CN118315105A - High-voltage-resistant cable and production process thereof - Google Patents

Abstract

The invention relates to a high-voltage-resistant cable which comprises a protective sleeve, a belting layer, an insulating layer, a conductor and a filling rope. The insulating layer is crosslinked polyethylene, and the crosslinked polyethylene comprises the following raw materials: low density polyethylene, cross-linking agent, methyl vinyl silicone rubber, ultraviolet resistant agent and voltage stabilizer. The methyl vinyl silicone rubber and the low-density polyethylene are used in combination, so that the insulation pressure resistance and the strength of the cable are improved. The synthesized ultraviolet resistant agent contains a diphenylamine antioxidant structure, a flexible polysiloxane chain, a3, 4-dihydroxybenzene structure and nano cerium oxide, and improves the oxidation resistance, ultraviolet ageing resistance, thermal stability and waterproofness of the cable. The synthesized voltage stabilizer contains a benzophenone structure, a benzothiadiazole structure, a piperazine ring, hydroxyl, carbon-carbon double bonds and the like, and improves the electrical aging resistance, the water tree aging resistance and the flame retardance of the cable.

Description

High-voltage-resistant cable and production process thereof

Technical Field

The invention belongs to the technical field of cable materials, and particularly relates to a high-voltage-resistant cable and a production process thereof.

Background

Power cables typically include several conductors, an insulation layer surrounding the conductors, an intermediate filled anchor layer, and an outermost insulation jacket. The insulating layer is typically polyvinyl chloride or crosslinked polyethylene insulating material. Compared with polyvinyl chloride insulated cable, the crosslinked polyethylene has the characteristics of simple structure, light weight, good heat resistance, strong loading capacity, no melting, chemical corrosion resistance, high mechanical strength and the like. However, in the use process of the crosslinked polyethylene insulating material, the crosslinked polyethylene insulating material is inevitably subjected to aging effects such as oxygen aging, photo aging, electrical aging, water tree aging and the like, so that insulation breakdown is caused, and the safe and stable operation of the cable is further affected.

The proper ultraviolet screening agent is selected, so that the photo-aging phenomenon of the insulating material can be effectively slowed down. At present, most of commercial organic ultraviolet screening agents are small molecules, are easy to directly undergo photoaging degradation and migration from a matrix to fail, and meanwhile, the poor thermal stability also makes the protection life of the organic ultraviolet screening agents limited. Inorganic ultraviolet screening agents have the advantages of good thermal stability, difficult free radical attack and the like, but have poor compatibility with polymer matrixes, and have large refractive index difference, so that the system is easily opaque, the appearance of the materials is influenced, most inorganic ultraviolet screening agents belong to semiconductor materials, have high photocatalytic activity, can initiate optical reaction under ultraviolet light, accelerate the ageing and degradation of the polymer matrixes, shorten the service life of the protected materials, and limit the use of the inorganic ultraviolet screening agents. In view of this, finding a suitable ultraviolet screening agent, overcoming the drawbacks of the existing ultraviolet screening agents, is still an objective that the present-day scholars strive to pursue.

The electrical aging of the cable insulation material refers to electrical branch aging, which is a cumulative breakdown phenomenon related to charge movement and trap distribution, and in the process of capturing and compositing electrons, hot electrons acquire energy to impact and destroy molecular chains of polymers, so that dendritic electron channels are formed. The voltage stabilizer is an anti-aging agent for improving the electrical resistance of the crosslinked polyethylene insulating material by inhibiting electrical dendrite, the added voltage stabilizer is easy to migrate and lose efficacy, and the crosslinked polyethylene material has certain flammability, so that a proper voltage stabilizer needs to be found to improve the current problems.

Disclosure of Invention

In order to solve the technical problems, the invention provides a high-voltage-resistant cable and a production process thereof.

The aim of the invention can be achieved by the following technical scheme: a high-voltage cable comprises a protective sleeve, a belting layer, an insulating layer, a conductor and a filling rope, wherein the insulating layer is coated on the periphery of the conductor, the filling rope is filled between the insulating layer and the belting layer, and the protective sleeve is coated on the periphery of the belting layer.

Further, the sheath pipe is a high-density polyethylene sheath pipe, the wrapping tape layer is formed by flame-retardant wrapping tape, the conductor is a copper conductor, the filling rope is a polypropylene filling rope, the insulating layer is crosslinked polyethylene, and the crosslinked polyethylene comprises the following raw materials in parts by weight: 150-160 parts of low-density polyethylene, 10-12 parts of cross-linking agent, 30-40 parts of methyl vinyl silicone rubber, 6.5-7.5 parts of ultraviolet resistance agent and 5.5-6.5 parts of voltage stabilizer.

Further, the cross-linking agent is benzoyl peroxide.

The ultraviolet resistance agent is prepared through the following steps:

Step A1: adding o-aminodiphenylamine, potassium carbonate and dimethyl sulfoxide into a flask to obtain a mixed solution a, adding 3, 4-dihydroxybenzoyl chloride into a dimethyl sulfoxide solution to obtain a mixed solution b, slowly dropwise adding the mixed solution b into the mixed solution a under the ice water bath at the temperature of 0 ℃, heating to 50-60 ℃ after dropwise adding, reacting at constant temperature for 6-8h, and distilling under reduced pressure to obtain an intermediate 1;

Further, the dosage ratio of the 3, 4-dihydroxybenzoyl chloride, the o-aminodiphenylamine, the potassium carbonate and the dimethyl sulfoxide is 0.1 mol:0.1 mol:0.01-0.015 mol:100 mL;

In the reaction process of the step A1, the o-aminodiphenylamine reacts with 3, 4-dihydroxybenzoyl chloride to generate an amidated product intermediate 1. Intermediate 1 has the structure shown below:

Step A2: toluene, hydrogen-containing silicone oil, hydroquinone and cis-dichloro bis (pyridyl) platinum are added into a three-neck flask according to a certain proportion, stirred and nitrogen is introduced for protection, 7-bromohept-1-en-3-one is dropwise added, the temperature is slowly increased to 70-80 ℃, the stirring reaction is carried out for 3-4 hours, and vacuum pumping is carried out, thus obtaining an intermediate 2;

