CN107828187B - Corrosion-resistant insulating material for underground cable and preparation method thereof - Google Patents
Corrosion-resistant insulating material for underground cable and preparation method thereof Download PDFInfo
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- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- H—ELECTRICITY
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/40—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes epoxy resins
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- C08K2003/2241—Titanium dioxide
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Abstract
The invention provides a corrosion-resistant insulating material for underground cables and a preparation method thereof, belonging to the technical field of insulating materials, and comprising the following components in percentage by weight: 20-28 parts of epoxy resin, 12-18 parts of polytetrafluoroethylene, 3.8-5.5 parts of coupling agent, 12-17 parts of nano oxide, 4.5-5.6 parts of polydiallyl propyl dimethyl ammonium chloride, 17-22 parts of polyvinylidene fluoride, 35-44 parts of N, N-dimethylacetamide, 6.7-7.2 parts of waterproof agent, 8.9-9.6 parts of corrosion inhibitor, 3.4-4.7 parts of inhibitor, 3.3-4.2 parts of flame retardant, 20-26 parts of acetone and 40-55 parts of water. The insulating material prepared by the invention has good mechanical property and flame retardant property, strong water resistance and corrosion resistance and excellent comprehensive performance, and is suitable for underground humid and cold environments.
Description
Technical Field
The invention relates to the technical field of insulating materials, in particular to a corrosion-resistant insulating material for an underground cable and a preparation method thereof.
Background
After the modern society, due to the reasons of urban land shortage, high traffic pressure, city appearance construction and the like, a plurality of cables are also increasingly overhead to the underground. Compared with an overhead line, the underground cable has the advantages of small occupied area, reliable power transmission, strong anti-interference capability and the like.
The power cable is generally laid under the ground surface and is commonly used as a power lead-in or lead-out wire for power plants, substations and factories and mining enterprises. Compared with the overhead line, the power cable is less influenced by the weather because of being laid below the ground surface, is safe and reliable, is concealed and durable, but has higher material cost, laying cost and maintenance cost and is difficult to overhaul and troubleshoot. Once an underground cable is damaged, the maintenance of the cable is time-consuming and labor-consuming, the life of residents and the production stoppage of factories are seriously affected, and particularly, the loss caused by scientific research units such as industrial and mining hospitals cannot be measured.
The electric wires and cables for low-voltage distribution networks and electrical equipment usually adopt plastic-coated electric wires with polyvinyl chloride sheaths as electric energy transmission lines, and the electric wires are generally buried in walls or underground through pipes and can also be laid in a sampling and exposed laying mode. Sparks generated by poor insulation of the electric wires are easy to cause fire disasters in factory buildings, houses, public places and the like, and casualties and property loss are caused. Therefore, the development of the waterproof and corrosion-resistant insulating material with excellent performance for the underground cable has important significance for ensuring the smooth and safe operation of the underground cable and the normal operation of the life and production of people.
The patent document with publication number CN105885355A discloses a high heat-resistant mixed insulating material and a preparation method thereof, wherein the insulating material comprises, by weight, 30-40 parts of epoxy resin, 10-20 parts of polytetrafluoroethylene, 10-20 parts of polypropylene reinforced fiber, 4-10 parts of silica powder, 10-25 parts of nano zinc oxide, 10-15 parts of nano calcium carbonate, 3-8 parts of silane coupling agent, 10-20 parts of nano aluminum oxide, 5-10 parts of dibenzoyl peroxide and 7-12 parts of plasticizer. However, tests prove that the insulating material prepared by the method has poor water resistance, acid and alkali corrosion resistance, is not suitable for being used in humid and cold environments, is used for underground cables, and has short service life.
