quality level of the semiconductive shielding layer and narrow the gap with the foreign advanced level. The main reasons limiting the localization of the semiconductive shielding material for medium and high voltage power cables are the lack of special resin with excellent performance and the immature technology for preparing the ultrapure material. Because the electric field intensity in the insulating layer of the medium-high voltage power cable is very high, the small defects on any semi-conductive shielding layer can cause serious electric field deformation, partial discharge occurs, and finally, the phenomenon of generating branches is caused. Therefore, the semiconductive shield used for medium and high voltage power cables requires an extruded surface with a high degree of smoothness.
Research and development of the semiconductive shielding material have been started from the past century and fifty years abroad. In the sixties, the commercialization of polymers such as ethylene-vinyl acetate copolymer has accelerated the research and development of cable shielding materials. After seventy years, semiconductive shielding materials with practical application values have been developed abroad and successfully put into use. However, our research on semiconductive shields began at the end of the last century, and began later than in developed countries. The raw materials of the cable such as EVA, high-purity polyethylene and the like are mostly imported, and the conductive carbon black produced at home has a large gap with foreign countries. The shielding material produced in China has serious defects in the aspect of electrical performance, and compared with foreign products, the shielding material has more bulges or burrs on the surface and is not smooth enough. A semiconductive shielding material (CN 106279929A) for a cable is developed by national power grid companies and comprises the following raw materials in percentage by weight: 40-80% of polyethylene, 5-20% of ethylene-vinyl acetate copolymer, 15-40% of modified carbon black, 5-20% of auxiliary agent and 0.1-1.5% of cross-linking agent. The invention firstly proposes that the active metal is loaded on the carbon black, the space potential distribution on the carbon black is improved, the surface property of the carbon black can be improved to a certain extent, and the dispersion degree of the carbon black in the preparation process of the shielding material is improved, so that the excellent shielding material with smooth surface and small contact hole with a conductor is prepared.
However, after market practice reaction, the shielding material of the cable still has a technical problem of insufficient shielding effect, and research and development personnel find that the volume resistivity of the shielding material of the cable is still high and the amount of impurities above 50 μm is still large through detection, which finally results in that the requirement of high shielding effect cannot be met.
Disclosure of Invention
The technical problems that the volume resistivity of a cable shielding material is still high, the quantity of impurities more than 50 mu m is still large, and the shielding effect of a cable is difficult to meet high-end requirements in the prior art are solved.
The invention provides the following technical scheme:
a high-stability waterproof cable comprises a conductor, a semi-conductive shielding layer, an insulating layer, a waterproof layer, an armor layer and a sheath from inside to outside, wherein the semi-conductive shielding layer is made of a semi-conductive shielding material.
The semiconductive shielding material comprises the following raw materials in percentage by weight: 50% of polyethylene, 20% of ethylene-vinyl acetate copolymer, 19% of modified carbon black, 10% of diethyl carbonate, 0.5% of cross-linking agent and 0.5% of antioxidant.
The preparation method of the modified carbon black comprises the following steps:
step 1: pretreating carbon black, namely soaking the carbon black in alkali liquor for 24 hours, soaking the carbon black in nitric acid for 24 hours after washing, washing the carbon black by deionized water, and calcining and activating the carbon black in an inert atmosphere to obtain activated carbon black;
step 2: adding activated carbon black to Ni2+And Co2+Adding ammonia water into the aqueous solution of (1) to adjust the pH value to 9-10, stirring, carrying out vacuum filtration, cleaning, drying, and calcining under inert atmosphere to obtain the carbon black loaded with active metal; calculated by a nickel simple substance and a cobalt simple substance, the modified carbon black contains 15 wt% of nickel and 3 wt% of cobalt;
and step 3: dispersing the carbon black loaded with the active metal into an ethanol solution, adding a modifier, stirring and reacting for 4-8 hours, and performing centrifugal separation, washing and drying to obtain modified carbon black; the amount of the modifier is 5wt% of the carbon black loaded with the active metal, and the particle size of the modified carbon black is 100-1000 nm.
The modifier in the step 3 is formed by mixing a compound (1) and dialkyl sulfosuccinate according to the weight ratio of 1: 1;
the structural formula of the compound (1) is as follows:
the cross-linking agent is one of triallyl isocyanurate and trimethylolpropane trimethacrylate.
The antioxidant is one of antioxidant 1010, antioxidant 1024 and antioxidant 1035.