Further, the dosage ratio of the 7-bromohept-1-en-3-one, toluene, hydrogen-containing silicone oil, hydroquinone and cis-dichloro bis (pyridyl) platinum is 1-1.5 mol:100 ml:1 mol:0.5 mol:0.015-0.020 mol;

in the reaction process of the step A2, hydrogen-containing silicone oil reacts with 7-bromohept-1-en-3-one under the catalysis of cis-dichloro bis (pyridyl) platinum, and Si-H bonds are added with C=C bonds to generate an intermediate 2. Intermediate 2 structure is shown below:

step A3: adding the intermediate 2, the intermediate 1 and methanol into a flask, adding 2-dicyclohexylphosphorus-2 ' -4' -6' -triisopropylbiphenyl, tris (dibenzylideneacetone) dipalladium and potassium carbonate, carrying out reflux stirring reaction for 4-5h at 80 ℃ under the protection of nitrogen, and carrying out vacuum drying at 50 ℃ to obtain an intermediate 3;

Further, the dosage ratio of the intermediate 2, the intermediate 1, methanol, 2-dicyclohexylphosphorus-2 ' -4' -6' -triisopropylbiphenyl, tris (dibenzylideneacetone) dipalladium and potassium carbonate is 0.06 mol:0.06 mol:300-350 mL:0.0025 g:0.0025 g:0.15-0.18 mol;

in the reaction process of the step A3, the intermediate 2 and the intermediate 1 undergo dehydrobromination coupling reaction to generate an intermediate 3. Intermediate 3 has the structure shown below:

Step A4: adding the nano cerium oxide powder into an ethanol water solution, and stirring for 10min to obtain a mixed solution c; adding the intermediate 3 into ethanol water solution, and stirring for 20min to obtain a mixed solution d; adding the mixed solution c and the mixed solution d into a flask, performing ultrasonic dispersion for 40min to obtain a mixed system, adding an acetic acid solution into the mixed system under stirring, adjusting the pH of the mixed system to 5.5-6.5, heating to 50 ℃, stirring for reaction for 10h, cooling to room temperature, performing centrifugal separation, washing with absolute ethyl alcohol for three times, drying at 70 ℃ for 12h in an oven, and grinding to obtain the ultraviolet resistant agent;

Further, the dosage ratio of the nano cerium oxide powder to the intermediate 3 to the ethanol aqueous solution to the acetic acid solution is 0.1g to 0.0012mol to 55mL to 0.3-0.4mL, the volume fraction of the ethanol aqueous solution is 10%, and the concentration of the acetic acid solution is 1mol/L;

In the reaction process of the step A4, hydroxyl on the surface of the nano cerium oxide is grafted with the intermediate 3 to generate the ultraviolet resistant agent. In the ultraviolet resistant agent, the diphenylamine antioxidant structure inhibits or delays the breakage of polymer molecular chains to generate free radicals, and prevents the high polymer material from oxidative aging; the flexible polysiloxane chain has higher thermal stability, so that the thermal stability of the ultraviolet resistance agent is improved; after grafting with the intermediate 3, the compatibility and the dispersibility of the nano cerium oxide and the polymer are increased, the 3, 4-dihydroxybenzene structure has strong ultraviolet resistance, and the ultraviolet absorption effect of the ultraviolet resistance agent is greatly improved.

The voltage stabilizer is prepared through the following steps:

Step B1: adding maleic anhydride and 2, 4-dihydroxybenzophenone into a flask filled with tetrahydrofuran, then dropwise adding concentrated sulfuric acid, heating to 70-80 ℃, carrying out reflux stirring reaction for 9-10h to obtain a reaction solution, pouring the reaction solution into deionized water, standing for 10-20min, centrifuging, taking out lower oily substance, and drying in a vacuum drying oven at 80 ℃ for 2-4h to obtain an intermediate a;

further, the dosage ratio of the maleic anhydride to the 2, 4-dihydroxybenzophenone to the concentrated sulfuric acid to the deionized water is 0.11 mol:0.10 mol:10-12 mL:200 mL, and the mass fraction of the concentrated sulfuric acid is 98%;

In the reaction process of the step B1, maleic anhydride and phenolic hydroxyl with smaller steric hindrance in 2, 4-dihydroxybenzophenone are subjected to esterification reaction to generate an intermediate a. The structure of intermediate a is as follows:

step B2: in a nitrogen atmosphere, adding the intermediate a into a round-bottomed flask, heating to 45 ℃, adding tetrabutylammonium bromide, starting stirring, slowly dripping epichlorohydrin into the round-bottomed flask, and stirring for reaction for 5-6h to obtain an intermediate b;

Further, the dosage ratio of the intermediate a, tetrabutylammonium bromide and epichlorohydrin is 0.1 mol:0.001-0.0012 mol:0.1 mol;

in the reaction process of the step B2, the intermediate a and the epichlorohydrin are subjected to ring opening to generate an intermediate B. The structure of intermediate b is as follows:

Step B3: adding 2- (4- (benzo [ C ] [1,2,5] thiadiazol-5-ylmethyl) piperazin-1-yl) ethane-1-ol into DMF, adding an intermediate b and sodium hydroxide under stirring, stirring and reacting for 4-4.5h at 40 ℃, filtering, washing with water, and drying to obtain a voltage stabilizer;

Further, the dosage ratio of 2- (4- (benzo [ C ] [1,2,5] thiadiazol-5-ylmethyl) piperazin-1-yl) ethane-1-ol, DMF, intermediate b and sodium hydroxide is as follows: 0.1 mol:180 mL:0.1 mol:0.1-0.2 g;