Patent document No. CN107141663A discloses a preparation method of a field corrosion-resistant composite cable insulation material, which is characterized by comprising the following steps: (1) carrying out primary banburying on fluororubber, carbon black, ethyl orthosilicate, simethicone, polyvinyl alcohol and carbon fiber to obtain a primary banburying material; (2) carrying out secondary banburying on the primary banburying material, white carbon black, rare earth oxide and zinc oxide to obtain a secondary banburying material; (3) extruding the secondary internal mixed material in an extruder; wherein, the temperature of the secondary banburying is 20-70 ℃ higher than that of the primary banburying. The composite cable insulating material prepared by the invention has good strength and corrosion resistance, and the preparation method of the composite cable insulating material is simple, easy to popularize and has high application value. However, the tensile strength of the insulating material is at most 20.1N/mm2The maximum breaking elongation is 422.8%, the mechanical property needs to be improved, and the preparation method of the invention only carries out banburying on the raw materials twice without carrying out treatments such as drying, modification and the like, thus causing insufficient purity and poorer comprehensive performance of the material.
Disclosure of Invention
In view of the above, the invention provides a corrosion-resistant insulating material for underground cables, which has good mechanical properties, water resistance, corrosion resistance and excellent insulating properties, and a preparation method thereof.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a corrosion-resistant insulating material for underground cables comprises the following components in percentage by weight: 20-28 parts of epoxy resin, 12-18 parts of polytetrafluoroethylene, 3.8-5.5 parts of coupling agent, 12-17 parts of nano oxide, 4.5-5.6 parts of polydiallyl propyl dimethyl ammonium chloride, 17-22 parts of polyvinylidene fluoride, 35-44 parts of N, N-dimethylacetamide, 6.7-7.2 parts of waterproof agent, 8.9-9.6 parts of corrosion inhibitor, 3.4-4.7 parts of inhibitor, 3.3-4.2 parts of flame retardant, 20-26 parts of acetone and 40-55 parts of water.
Further, the coupling agent is 3-aminopropyltriethoxysilane or 3-glycidoxypropyltrimethoxysilane.
Further, the nano oxide is a mixture of nano magnesium oxide, nano silicon dioxide and nano titanium dioxide, and the weight ratio of the nano magnesium oxide to the nano titanium dioxide is as follows: nano silicon dioxide: the ratio of the nano titanium dioxide is 4:3: 3.
Further, the waterproof agent is sodium methyl silicate or potassium methyl silicate.
Further, the corrosion-resistant agent is one or two of polyaspartic acid and hexamethylenetetramine.
Further, the corrosion resistant agent is a mixture of polyaspartic acid and hexamethylenetetramine, and the weight ratio of polyaspartic acid: hexamethylenetetramine is 3: 7.
further, the inhibitor is styrene or hydroquinone.
Further, the flame retardant is one or more of a flame retardant DDP, a flame retardant DOPO and tricresyl phosphate.
Further, the flame retardant is a mixture of a flame retardant DDP, a flame retardant DOPO and tricresyl phosphate, and the weight ratio of the flame retardant DDP: flame retardant DOPO: trimethylbenzene phosphate was 3:2: 5.
Further, a preparation method of the corrosion-resistant insulating material for the underground cable comprises the following steps:
1) placing 12-17 parts by weight of nano oxide in a vacuum drying oven at 80 ℃ for drying for 13-14h, mixing with 20-26 parts by weight of acetone, adding 3.8-5.5 parts by weight of coupling agent, placing in a magnetic stirrer for stirring at the rotation speed of 300-400r/min and the stirring time of 2-4h at 20-25 ℃, performing suction filtration, drying the filtrate in an oven at 75-80 ℃ for 6-8h, and grinding to obtain surface-modified nano oxide powder;
2) placing 17-22 parts by weight of polyvinylidene fluoride and 35-44 parts by weight of N, N-dimethylacetamide into a reaction kettle, introducing nitrogen, controlling the temperature of the reaction kettle at 90-120 ℃, stirring at the rotation speed of 200-300r/min, and stirring for 2-3h to obtain a first mixture;
3) mixing 20-28 parts by weight of epoxy resin, 12-18 parts by weight of polytetrafluoroethylene, 4.5-5.6 parts by weight of poly-diallyldimethylammonium chloride and 40-55 parts by weight of water, placing the mixture on a magnetic stirrer, and stirring for 4-6 hours at the temperature of 20-25 ℃ at the stirring speed of 600-800r/min to obtain a second mixture;
4) adding the nano oxide powder obtained in the step 1) and the mixture I obtained in the step 2) into the mixture II obtained in the step 3), and placing the mixture I into an internal mixer for mixing for 10-15min at the mixing temperature of 115 ℃ and 130 ℃ to obtain a primary mixed material;
5) adding 6.7-7.2 parts by weight of a waterproof agent, 8.9-9.6 parts by weight of an anticorrosion agent, 3.4-4.7 parts by weight of an inhibitor and 3.3-4.2 parts by weight of a flame retardant into the primary mixed material obtained in the step 4), and continuously mixing for 40-60min in an internal mixer at the mixing temperature of 115 ℃ and 130 ℃ to obtain the finished product.