The calcination temperature in the step 1 is 150-200 ℃.
The calcination temperature in the step 2 is 300-350 ℃, and the calcination time is 3-7 h.
The technical scheme of the invention has the following beneficial effects:
(1) compared with the prior art, the volume resistivity (omega. m) of the shielding material prepared by the invention can reach 19, the number of impurities with the size of more than 50 mu m is eliminated, and the shielding effect and the stability of the cable are greatly improved;
(2) the compound (1) and dialkyl sulfosuccinate are used for carrying out compound synergistic modification on the carbon black, so that the dispersion effect of the carbon black can be greatly improved, the carbon black can be uniformly distributed in a shielding material, the shielding effect of the carbon black in a cable can be fully exerted, and the stability of the cable can be ensured;
(3) compared with the loaded nickel and aluminum, the nickel and cobalt are used as the loaded active metal of the carbon black, so that the space potential distribution and the surface property of the carbon black are improved, the dispersion degree of the carbon black in the preparation process of the shielding material is improved, and the stability of the cable is ensured.
(4) The cable comprises the waterproof layer, so that the waterproof effect of the cable can be ensured.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the following examples and comparative examples.
Example 1
A high-stability waterproof cable comprises a conductor, a semi-conductive shielding layer, an insulating layer, a waterproof layer, an armor layer and a sheath from inside to outside, wherein the semi-conductive shielding layer is made of a semi-conductive shielding material.
The semiconductive shielding material comprises the following raw materials in percentage by weight: 50% of polyethylene, 20% of ethylene-vinyl acetate copolymer, 19% of modified carbon black, 10% of diethyl carbonate, 0.5% of cross-linking agent and 0.5% of antioxidant.
The preparation method of the modified carbon black comprises the following steps:
step 1: pretreating carbon black, namely soaking the carbon black in alkali liquor for 24 hours, soaking the carbon black in nitric acid for 24 hours after washing, washing the carbon black by deionized water, and calcining and activating the carbon black in an inert atmosphere to obtain activated carbon black;
step 2: adding activated carbon black to Ni2+And Co2+Adding ammonia water into the aqueous solution of (1) to adjust the pH value to 9, stirring, carrying out vacuum filtration, cleaning, drying and calcining under inert atmosphere to obtain the carbon black loaded with the active metal; calculated by a nickel simple substance and a cobalt simple substance, the modified carbon black contains 15 wt% of nickel and 3 wt% of cobalt;
and step 3: dispersing the carbon black loaded with the active metal into an ethanol solution, adding a modifier, stirring and reacting for 4-8 hours, and performing centrifugal separation, washing and drying to obtain modified carbon black; the amount of the modifier is 5wt% of the carbon black loaded with the active metal, and the particle size of the modified carbon black is 100-1000 nm.
The modifier in the step 3 is formed by mixing a compound (1) and dialkyl sulfosuccinate according to the weight ratio of 1: 1;
the structural formula of the compound (1) is as follows:
wherein the crosslinking agent is triallyl isocyanurate, the antioxidant is antioxidant 1010, the calcination temperature in the step 1 is 150 ℃, the calcination temperature in the step 2 is 300 ℃, and the calcination time is 3 hours.
Example 2
A high-stability waterproof cable comprises a conductor, a semi-conductive shielding layer, an insulating layer, a waterproof layer, an armor layer and a sheath from inside to outside, wherein the semi-conductive shielding layer is made of a semi-conductive shielding material.
The semiconductive shielding material comprises the following raw materials in percentage by weight: 50% of polyethylene, 20% of ethylene-vinyl acetate copolymer, 19% of modified carbon black, 10% of diethyl carbonate, 0.5% of cross-linking agent and 0.5% of antioxidant.
The preparation method of the modified carbon black comprises the following steps:
step 1: pretreating carbon black, namely soaking the carbon black in alkali liquor for 24 hours, soaking the carbon black in nitric acid for 24 hours after washing, washing the carbon black by deionized water, and calcining and activating the carbon black in an inert atmosphere to obtain activated carbon black;
step 2: adding activated carbon black to Ni2+And Co2+Adding ammonia water into the aqueous solution of (1) to adjust the pH value to 9, stirring, carrying out vacuum filtration, cleaning, drying and calcining under inert atmosphere to obtain the carbon black loaded with the active metal; calculated by a nickel simple substance and a cobalt simple substance, the modified carbon black contains 15 wt% of nickel and 3 wt% of cobalt;
and step 3: dispersing the carbon black loaded with the active metal into an ethanol solution, adding a modifier, stirring and reacting for 4-8 hours, and performing centrifugal separation, washing and drying to obtain modified carbon black; the amount of the modifier is 5wt% of the carbon black loaded with the active metal, and the particle size of the modified carbon black is 100-1000 nm.