In the reaction process of the step B3, 2- (4- (benzo [ C ] [1,2,5] thiadiazol-5-ylmethyl) piperazin-1-yl) ethane-1-ol and the intermediate B are subjected to etherification reaction to obtain the voltage stabilizer. In the voltage stabilizer, a benzophenone structure captures hot electrons under a high electric field and absorbs the energy of the hot electrons in an excitation mode, and meanwhile, the keto-enol tautomerism reaction also consumes electron energy, so that the influence of electrons on a molecular chain is weakened, the breakage of a polymer chain is inhibited, and the voltage stabilizer has good electrical branch resistance; the benzothiadiazole structure has larger electron affinity energy, the electron affinity energy has the largest influence on the efficiency of the voltage stabilizer, and the larger the electron affinity energy is, the better the voltage branch inhibiting capability is, so that the voltage stabilizer has the capability of inhibiting the voltage branch; the piperazine ring and the thiadiazole structure contain more nitrogen atoms, and when the piperazine ring and the thiadiazole structure are heated and decomposed, a large amount of inert gases are generated, the inert gases play a role in absorbing heat and isolating oxygen, most of heat is consumed by an endothermic reaction generated in the decomposition process, the surface temperature of the material is reduced, and the purposes of further preventing combustion and flame propagation are also achieved; unsaturated double bond, make the stabiliser can be grafted into crosslinked polyethylene through the free radical reaction, avoid migrating the inefficacy; the hydroxyl, carbonyl and nitrogen atoms can generate hydrogen bond association with water molecules, so that diffusion is prevented to form water drops, the growth of water trees is inhibited, and the water tree aging resistance is achieved.

The structure of the stabilizer is as follows:

The invention has the beneficial effects that: the high-voltage cable prepared by the invention comprises a protective sleeve, wherein a wrapping band layer is arranged in the protective sleeve, a plurality of conductors are arranged in the wrapping band layer, an insulating layer is arranged on the periphery of each conductor, and filling ropes are filled between the wrapping band and the insulating layer. The insulating layer is crosslinked polyethylene, and the crosslinked polyethylene comprises raw materials of low-density polyethylene, a crosslinking agent, methyl vinyl silicone rubber, an ultraviolet resistance agent and a voltage stabilizer. The insulating layer is formed by mixing low-density polyethylene with excellent electrical insulation performance and methyl vinyl silicone rubber with small compression deformation, so that the insulating pressure resistance of the material is outstanding, and the strength of the cable is improved due to good dispersion and compatibility of the methyl vinyl silicone rubber in the low-density polyethylene. In the synthesized ultraviolet resistant agent, the diphenylamine antioxidant structure inhibits or delays the generation of free radicals by breaking polymer molecular chains, prevents the oxidative aging of crosslinked polyethylene and prolongs the service life of the cable; the flexible polysiloxane chain has higher thermal stability and is mutually entangled with the crosslinked polyethylene chain to form a three-dimensional network, so that the thermal stability and the water resistance of the crosslinked polyethylene are improved, and the thermal stability and the water resistance of the cable are improved; after grafting with the intermediate 3, the compatibility and the dispersibility of the nano cerium oxide and the polymer are increased, and the 3, 4-dihydroxybenzene structure is not easy to migrate and lose effectiveness in a matrix along with the entanglement of the polysiloxane chain and the crosslinked polyethylene chain, so that the ultraviolet aging resistance of the cable is greatly improved. In addition, the thermal oxidative aging phenomenon still exists in the methyl vinyl silicone rubber at a high temperature, and the addition of cerium oxide helps to promote the thermal oxidative aging resistance of the methyl vinyl silicone rubber.

In the synthesized voltage stabilizer, a benzophenone structure captures hot electrons under a high electric field, absorbs the energy of the hot electrons in an excitation mode, and simultaneously, the keto-enol tautomerism reaction consumes electron energy, so that the influence of electrons on a molecular chain is weakened, the breakage of a polymer chain is inhibited, the breakdown field strength and the electrical branch resistance of an insulating layer are improved, and the electrical aging phenomenon of a cable is inhibited; the benzothiadiazole structure has larger electron affinity energy, the electron affinity energy has the largest influence on the efficiency of the voltage stabilizer, and the larger the electron affinity energy is, the better the electric branch inhibiting capability is, so that the electric branch inhibiting capability of the insulating layer is improved, and the electric aging resistance of the cable is further improved; the piperazine ring and the thiadiazole structure contain more nitrogen atoms, and when the piperazine ring and the thiadiazole structure are heated and decomposed, a large amount of inert gases are generated, the inert gases play a role in absorbing heat and isolating oxygen, most of heat is consumed by an endothermic reaction generated in the decomposition process, the surface temperature of an insulating layer is reduced, the purposes of further preventing combustion and spreading flame are also achieved, and the flame retardance of the cable is improved; unsaturated double bond, make the stabiliser can be grafted into crosslinked polyethylene through the free radical reaction, avoid migrating the inefficacy; the hydroxyl, carbonyl and nitrogen atoms can generate hydrogen bond association with water molecules, so that the water molecules are prevented from diffusing to form water drops, the growth of water trees is inhibited, and the water tree aging resistance of the cable is improved.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.

Fig. 1 is a schematic structural view of a high voltage cable according to the present invention.

In the drawings, the list of components represented by the various numbers is as follows:

A. a sheath tube; B. a tape layer; C. an insulating layer; D. a conductor; E. and (5) filling the rope.

Detailed Description

The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.

Example 1

An ultraviolet resistant agent is prepared by the following steps:

Step A1: adding o-aminodiphenylamine, potassium carbonate and dimethyl sulfoxide into a flask to obtain a mixed solution a, adding 3, 4-dihydroxybenzoyl chloride into a dimethyl sulfoxide solution to obtain a mixed solution b, slowly dropwise adding the mixed solution b into the mixed solution a under the ice water bath at the temperature of 0 ℃, heating to 50 ℃ after dropwise adding, reacting at constant temperature for 6 hours, and distilling under reduced pressure to obtain an intermediate 1; the dosage ratio of the 3, 4-dihydroxybenzoyl chloride to the o-aminodiphenylamine to the potassium carbonate to the dimethyl sulfoxide is 0.1 mol:0.1 mol:0.01 mol:100 mL;