The invention has the beneficial effects that: the epoxy resin is used as an anti-corrosion material, has good water resistance and leakage resistance, higher strength, strong adhesive force, good dielectric property and small deformation shrinkage, and can improve the stability and flexibility of the material. The epoxy resin adopted by the invention is novolac epoxy resin, and has good mechanical property and better heat resistance.
The polytetrafluoroethylene has excellent heat resistance and low temperature resistance, small dielectric constant, extremely high insulation resistance, excellent insulation performance, stable chemical performance and good mechanical performance.
The coupling agent is adopted to modify the nano oxide, so that the lipophilicity of the nano particles is improved, the nano particles are easier to disperse in an organic solvent, the compatibility among molecules is enhanced, a good interface phenomenon is shown, and the mechanical property of the material is improved.
The polydiallyl propyl dimethyl ammonium chloride is organically combined with the nano oxide particles, so that the corrosion resistance of the material is improved, and the curing effect of the epoxy resin is enhanced. The polyvinylidene fluoride is combined with the N, N-dimethylacetamide, so that the impact strength and the toughness of the material are improved, the wear resistance of the material is enhanced, and meanwhile, the polyvinylidene fluoride has excellent chemical corrosion resistance and is combined with the epoxy resin and the polytetrafluoroethylene to jointly improve the comprehensive performance of the material. In the process of mixing polyvinylidene fluoride and N, N-dimethylacetamide, nitrogen is introduced, so that the mixing of gas impurities in the air is reduced, and the purity of each component is ensured.
The water repellent enhances hydrophobicity, improves the impermeability and moisture resistance of the material, improves the acid and alkali resistance of the material due to corrosion resistance, enhances chemical stability, and prolongs the service life of the material. The inhibitor can inhibit space charge distribution, improve the insulating property of the material, and simultaneously has corrosion resistance and corrosion inhibition effects by combining with a corrosion resistance agent. The flame retardant has a high oxygen index, is organically combined with each component, has a good flame retardant effect, enhances the safety performance of the underground cable, and uses acetone as an organic solvent.
The corrosion-resistant insulating material for the underground cable, which is prepared by organically combining various materials and exerting the synergistic effect of the components, can effectively inhibit space charge aggregation in the cable insulating material, and has excellent corrosion resistance and insulating property and a dielectric constant below 1.5. Meanwhile, the flame-retardant waterproof flame-retardant rubber has good waterproof and flame-retardant properties, excellent mechanical properties, tensile strength of more than 23.5MPa, elongation at break of more than 520 percent and excellent comprehensive properties.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention are clearly and completely described below. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention, are within the scope of the invention.
Example one
A corrosion-resistant insulating material for underground cables comprises the following components in percentage by weight: 20 parts of epoxy resin, 12 parts of polytetrafluoroethylene, 3.8 parts of 3-aminopropyltriethoxysilane, 12 parts of nano oxide, 4.5 parts of polydiallyl dimethyl ammonium chloride, 17 parts of polyvinylidene fluoride, 35 parts of N, N-dimethylacetamide, 6.7 parts of sodium methylsilicate, 8.9 parts of polyaspartic acid, 3.4 parts of styrene, 3.3 parts of flame retardant DDP, 20 parts of acetone and 40 parts of water.