The modifier in the step 3 is formed by mixing a compound (1) and dialkyl sulfosuccinate according to the weight ratio of 1: 1;
the structural formula of the compound (1) is as follows:
wherein the crosslinking agent is trimethylolpropane trimethacrylate, the antioxidant is an antioxidant 1024, the calcining temperature in the step 1 is 170 ℃, the calcining temperature in the step 2 is 320 ℃, and the calcining time is 5 hours.
Example 3
A high-stability waterproof cable comprises a conductor, a semi-conductive shielding layer, an insulating layer, a waterproof layer, an armor layer and a sheath from inside to outside, wherein the semi-conductive shielding layer is made of a semi-conductive shielding material.
The semiconductive shielding material comprises the following raw materials in percentage by weight: 50% of polyethylene, 20% of ethylene-vinyl acetate copolymer, 19% of modified carbon black, 10% of diethyl carbonate, 0.5% of cross-linking agent and 0.5% of antioxidant.
The preparation method of the modified carbon black comprises the following steps:
step 1: pretreating carbon black, namely soaking the carbon black in alkali liquor for 24 hours, soaking the carbon black in nitric acid for 24 hours after washing, washing the carbon black by deionized water, and calcining and activating the carbon black in an inert atmosphere to obtain activated carbon black;
step 2: adding activated carbon black to Ni2+And Co2+Adding ammonia water into the aqueous solution of (1) to adjust the pH value to 10, stirring, carrying out vacuum filtration, cleaning, drying and calcining under inert atmosphere to obtain the carbon black loaded with active metal; calculated by a nickel simple substance and a cobalt simple substance, the modified carbon black contains 15 wt% of nickel and 3 wt% of cobalt;
and step 3: dispersing the carbon black loaded with the active metal into an ethanol solution, adding a modifier, stirring and reacting for 4-8 hours, and performing centrifugal separation, washing and drying to obtain modified carbon black; the amount of the modifier is 5wt% of the carbon black loaded with the active metal, and the particle size of the modified carbon black is 100-1000 nm.
The modifier in the step 3 is formed by mixing a compound (1) and dialkyl sulfosuccinate according to the weight ratio of 1: 1;
the structural formula of the compound (1) is as follows:
wherein the crosslinking agent is trimethylolpropane trimethacrylate, the antioxidant is an antioxidant 1035, the calcination temperature in the step 1 is 200 ℃, the calcination temperature in the step 2 is 350 ℃, and the calcination time is 7 hours.
Comparative example 1
A high-stability waterproof cable comprises a conductor, a semi-conductive shielding layer, an insulating layer, a waterproof layer, an armor layer and a sheath from inside to outside, wherein the semi-conductive shielding layer is made of a semi-conductive shielding material.
The semiconductive shielding material comprises the following raw materials in percentage by weight: 50% of polyethylene, 20% of ethylene-vinyl acetate copolymer, 19% of modified carbon black, 10% of diethyl carbonate, 0.5% of cross-linking agent and 0.5% of antioxidant.
The preparation method of the modified carbon black comprises the following steps:
step 1: pretreating carbon black, namely soaking the carbon black in alkali liquor for 24 hours, soaking the carbon black in nitric acid for 24 hours after washing, washing the carbon black by deionized water, and calcining and activating the carbon black in an inert atmosphere to obtain activated carbon black;
step 2: adding activated carbon black to Ni2+And Al3+Adding ammonia water into the aqueous solution of (1) to adjust the pH value to 9, stirring, carrying out vacuum filtration, cleaning, drying and calcining under inert atmosphere to obtain the carbon black loaded with the active metal; the modified carbon black contains 15 wt% of nickel and 3 wt% of aluminum, calculated by nickel and aluminum;
and step 3: dispersing the carbon black loaded with the active metal into an ethanol solution, adding a modifier, stirring and reacting for 4-8 hours, and performing centrifugal separation, washing and drying to obtain modified carbon black; the amount of the modifier is 5wt% of the carbon black loaded with the active metal, and the particle size of the modified carbon black is 100-1000 nm.