Step A2: toluene, hydrogen-containing silicone oil, hydroquinone and cis-dichloro bis (pyridyl) platinum are added into a three-neck flask according to a certain proportion, stirred and nitrogen is introduced for protection, 7-bromohept-1-en-3-one is dropwise added, the temperature is slowly increased to 70 ℃, stirring is carried out for 3 hours, and vacuum pumping is carried out, thus obtaining an intermediate 2; the dosage ratio of the 7-bromohept-1-en-3-one, the toluene, the hydrogen-containing silicone oil, the hydroquinone and the cis-dichloro bis (pyridyl) platinum is 1 mol:100 ml:1 mol:0.5 mol:0.015 mol;

step A3: adding the intermediate 2, the intermediate 1 and methanol into a flask, adding 2-dicyclohexylphosphorus-2 ' -4' -6' -triisopropylbiphenyl, tris (dibenzylideneacetone) dipalladium and potassium carbonate, carrying out reflux stirring reaction for 4 hours at 80 ℃ under the protection of nitrogen, and carrying out vacuum drying at 50 ℃ to obtain an intermediate 3; the dosage ratio of the intermediate 2, the intermediate 1, the methanol, the 2-dicyclohexylphosphorus-2 ' -4' -6' -triisopropylbiphenyl, the tris (dibenzylideneacetone) dipalladium and the potassium carbonate is 0.06 mol:0.06 mol:300 mL:0.0025 g:0.0025 g:0.15 mol;

Step A4: adding the nano cerium oxide powder into an ethanol water solution, and stirring for 10min to obtain a mixed solution c; adding the intermediate 3 into ethanol water solution, and stirring for 20min to obtain a mixed solution d; adding the mixed solution c and the mixed solution d into a flask, performing ultrasonic dispersion for 40min to obtain a mixed system, adding an acetic acid solution into the mixed system under stirring, adjusting the pH of the mixed system to 5.5, heating to 50 ℃, stirring for reaction for 10h, cooling to room temperature, performing centrifugal separation, washing with absolute ethanol for three times, drying at 70 ℃ for 12h in an oven, and grinding to obtain the ultraviolet resistant agent; the dosage ratio of the nano cerium oxide powder to the intermediate 3 to the ethanol aqueous solution to the acetic acid solution is 0.1g to 0.0012mol to 55mL to 0.3mL, the volume fraction of the ethanol aqueous solution is 10%, and the concentration of the acetic acid solution is 1mol/L.

Example 2

An ultraviolet resistant agent is prepared by the following steps:

Step A1: adding o-aminodiphenylamine, potassium carbonate and dimethyl sulfoxide into a flask to obtain a mixed solution a, adding 3, 4-dihydroxybenzoyl chloride into a dimethyl sulfoxide solution to obtain a mixed solution b, slowly dropwise adding the mixed solution b into the mixed solution a under the ice water bath at the temperature of 0 ℃, heating to 55 ℃ after dropwise adding, reacting at constant temperature for 7h, and distilling under reduced pressure to obtain an intermediate 1; the dosage ratio of the 3, 4-dihydroxybenzoyl chloride to the o-aminodiphenylamine to the potassium carbonate to the dimethyl sulfoxide is 0.1 mol:0.1 mol:0.012 mol:100 mL;

Step A2: toluene, hydrogen-containing silicone oil, hydroquinone and cis-dichloro bis (pyridyl) platinum are added into a three-neck flask according to a certain proportion, stirred and nitrogen is introduced for protection, 7-bromohept-1-en-3-one is dropwise added, the temperature is slowly increased to 75 ℃, the stirring reaction is carried out for 3.5 hours, and vacuum pumping is carried out, thus obtaining an intermediate 2; the dosage ratio of the 7-bromohept-1-en-3-one, the toluene, the hydrogen-containing silicone oil, the hydroquinone and the cis-dichloro bis (pyridyl) platinum is 1.2 mol:100 ml:1 mol:0.5 mol:0.017 mol;

Step A3: adding the intermediate 2, the intermediate 1 and methanol into a flask, adding 2-dicyclohexylphosphorus-2 ' -4' -6' -triisopropylbiphenyl, tris (dibenzylideneacetone) dipalladium and potassium carbonate, carrying out reflux stirring reaction for 4.5h at 80 ℃ under the protection of nitrogen, and carrying out vacuum drying at 50 ℃ to obtain an intermediate 3; the dosage ratio of the intermediate 2, the intermediate 1, the methanol, the 2-dicyclohexylphosphorus-2 ' -4' -6' -triisopropylbiphenyl, the tris (dibenzylideneacetone) dipalladium and the potassium carbonate is 0.06 mol:0.06 mol:320 mL:0.0025 g:0.0025 g:0.16 mol;

Step A4: adding the nano cerium oxide powder into an ethanol water solution, and stirring for 10min to obtain a mixed solution c; adding the intermediate 3 into ethanol water solution, and stirring for 20min to obtain a mixed solution d; adding the mixed solution c and the mixed solution d into a flask, performing ultrasonic dispersion for 40min to obtain a mixed system, adding an acetic acid solution into the mixed system under stirring, adjusting the pH of the mixed system to 6.0, heating to 50 ℃, stirring for reaction for 10h, cooling to room temperature, performing centrifugal separation, washing with absolute ethanol for three times, drying at 70 ℃ for 12h in an oven, and grinding to obtain the ultraviolet resistant agent; the dosage ratio of the nano cerium oxide powder to the intermediate 3 to the ethanol aqueous solution to the acetic acid solution is 0.1g to 0.0012mol to 55mL to 0.35mL, the volume fraction of the ethanol aqueous solution is 10%, and the concentration of the acetic acid solution is 1mol/L.