The nano oxide is a mixture of nano magnesium oxide, nano silicon dioxide and nano titanium dioxide, and the weight ratio of the nano magnesium oxide to the nano silicon dioxide is as follows: nano silicon dioxide: the ratio of the nano titanium dioxide is 4:3: 3.
A method of making a corrosion resistant insulation for underground cables comprising the steps of:
1) placing 12 parts by weight of nano oxide in a vacuum drying oven at 80 ℃ for drying for 13 hours, mixing with 20 parts by weight of acetone, adding 3.8 parts by weight of 3-aminopropyltriethoxysilane, placing in a magnetic stirrer for stirring at 20-25 ℃, controlling the rotating speed to be 300r/min and the stirring time to be 2 hours, performing suction filtration, drying the filtrate in an oven at 75 ℃ for 6 hours, and grinding to obtain surface-modified nano oxide powder;
2) placing 17 parts by weight of polyvinylidene fluoride and 35 parts by weight of N, N-dimethylacetamide into a reaction kettle, introducing nitrogen, controlling the temperature of the reaction kettle at 90 ℃, and stirring for 2 hours at a stirring speed of 200r/min to obtain a first mixture;
3) mixing 20 parts by weight of epoxy resin, 12 parts by weight of polytetrafluoroethylene, 4.5 parts by weight of poly-diallyldimethylammonium chloride and 40 parts by weight of water, placing the mixture on a magnetic stirrer, and stirring for 4 hours at the temperature of between 20 and 25 ℃ at the stirring speed of 600r/min to obtain a mixture II;
4) adding the nano oxide powder obtained in the step 1) and the mixture I obtained in the step 2) into the mixture II obtained in the step 3), and placing the mixture I into an internal mixer for mixing for 10min, wherein the mixing temperature is 115 ℃ to obtain a primary mixed material;
5) adding 6.7 parts by weight of sodium methyl silicate, 8.9 parts by weight of polyaspartic acid, 3.4 parts by weight of styrene and 3.3 parts by weight of flame retardant DDP into the primary mixed material obtained in the step 4), and continuously mixing for 40min in an internal mixer at the mixing temperature of 115 ℃ to obtain the flame retardant.
Example two
A corrosion-resistant insulating material for underground cables comprises the following components in percentage by weight: 21 parts of epoxy resin, 13 parts of polytetrafluoroethylene, 4 parts of 3-glycidyl ether oxypropyltrimethoxysilane, 13 parts of nano oxide, 4.6 parts of polydiallyl dimethyl ammonium chloride, 18 parts of polyvinylidene fluoride, 36 parts of N, N-dimethylacetamide, 6.8 parts of sodium methylsilicate, 9 parts of hexamethylenetetramine, 3.5 parts of styrene, 3.4 parts of flame retardant DOPO, 21 parts of acetone and 41 parts of water.
The nano oxide is a mixture of nano magnesium oxide, nano silicon dioxide and nano titanium dioxide, and the weight ratio of the nano magnesium oxide to the nano silicon dioxide is as follows: nano silicon dioxide: the ratio of the nano titanium dioxide is 4:3: 3.