The modifier in the step 3 is formed by mixing a compound (1) and dialkyl sulfosuccinate according to the weight ratio of 1: 1;
the structural formula of the compound (1) is as follows:
wherein the crosslinking agent is triallyl isocyanurate, the antioxidant is antioxidant 1010, the calcination temperature in the step 1 is 150 ℃, the calcination temperature in the step 2 is 300 ℃, and the calcination time is 3 hours.
Comparative example 2
A high-stability waterproof cable comprises a conductor, a semi-conductive shielding layer, an insulating layer, a waterproof layer, an armor layer and a sheath from inside to outside, wherein the semi-conductive shielding layer is made of a semi-conductive shielding material.
The semiconductive shielding material comprises the following raw materials in percentage by weight: 50% of polyethylene, 20% of ethylene-vinyl acetate copolymer, 19% of modified carbon black, 10% of diethyl carbonate, 0.5% of cross-linking agent and 0.5% of antioxidant.
The preparation method of the modified carbon black comprises the following steps:
step 1: pretreating carbon black, namely soaking the carbon black in alkali liquor for 24 hours, soaking the carbon black in nitric acid for 24 hours after washing, washing the carbon black by deionized water, and calcining and activating the carbon black in an inert atmosphere to obtain activated carbon black;
step 2: adding activated carbon black to Ni2+And Co2+Adding ammonia water into the aqueous solution of (1) to adjust the pH value to 9, stirring, carrying out vacuum filtration, cleaning, drying and calcining under inert atmosphere to obtain the carbon black loaded with the active metal; calculated by a nickel simple substance and a cobalt simple substance, the modified carbon black contains 15 wt% of nickel and 3 wt% of cobalt;
and step 3: dispersing the carbon black loaded with the active metal into an ethanol solution, adding a modifier, stirring and reacting for 4-8 hours, and performing centrifugal separation, washing and drying to obtain modified carbon black; the amount of the modifier is 5wt% of the carbon black loaded with the active metal, and the particle size of the modified carbon black is 100-1000 nm.
The modifier in the step 3 is only composed of the compound (1);
the structural formula of the compound (1) is as follows:
wherein the crosslinking agent is triallyl isocyanurate, the antioxidant is antioxidant 1010, the calcination temperature in the step 1 is 150 ℃, the calcination temperature in the step 2 is 300 ℃, and the calcination time is 3 hours.
Comparative example 3
A high-stability waterproof cable comprises a conductor, a semi-conductive shielding layer, an insulating layer, a waterproof layer, an armor layer and a sheath from inside to outside, wherein the semi-conductive shielding layer is made of a semi-conductive shielding material.
The semiconductive shielding material comprises the following raw materials in percentage by weight: 50% of polyethylene, 20% of ethylene-vinyl acetate copolymer, 19% of modified carbon black, 10% of diethyl carbonate, 0.5% of cross-linking agent and 0.5% of antioxidant.
The preparation method of the modified carbon black comprises the following steps:
step 1: pretreating carbon black, namely soaking the carbon black in alkali liquor for 24 hours, soaking the carbon black in nitric acid for 24 hours after washing, washing the carbon black by deionized water, and calcining and activating the carbon black in an inert atmosphere to obtain activated carbon black;
step 2: adding activated carbon black to Ni2+And Co2+Adding ammonia water into the aqueous solution of (1) to adjust the pH value to 9, stirring, carrying out vacuum filtration, cleaning, drying and calcining under inert atmosphere to obtain the carbon black loaded with the active metal; calculated by a nickel simple substance and a cobalt simple substance, the modified carbon black contains 15 wt% of nickel and 3 wt% of cobalt;
and step 3: dispersing the carbon black loaded with the active metal into an ethanol solution, adding a modifier, stirring and reacting for 4-8 hours, and performing centrifugal separation, washing and drying to obtain modified carbon black; the amount of the modifier is 5wt% of the carbon black loaded with the active metal, and the particle size of the modified carbon black is 100-1000 nm.
The modifier in step 3 consists of dialkyl sulfosuccinate only.
Wherein the crosslinking agent is triallyl isocyanurate, the antioxidant is antioxidant 1010, the calcination temperature in the step 1 is 150 ℃, the calcination temperature in the step 2 is 300 ℃, and the calcination time is 3 hours.