Example 3

An ultraviolet resistant agent is prepared by the following steps:

Step A1: adding o-aminodiphenylamine, potassium carbonate and dimethyl sulfoxide into a flask to obtain a mixed solution a, adding 3, 4-dihydroxybenzoyl chloride into a dimethyl sulfoxide solution to obtain a mixed solution b, slowly dropwise adding the mixed solution b into the mixed solution a under the ice water bath at the temperature of 0 ℃, heating to the temperature of 60 ℃ after the dropwise adding is finished, reacting for 8 hours at constant temperature, and distilling under reduced pressure to obtain an intermediate 1; the dosage ratio of the 3, 4-dihydroxybenzoyl chloride to the o-aminodiphenylamine to the potassium carbonate to the dimethyl sulfoxide is 0.1 mol:0.1 mol:0.015 mol:100 mL;

Step A2: toluene, hydrogen-containing silicone oil, hydroquinone and cis-dichloro bis (pyridyl) platinum are added into a three-neck flask according to a certain proportion, stirred and nitrogen is introduced for protection, 7-bromohept-1-en-3-one is dropwise added, the temperature is slowly increased to 80 ℃, the stirring reaction is carried out for 4 hours, and vacuum pumping is carried out, thus obtaining an intermediate 2; the dosage ratio of the 7-bromohept-1-en-3-one, the toluene, the hydrogen-containing silicone oil, the hydroquinone and the cis-dichloro bis (pyridyl) platinum is 1.5mol to 100ml to 1mol to 0.5mol to 0.020mol;

Step A3: adding the intermediate 2, the intermediate 1 and methanol into a flask, adding 2-dicyclohexylphosphorus-2 ' -4' -6' -triisopropylbiphenyl, tris (dibenzylideneacetone) dipalladium and potassium carbonate, carrying out reflux stirring reaction for 5h at 80 ℃ under the protection of nitrogen, and carrying out vacuum drying at 50 ℃ to obtain an intermediate 3; the dosage ratio of the intermediate 2, the intermediate 1, the methanol, the 2-dicyclohexylphosphorus-2 ' -4' -6' -triisopropylbiphenyl, the tris (dibenzylideneacetone) dipalladium and the potassium carbonate is 0.06 mol:0.06 mol:350 mL:0.0025 g:0.0025 g:0.18 mol;

Step A4: adding the nano cerium oxide powder into an ethanol water solution, and stirring for 10min to obtain a mixed solution c; adding the intermediate 3 into ethanol water solution, and stirring for 20min to obtain a mixed solution d; adding the mixed solution c and the mixed solution d into a flask, performing ultrasonic dispersion for 40min to obtain a mixed system, adding an acetic acid solution into the mixed system under stirring, adjusting the pH of the mixed system to 6.5, heating to 50 ℃, stirring for reaction for 10h, cooling to room temperature, performing centrifugal separation, washing with absolute ethanol for three times, drying at 70 ℃ for 12h in an oven, and grinding to obtain the ultraviolet resistant agent; the dosage ratio of the nano cerium oxide powder to the intermediate 3 to the ethanol aqueous solution to the acetic acid solution is 0.1g to 0.0012mol to 55mL to 0.4mL, the volume fraction of the ethanol aqueous solution is 10%, and the concentration of the acetic acid solution is 1mol/L.

Example 4

A voltage stabilizer prepared by the steps of:

step B1: adding maleic anhydride and 2, 4-dihydroxybenzophenone into a flask filled with tetrahydrofuran, then dropwise adding concentrated sulfuric acid, heating to 70 ℃, refluxing and stirring for reaction for 9 hours to obtain a reaction liquid, pouring the reaction liquid into deionized water, standing for 10 minutes, centrifuging, taking out lower oily substance, and drying in a vacuum drying oven at 80 ℃ for 2 hours to obtain an intermediate a; the dosage ratio of the maleic anhydride to the 2, 4-dihydroxybenzophenone to the concentrated sulfuric acid to the deionized water is 0.11 mol:0.10 mol:10 mL:200 mL, and the mass fraction of the concentrated sulfuric acid is 98%;

Step B2: in a nitrogen atmosphere, adding the intermediate a into a round-bottomed flask, heating to 45 ℃, adding tetrabutylammonium bromide, starting stirring, slowly dripping epichlorohydrin into the round-bottomed flask, and stirring for reacting for 5 hours to obtain an intermediate b; the dosage ratio of the intermediate a, tetrabutylammonium bromide and epichlorohydrin is 0.1 mol:0.001 mol:0.1 mol;

step B3: adding 2- (4- (benzo [ C ] [1,2,5] thiadiazol-5-ylmethyl) piperazin-1-yl) ethane-1-ol into DMF, adding an intermediate b and sodium hydroxide under stirring, stirring at 40 ℃ for reaction for 4 hours, filtering, washing with water, and drying to obtain a voltage stabilizer; the dosage ratio of 2- (4- (benzo [ C ] [1,2,5] thiadiazol-5-ylmethyl) piperazin-1-yl) ethane-1-ol, DMF, intermediate b and sodium hydroxide is as follows: 0.1 mol:180 mL:0.1 mol:0.1 g.

Example 5

A voltage stabilizer prepared by the steps of:

Step B1: adding maleic anhydride and 2, 4-dihydroxybenzophenone into a flask filled with tetrahydrofuran, then dropwise adding concentrated sulfuric acid, heating to 75 ℃, refluxing and stirring for reaction for 9.5 hours to obtain a reaction liquid, pouring the reaction liquid into deionized water, standing for 15 minutes, centrifuging, taking out a lower oily substance, and drying in a vacuum drying oven at 80 ℃ for 3 hours to obtain an intermediate a; the dosage ratio of the maleic anhydride to the 2, 4-dihydroxybenzophenone to the concentrated sulfuric acid to the deionized water is 0.11 mol:0.10 mol:11 mL:200 mL, and the mass fraction of the concentrated sulfuric acid is 98%;

Step B2: in a nitrogen atmosphere, adding the intermediate a into a round-bottomed flask, heating to 45 ℃, adding tetrabutylammonium bromide, starting stirring, slowly dripping epichlorohydrin into the round-bottomed flask, and stirring for reacting for 5.5h to obtain an intermediate b; the dosage ratio of the intermediate a, tetrabutylammonium bromide and epichlorohydrin is 0.1 mol:0.0011 mol:0.1 mol;

Step B3: adding 2- (4- (benzo [ C ] [1,2,5] thiadiazol-5-ylmethyl) piperazin-1-yl) ethane-1-ol into DMF, adding an intermediate b and sodium hydroxide under stirring, stirring at 40 ℃ for reaction for 4.2 hours, filtering, washing with water, and drying to obtain a voltage stabilizer; the dosage ratio of 2- (4- (benzo [ C ] [1,2,5] thiadiazol-5-ylmethyl) piperazin-1-yl) ethane-1-ol, DMF, intermediate b and sodium hydroxide is as follows: 0.1 mol:180 mL:0.1 mol:0.15 g.