A method of making a corrosion resistant insulation for underground cables comprising the steps of:
1) placing 13 parts by weight of nano oxide in a vacuum drying oven at 80 ℃ for drying for 13.5h, mixing with 21 parts by weight of acetone, adding 4 parts by weight of 3-glycidyl ether oxypropyltrimethoxysilane, placing in a magnetic stirrer for stirring at 20-25 ℃, rotating at 350r/min for 2.5h, performing suction filtration, drying the filtrate in an oven at 75 ℃ for 6.5h, and grinding to obtain surface-modified nano oxide powder;
2) placing 18 parts by weight of polyvinylidene fluoride and 36 parts by weight of N, N-dimethylacetamide into a reaction kettle, introducing nitrogen, controlling the temperature of the reaction kettle at 95 ℃, and stirring for 2.5 hours at a stirring speed of 250r/min to obtain a first mixture;
3) mixing 21 parts by weight of epoxy resin, 13 parts by weight of polytetrafluoroethylene, 4.6 parts by weight of poly-diallyldimethylammonium chloride and 41 parts by weight of water, placing the mixture on a magnetic stirrer, and stirring the mixture for 4.5 hours at the temperature of between 20 and 25 ℃ at the stirring speed of 650r/min to obtain a mixture II;
4) adding the nano oxide powder obtained in the step 1) and the mixture I obtained in the step 2) into the mixture II obtained in the step 3), and placing the mixture I into an internal mixer for mixing for 11min, wherein the mixing temperature is 120 ℃, so as to obtain a primary mixed material;
5) adding 6.8 parts by weight of sodium methyl silicate, 9 parts by weight of hexamethylenetetramine, 3.4 parts by weight of styrene and 3.3 parts by weight of flame retardant DOPO into the primary mixed material obtained in the step 4), and continuously mixing for 45min in an internal mixer at the mixing temperature of 120 ℃ to obtain the flame retardant DOPO.
EXAMPLE III
A corrosion-resistant insulating material for underground cables comprises the following components in percentage by weight: 23 parts of epoxy resin, 14 parts of polytetrafluoroethylene, 4.2 parts of 3-aminopropyltriethoxysilane, 14 parts of nano oxide, 4.8 parts of polydiallyl dimethyl ammonium chloride, 19 parts of polyvinylidene fluoride, 37 parts of N, N-dimethylacetamide, 6.9 parts of sodium methyl silicate, 9.2 parts of hexamethylenetetramine, 3.7 parts of hydroquinone, 3.6 parts of tricresyl phosphate, 22 parts of acetone and 43 parts of water.
The nano oxide is a mixture of nano magnesium oxide, nano silicon dioxide and nano titanium dioxide, and the weight ratio of the nano magnesium oxide to the nano silicon dioxide is as follows: nano silicon dioxide: the ratio of the nano titanium dioxide is 4:3: 3.
A method of making a corrosion resistant insulation for underground cables comprising the steps of:
1) placing 14 parts by weight of nano oxide in a vacuum drying oven at 80 ℃ for drying for 14 hours, mixing with 22 parts by weight of acetone, adding 4.2 parts by weight of 3-aminopropyltriethoxysilane, placing in a magnetic stirrer for stirring at 20-25 ℃, controlling the rotating speed to be 400r/min and the stirring time to be 3 hours, performing suction filtration, drying the filtrate in an oven at 80 ℃ for 7 hours, and grinding to obtain surface-modified nano oxide powder;
2) placing 19 parts by weight of polyvinylidene fluoride and 37 parts by weight of N, N-dimethylacetamide into a reaction kettle, introducing nitrogen, controlling the temperature of the reaction kettle at 100 ℃, and stirring for 3 hours at a stirring speed of 300r/min to obtain a first mixture;
3) mixing 23 parts by weight of epoxy resin, 14 parts by weight of polytetrafluoroethylene, 4.8 parts by weight of poly-diallyldimethylammonium chloride and 43 parts by weight of water, placing the mixture on a magnetic stirrer, and stirring for 5 hours at the temperature of between 20 and 25 ℃ at the stirring speed of 700r/min to obtain a mixture II;
4) adding the nano oxide powder obtained in the step 1) and the mixture I obtained in the step 2) into the mixture II obtained in the step 3), and placing the mixture I into an internal mixer for mixing for 12min, wherein the mixing temperature is 125 ℃, so as to obtain a primary mixed material;
5) adding 6.9 parts by weight of sodium methyl silicate, 9.2 parts by weight of hexamethylenetetramine, 3.7 parts by weight of hydroquinone and 3.6 parts by weight of tricresyl phosphate into the primary mixed material obtained in the step 4), and continuously mixing for 50min in an internal mixer at the mixing temperature of 125 ℃ to obtain the composite material.