And (3) effect characterization: the semiconductive shielding materials prepared in example 1 and comparative examples 1 to 3 were tested, and two main indicators were tested: (1) volume resistivity (Ω. m); (2) the number of impurities is more than 50 μm.
The following table details the kind of active metal, the constitution of the dispersant, the volume resistivity (Ω. m), and the amount of impurities of 50 μm or more in example 1 and comparative examples 1 to 3.
| Numbering | Reactive metal | Dispersing agent | Volume resistivity (omega. m) | Number of impurities of 50 μm or more |
| Example 1 | Nickel, cobalt | Compound (1): dialkyl sulfosuccinate =1:1 | 19 | 0 |
| Comparative example 1 | Nickel, aluminium | Compound (1): dialkyl sulfosuccinate =1:1 | 24 | 2 |
| Comparative example 2 | Nickel, cobalt | Compound (1) | 28 | 3 |
| Comparative example 3 | Nickel, cobalt | Dialkyl sulfosuccinates | 29 | 3 |
| CN106279929 A | Nickel, aluminium | Is free of | 32~35 | 5~6 |
The above results show that: (1) compared with the prior art, the volume resistivity (omega. m) of the shielding material prepared by the invention can reach 19, the number of impurities with the size of more than 50 micrometers is eliminated, and the shielding effect and the stability of the cable are greatly improved; (2) from the results of the embodiment 1 and the comparative examples 2 to 3, it can be seen that the compound (1) and the dialkyl sulfosuccinate are used for carrying out composite synergistic modification on the carbon black, so that the dispersion effect of the carbon black can be greatly improved, the uniform distribution of the carbon black in a shielding material is facilitated, the shielding effect of the carbon black in a cable is fully exerted, and the stability of the cable is ensured; (3) it can be seen from example 1 and comparative example 1 that, compared with nickel and aluminum, nickel and cobalt are used as the active metal for loading carbon black, which is more beneficial to improve the space potential distribution and surface property of carbon black, improve the dispersion degree of carbon black in the preparation process of the shielding material, and ensure the stability of the cable.
Claims (5)
1. A high-stability waterproof cable is characterized by comprising a conductor, a semi-conductive shielding layer, an insulating layer, a waterproof layer, an armor layer and a sheath from inside to outside, wherein the semi-conductive shielding layer is made of a semi-conductive shielding material; the semiconductive shielding material comprises the following raw materials in percentage by weight: 50% of polyethylene, 20% of ethylene-vinyl acetate copolymer, 19% of modified carbon black, 10% of diethyl carbonate, 0.5% of cross-linking agent and 0.5% of antioxidant; the preparation method of the modified carbon black comprises the following steps:
step 1: pretreating carbon black, namely soaking the carbon black in alkali liquor for 24 hours, soaking the carbon black in nitric acid for 24 hours after washing, washing the carbon black by deionized water, and calcining and activating the carbon black in an inert atmosphere to obtain activated carbon black;
step 2: adding activated carbon black to Ni2+And Co2+Adding ammonia water into the aqueous solution of (1) to adjust the pH value to 9-10, stirring, carrying out vacuum filtration, cleaning, drying, and calcining under inert atmosphere to obtain the carbon black loaded with active metal; calculated by a nickel simple substance and a cobalt simple substance, the modified carbon black contains 15 wt% of nickel and 3 wt% of cobalt;
and step 3: dispersing the carbon black loaded with the active metal into an ethanol solution, adding a modifier, stirring and reacting for 4-8 hours, and performing centrifugal separation, washing and drying to obtain modified carbon black; the amount of the modifier is 5wt% of the carbon black loaded with the active metal, and the particle size of the modified carbon black is 100-1000 nm;
the modifier in the step 3 is formed by mixing a compound (1) and dialkyl sulfosuccinate according to the weight ratio of 1: 1;
the structural formula of the compound (1) is as follows:
2. the highly stable waterproof cable according to claim 1, wherein said crosslinking agent is one of triallyl isocyanurate and trimethylolpropane trimethacrylate.
3. The high stability waterproof cable of claim 1, wherein said antioxidant is one of antioxidant 1010, antioxidant 1024, antioxidant 1035.
4. The high-stability waterproof cable according to claim 1, wherein the calcination temperature in step 1 is 150-200 ℃.
5. The waterproof cable as claimed in claim 1, wherein the calcination temperature in step 2 is 300-350 ℃ and the calcination time is 3-7 h.
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2019
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