Example 6

A voltage stabilizer prepared by the steps of:

Step B1: adding maleic anhydride and 2, 4-dihydroxybenzophenone into a flask filled with tetrahydrofuran, then dropwise adding concentrated sulfuric acid, heating to 80 ℃, carrying out reflux stirring reaction for 10 hours to obtain a reaction liquid, pouring the reaction liquid into deionized water, standing for 20 minutes, centrifuging, taking out lower oily substance, and drying in a vacuum drying oven at 80 ℃ for 4 hours to obtain an intermediate a; the dosage ratio of the maleic anhydride to the 2, 4-dihydroxybenzophenone to the concentrated sulfuric acid to the deionized water is 0.11 mol:0.10 mol:12 mL:200 mL, and the mass fraction of the concentrated sulfuric acid is 98%;

Step B2: in a nitrogen atmosphere, adding the intermediate a into a round-bottomed flask, heating to 45 ℃, adding tetrabutylammonium bromide, starting stirring, slowly dripping epichlorohydrin into the round-bottomed flask, and stirring for reaction for 6 hours to obtain an intermediate b; the dosage ratio of the intermediate a, tetrabutylammonium bromide and epichlorohydrin is 0.1 mol:0.0012 mol:0.1 mol;

Step B3: adding 2- (4- (benzo [ C ] [1,2,5] thiadiazol-5-ylmethyl) piperazin-1-yl) ethane-1-ol into DMF, adding an intermediate b and sodium hydroxide under stirring, stirring at 40 ℃ for reaction for 4.5 hours, filtering, washing with water, and drying to obtain a voltage stabilizer; the dosage ratio of 2- (4- (benzo [ C ] [1,2,5] thiadiazol-5-ylmethyl) piperazin-1-yl) ethane-1-ol, DMF, intermediate b and sodium hydroxide is as follows: 0.1 mol:180 mL:0.1 mol:0.2 g.

Example 7

The high-voltage cable shown in fig. 1 comprises a protective sleeve A, a wrapping band layer B, an insulating layer C, a conductor D and a filling rope E, wherein the insulating layer C is coated on the periphery of the conductor D, the filling rope E is filled between the insulating layer C and the wrapping band layer B, and the protective sleeve A is coated on the periphery of the wrapping band layer B. The sheath pipe A is a high-density polyethylene sheath pipe, the tape layer B is formed by flame-retardant tapes, the conductor D is a copper conductor, the filling rope E is a polypropylene filling rope, the insulating layer C is crosslinked polyethylene, and the crosslinked polyethylene comprises the following raw materials in parts by weight: 150 parts of low-density polyethylene, 10 parts of cross-linking agent, 30 parts of methyl vinyl silicone rubber, 6.5 parts of ultraviolet resistance agent and 5.5 parts of voltage stabilizer.

The high-voltage-resistant cable is prepared through the following steps:

Step S1: putting low-density polyethylene into a rheometer, carrying out melt blending, mixing for 4min at 105 ℃ and a rotating speed of 50r/min, then adding the voltage stabilizer and the cross-linking agent obtained in the example 4, mixing for 3min, then adding methyl vinyl silicone rubber and the ultraviolet resistant agent obtained in the example 1, and finally mixing for 10min to obtain the cross-linked polyethylene;

Step S2: extruding the crosslinked polyethylene outside the copper conductor by using an extruder to form an insulating layer coated on the periphery of the conductor, and performing annealing treatment after extrusion to obtain a cable core; placing a cable core and a polypropylene filling rope, wrapping with a flame-retardant wrapping tape to form a wrapping tape layer, filling the polypropylene filling rope between the wrapping tape layer and the insulating layer, extruding and wrapping the high-density polyethylene outside the wrapping tape layer on a sheath layer outside the wrapping tape layer by using an extruder, and performing annealing treatment after extrusion to obtain the high-voltage-resistant cable.

Example 8

The high-voltage cable shown in fig. 1 comprises a protective sleeve A, a wrapping band layer B, an insulating layer C, a conductor D and a filling rope E, wherein the insulating layer C is coated on the periphery of the conductor D, the filling rope E is filled between the insulating layer C and the wrapping band layer B, and the protective sleeve A is coated on the periphery of the wrapping band layer B. The sheath pipe A is a high-density polyethylene sheath pipe, the tape layer B is formed by flame-retardant tapes, the conductor D is a copper conductor, the filling rope E is a polypropylene filling rope, the insulating layer C is crosslinked polyethylene, and the crosslinked polyethylene comprises the following raw materials in parts by weight: 155 parts of low-density polyethylene, 11 parts of a cross-linking agent, 35 parts of methyl vinyl silicone rubber, 7 parts of an ultraviolet resistance agent and 6 parts of a voltage stabilizer.

The high-voltage-resistant cable is prepared through the following steps:

Step S1: putting low-density polyethylene into a rheometer, carrying out melt blending, mixing for 5min at 105 ℃ and a rotating speed of 50r/min, then adding the voltage stabilizer and the cross-linking agent obtained in the example 5, mixing for 3min, then adding methyl vinyl silicone rubber and the ultraviolet resistant agent obtained in the example 2, and finally mixing for 12min to obtain the cross-linked polyethylene;

Step S2: extruding the crosslinked polyethylene outside the copper conductor by using an extruder to form an insulating layer coated on the periphery of the conductor, and performing annealing treatment after extrusion to obtain a cable core; placing a cable core and a polypropylene filling rope, wrapping with a flame-retardant wrapping tape to form a wrapping tape layer, filling the polypropylene filling rope between the wrapping tape layer and the insulating layer, extruding and wrapping the high-density polyethylene outside the wrapping tape layer on a sheath layer outside the wrapping tape layer by using an extruder, and performing annealing treatment after extrusion to obtain the high-voltage-resistant cable.