Example four
A corrosion-resistant insulating material for underground cables comprises the same components and the content as the third embodiment.
A method of making a corrosion resistant insulation for underground cables comprising the steps of:
1) placing 14 parts by weight of nano oxide in a vacuum drying oven at 80 ℃ for drying for 14 hours, mixing with 22 parts by weight of acetone, adding 4.2 parts by weight of 3-aminopropyltriethoxysilane, placing in a magnetic stirrer for stirring at 20-25 ℃, controlling the rotating speed to be 400r/min and the stirring time to be 3 hours, performing suction filtration, drying the filtrate in an oven at 80 ℃ for 8 hours, and grinding to obtain surface-modified nano oxide powder;
2) placing 19 parts by weight of polyvinylidene fluoride and 37 parts by weight of N, N-dimethylacetamide into a reaction kettle, introducing nitrogen, controlling the temperature of the reaction kettle at 100 ℃, and stirring for 3 hours at a stirring speed of 300r/min to obtain a first mixture;
3) mixing 22 parts by weight of epoxy resin, 14 parts by weight of polytetrafluoroethylene, 4.8 parts by weight of poly-diallyldimethylammonium chloride and 43 parts by weight of water, placing the mixture on a magnetic stirrer, and stirring for 5 hours at the temperature of 20-25 ℃ at the stirring speed of 800r/min to obtain a mixture II;
4) adding the nano oxide powder obtained in the step 1) and the mixture I obtained in the step 2) into the mixture II obtained in the step 3), and placing the mixture I into an internal mixer for mixing for 15min, wherein the mixing temperature is 130 ℃, so as to obtain a primary mixed material;
5) adding 6.9 parts by weight of sodium methyl silicate, 9.2 parts by weight of hexamethylenetetramine, 3.7 parts by weight of hydroquinone and 3.6 parts by weight of tricresyl phosphate into the primary mixed material obtained in the step 4), and continuously mixing for 60min in an internal mixer at the mixing temperature of 130 ℃ to obtain the composite material.
EXAMPLE five
A corrosion-resistant insulating material for underground cables comprises the following components in percentage by weight: 25 parts of epoxy resin, 15 parts of polytetrafluoroethylene, 4.5 parts of 3-glycidyl ether oxypropyltrimethoxysilane, 15 parts of nano oxide, 5 parts of polydiallyl dimethyl ammonium chloride, 19 parts of polyvinylidene fluoride, 39 parts of N, N-dimethylacetamide, 7.0 parts of potassium methylsilicate, 9.2 parts of corrosion inhibitor, 4 parts of hydroquinone, 3.8 parts of flame retardant, 24 parts of acetone and 48 parts of water.
The nano oxide is a mixture of nano magnesium oxide, nano silicon dioxide and nano titanium dioxide, and the weight ratio of the nano magnesium oxide to the nano silicon dioxide is as follows: nano silicon dioxide: the ratio of the nano titanium dioxide is 4:3: 3.
The corrosion-resistant agent is a mixture of polyaspartic acid and hexamethylenetetramine, and the weight ratio of polyaspartic acid: hexamethylenetetramine is 3: 7.
the flame retardant is flame retardant DDP, flame retardant DOPO and tricresyl phosphate, and the weight ratio of the flame retardant DDP: flame retardant DOPO: trimethylbenzene phosphate was 3:2: 5.