Example 9

The high-voltage cable shown in fig. 1 comprises a protective sleeve A, a wrapping band layer B, an insulating layer C, a conductor D and a filling rope E, wherein the insulating layer C is coated on the periphery of the conductor D, the filling rope E is filled between the insulating layer C and the wrapping band layer B, and the protective sleeve A is coated on the periphery of the wrapping band layer B. The sheath pipe A is a high-density polyethylene sheath pipe, the tape layer B is formed by flame-retardant tapes, the conductor D is a copper conductor, the filling rope E is a polypropylene filling rope, the insulating layer C is crosslinked polyethylene, and the crosslinked polyethylene comprises the following raw materials in parts by weight: 160 parts of low-density polyethylene, 12 parts of cross-linking agent, 40 parts of methyl vinyl silicone rubber, 7.5 parts of ultraviolet resistance agent and 6.5 parts of voltage stabilizer.

The high-voltage-resistant cable is prepared through the following steps:

step S1: putting low-density polyethylene into a rheometer, carrying out melt blending, mixing for 6min at 110 ℃ and a rotating speed of 50r/min, then adding the voltage stabilizer and the cross-linking agent obtained in the example 6, mixing for 3min, adding methyl vinyl silicone rubber and the ultraviolet resistant agent obtained in the example 3, and finally mixing for 15min to obtain the cross-linked polyethylene;

Step S2: extruding the crosslinked polyethylene outside the copper conductor by using an extruder to form an insulating layer coated on the periphery of the conductor, and performing annealing treatment after extrusion to obtain a cable core; placing a cable core and a polypropylene filling rope, wrapping with a flame-retardant wrapping tape to form a wrapping tape layer, filling the polypropylene filling rope between the wrapping tape layer and the insulating layer, extruding and wrapping the high-density polyethylene outside the wrapping tape layer on a sheath layer outside the wrapping tape layer by using an extruder, and performing annealing treatment after extrusion to obtain the high-voltage-resistant cable.

Comparative example 1

The comparative example is a commercially available pressure-resistant cable.

Comparative example 2

The ultraviolet resistance agent is changed into 3, 4-dihydroxybenzoic acid ethyl ester modified nano cerium oxide, and the other parts are completely identical to the embodiment 9, so that the high-voltage cable is prepared.

Comparative example 3

The voltage stabilizer was changed to an intermediate a, which is an esterification reaction product of 2, 4-dihydroxybenzophenone and maleic anhydride, and the same procedure as in example 9 was followed to obtain a high voltage cable.

The high withstand voltage cable prepared by the present invention was further tested for effect as follows.

For testing the high withstand voltage cable prepared by the invention, the test is carried out according to GB/T2951-2008 general test method for cable and optical cable insulation and sheath materials, ASTM D624, GB/T11017.1, method for rated voltage 110kV crosslinked polyethylene insulation power cable and accessories thereof, ultraviolet aging condition of 0.89W/m ², temperature of 50 ℃ and aging time of 500h, GB/T2406-93 plastic combustion performance test method and the like, and the results are shown in Table 1.

Table 1:

the test method of the alternating current and direct current breakdown field strength in table 1 is: applying a linearly-raised alternating current or direct current voltage to a film sample of the crosslinked polyethylene material with the thickness of 100 mu m until the pattern breaks down, and obtaining average alternating current and direct current breakdown field strengths of 10 samples;

The test method of the average electrical branch initiation voltage in table 1 is: and (3) performing an electric branch initiation voltage test on the crosslinked polyethylene material by adopting a needle-plate electrode structure, wherein the needle-plate distance is 3mm, the curvature radius of the needle point is 5 mu m, and the boosting mode is linear boosting, so that the average electric branch initiation voltage of 10 samples is obtained.

From the data in table 1, comparing example 7, example 8 and example 9 with comparative example 1, it is known that the high voltage cable of the present invention has higher thermal stability, strength, water resistance, oxidation aging resistance and ultraviolet aging resistance than the commercially available high voltage cable; example 9 compared with comparative example 2 shows that the synthetic ultraviolet resistance agent is used, and the diphenylamine antioxidant structure, the flexible polysiloxane chain, the 3, 4-dihydroxybenzene structure and the nano cerium oxide are introduced, so that the thermal stability, the water resistance, the oxidation aging resistance and the ultraviolet aging resistance of the high-voltage cable are improved; as is clear from comparison of example 9 with comparative example 3, the use of the voltage stabilizer improves the flame retardancy and the electrical aging resistance of the high voltage cable.

The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.

Claims (10)

1. A high withstand voltage cable, characterized in that: the cable comprises a protective sleeve A, a belting layer B, an insulating layer C, a conductor D and a filling rope E, wherein the insulating layer C is coated on the periphery of the conductor D, the filling rope E is filled between the insulating layer C and the belting layer B, and the protective sleeve A is coated on the periphery of the belting layer B; the sheath pipe A is a high-density polyethylene sheath pipe, the tape layer B is formed by flame-retardant tapes, the conductor D is a copper conductor, the filling rope E is a polypropylene filling rope, the insulating layer C is crosslinked polyethylene, and the crosslinked polyethylene comprises the following raw materials in parts by weight: 150-160 parts of low-density polyethylene, 10-12 parts of cross-linking agent, 30-40 parts of methyl vinyl silicone rubber, 6.5-7.5 parts of ultraviolet resistance agent and 5.5-6.5 parts of voltage stabilizer; the cross-linking agent is benzoyl peroxide.

2. A high withstand voltage cable according to claim 1, characterized in that: the ultraviolet resistance agent is prepared through the following steps:

Step A1: adding o-aminodiphenylamine, potassium carbonate and dimethyl sulfoxide into a flask to obtain a mixed solution a, adding 3, 4-dihydroxybenzoyl chloride into a dimethyl sulfoxide solution to obtain a mixed solution b, slowly dropwise adding the mixed solution b into the mixed solution a under the ice water bath at the temperature of 0 ℃, heating to 50-60 ℃ after dropwise adding, reacting at constant temperature for 6-8h, and distilling under reduced pressure to obtain an intermediate 1;

Step A2: toluene, hydrogen-containing silicone oil, hydroquinone and cis-dichloro bis (pyridyl) platinum are added into a three-neck flask according to a certain proportion, stirred and nitrogen is introduced for protection, 7-bromohept-1-en-3-one is dropwise added, the temperature is slowly increased to 70-80 ℃, the stirring reaction is carried out for 3-4 hours, and vacuum pumping is carried out, thus obtaining an intermediate 2;

step A3: adding the intermediate 2, the intermediate 1 and methanol into a flask, adding 2-dicyclohexylphosphorus-2 ' -4' -6' -triisopropylbiphenyl, tris (dibenzylideneacetone) dipalladium and potassium carbonate, carrying out reflux stirring reaction for 4-5h at 80 ℃ under the protection of nitrogen, and carrying out vacuum drying at 50 ℃ to obtain an intermediate 3;

step A4: adding the nano cerium oxide powder into an ethanol water solution, and stirring for 10min to obtain a mixed solution c; adding the intermediate 3 into ethanol water solution, and stirring for 20min to obtain a mixed solution d; adding the mixed solution c and the mixed solution d into a flask, performing ultrasonic dispersion for 40min to obtain a mixed system, adding an acetic acid solution into the mixed system under stirring, adjusting the pH of the mixed system to 5.5-6.5, heating to 50 ℃, stirring for reaction for 10h, cooling to room temperature, performing centrifugal separation, washing with absolute ethyl alcohol for three times, drying at 70 ℃ for 12h, and grinding to obtain the ultraviolet resistant agent.

3. A high withstand voltage cable according to claim 2, characterized in that: the voltage stabilizer is prepared through the following steps:

Step B1: adding maleic anhydride and 2, 4-dihydroxybenzophenone into a flask filled with tetrahydrofuran, then dropwise adding concentrated sulfuric acid, heating to 70-80 ℃, carrying out reflux stirring reaction for 9-10h to obtain a reaction solution, pouring the reaction solution into deionized water, standing for 10-20min, centrifuging, taking out lower oily substance, and drying in a vacuum drying oven at 80 ℃ for 2-4h to obtain an intermediate a;

step B2: in a nitrogen atmosphere, adding the intermediate a into a round-bottomed flask, heating to 45 ℃, adding tetrabutylammonium bromide, starting stirring, slowly dripping epichlorohydrin into the round-bottomed flask, and stirring for reaction for 5-6h to obtain an intermediate b;

Step B3: adding 2- (4- (benzo [ C ] [1,2,5] thiadiazole-5-yl methyl) piperazin-1-yl) ethane-1-alcohol into DMF, adding an intermediate b and sodium hydroxide under stirring, stirring and reacting for 4-4.5h at 40 ℃, filtering, washing with water, and drying to obtain the voltage stabilizer.

4. A high withstand voltage cable according to claim 2, characterized in that: in the step A1, the dosage ratio of the 3, 4-dihydroxybenzoyl chloride, the o-aminodiphenylamine, the potassium carbonate and the dimethyl sulfoxide is 0.1 mol:0.1 mol:0.01-0.015 mol:100 mL;

In the step A2, the dosage ratio of 7-bromohept-1-en-3-one, toluene, hydrogen-containing silicone oil, hydroquinone and cis-dichloro bis (pyridyl) platinum is 1-1.5 mol:100 ml:1 mol:0.5 mol:0.015-0.020 mol.

5. A high withstand voltage cable according to claim 1, characterized in that: in the step A3, the dosage ratio of the intermediate 2, the intermediate 1, the methanol, the 2-dicyclohexylphosphorus-2 ' -4' -6' -triisopropylbiphenyl, the tris (dibenzylideneacetone) dipalladium and the potassium carbonate is 0.06 mol:0.06 mol:300-350 mL:0.0025 g:0.0025 g:0.15-0.18 mol.

6. A high withstand voltage cable according to claim 1, characterized in that: in the step A4, the dosage ratio of the nano cerium oxide powder to the intermediate 3 to the ethanol aqueous solution to the acetic acid solution is 0.1g to 0.0012mol to 55mL to 0.3-0.4mL, the volume fraction of the ethanol aqueous solution is 10%, and the concentration of the acetic acid solution is 1mol/L.

7. A high withstand voltage cable according to claim 3, characterized in that: in the step B1, the dosage ratio of the maleic anhydride, the 2, 4-dihydroxybenzophenone, the concentrated sulfuric acid and the deionized water is 0.11 mol:0.10 mol:10-12 mL:200 mL, and the mass fraction of the concentrated sulfuric acid is 98%.

8. A high withstand voltage cable according to claim 3, characterized in that: in the step B2, the dosage ratio of the intermediate a, tetrabutylammonium bromide and epichlorohydrin is 0.1 mol:0.001-0.0012 mol:0.1 mol.

9. A high withstand voltage cable according to claim 3, characterized in that: in step B3, the ratio of 2- (4- (benzo [ C ] [1,2,5] thiadiazol-5-ylmethyl) piperazin-1-yl) ethan-1-ol, DMF, intermediate B and sodium hydroxide is: 0.1 mol:180 mL, 0.1 mol:0.1-0.2 g.

10. The production process of the high-voltage cable according to claim 2, wherein: the preparation method comprises the following steps:

Step S1: putting low-density polyethylene into a rheometer, carrying out melt blending, mixing for 4-6min at 105-110 ℃ and a rotating speed of 50r/min, then adding a pressure stabilizer and a cross-linking agent, mixing for 3min, then adding methyl vinyl silicone rubber and an ultraviolet resistant agent, and finally mixing for 10-15min to obtain cross-linked polyethylene;

Step S2: extruding the crosslinked polyethylene outside the copper conductor by using an extruder to form an insulating layer coated on the periphery of the conductor, and performing annealing treatment after extrusion to obtain a cable core; placing a cable core and a polypropylene filling rope, wrapping with a flame-retardant wrapping tape to form a wrapping tape layer, filling the polypropylene filling rope between the wrapping tape layer and the insulating layer, extruding and wrapping the high-density polyethylene outside the wrapping tape layer on a sheath layer outside the wrapping tape layer by using an extruder, and performing annealing treatment after extrusion to obtain the high-voltage-resistant cable.