A method of making a corrosion resistant insulation for underground cables comprising the steps of:
1) placing 15 parts by weight of nano oxide in a vacuum drying oven at 80 ℃ for drying for 14h, mixing with 24 parts by weight of acetone, adding 4.5 parts by weight of 3-glycidyl ether oxypropyl trimethoxysilane, placing in a magnetic stirrer for stirring, carrying out suction filtration at 20-25 ℃ at the rotating speed of 350r/min for 3h, drying the filtrate in an oven at 75 ℃ for 7h, and grinding to obtain surface-modified nano oxide powder;
2) placing 19 parts by weight of polyvinylidene fluoride and 39 parts by weight of N, N-dimethylacetamide into a reaction kettle, introducing nitrogen, controlling the temperature of the reaction kettle at 110 ℃, and stirring for 3 hours at a stirring speed of 250r/min to obtain a first mixture;
3) mixing 25 parts by weight of epoxy resin, 15 parts by weight of polytetrafluoroethylene, 5 parts by weight of poly-diallyldimethylammonium chloride and 48 parts by weight of water, placing the mixture on a magnetic stirrer, and stirring for 5 hours at the temperature of between 20 and 25 ℃ at the stirring speed of 700r/min to obtain a mixture II;
4) adding the nano oxide powder obtained in the step 1) and the mixture I obtained in the step 2) into the mixture II obtained in the step 3), and placing the mixture I into an internal mixer for mixing for 13min, wherein the mixing temperature is 120 ℃, so as to obtain a primary mixed material;
5) adding 7.0 parts by weight of sodium methyl silicate, 9.2 parts by weight of corrosion resistant agent, 4 parts by weight of hydroquinone and 3.8 parts by weight of flame retardant into the primary mixed material obtained in the step 4), and continuously mixing for 50min in an internal mixer at the mixing temperature of 120 ℃ to obtain the flame-retardant and corrosion-resistant rubber.
EXAMPLE six
The corrosion-resistant insulating material for underground cables comprises the same components and content as those in the fifth embodiment, but is different from the fifth embodiment in that the flame retardant used in the fifth embodiment is a flame retardant DDP.
The preparation method of the corrosion-resistant insulating material for the underground cable is the same as that of the fifth embodiment.
EXAMPLE seven
A corrosion-resistant insulating material for underground cables comprises the following components in percentage by weight: 27 parts of epoxy resin, 16 parts of polytetrafluoroethylene, 5.2 parts of 3-glycidyl ether oxypropyltrimethoxysilane, 16 parts of nano oxide, 5.4 parts of polydiallyl dimethyl ammonium chloride, 20 parts of polyvinylidene fluoride, 42 parts of N, N-dimethylacetamide, 7.1 parts of sodium methyl silicate, 9.4 parts of polyaspartic acid, 4.6 parts of styrene, 4.1 parts of flame retardant, 25 parts of acetone and 54 parts of water.
The nano oxide is a mixture of nano magnesium oxide, nano silicon dioxide and nano titanium dioxide, and the weight ratio of the nano magnesium oxide to the nano silicon dioxide is as follows: nano silicon dioxide: the ratio of the nano titanium dioxide is 4:3: 3.
The flame retardant is flame retardant DDP, flame retardant DOPO and tricresyl phosphate, and the weight ratio of the flame retardant DDP: flame retardant DOPO: trimethylbenzene phosphate was 3:2: 5.
A method of making a corrosion resistant insulation for underground cables comprising the steps of:
1) placing 16 parts by weight of nano oxide in a vacuum drying oven at 80 ℃ for drying for 14h, mixing with 25 parts by weight of acetone, adding 5.2 parts by weight of 3-glycidyl ether oxypropyl trimethoxysilane, placing in a magnetic stirrer for stirring, carrying out suction filtration at 20-25 ℃ at the rotating speed of 300r/min for 3h, drying the filtrate in an oven at 80 ℃ for 7.5h, and grinding to obtain surface-modified nano oxide powder;
2) placing 20 parts by weight of polyvinylidene fluoride and 42 parts by weight of N, N-dimethylacetamide into a reaction kettle, introducing nitrogen, controlling the temperature of the reaction kettle at 115 ℃, and stirring for 3 hours at a stirring speed of 250r/min to obtain a first mixture;
3) mixing 27 parts by weight of epoxy resin, 16 parts by weight of polytetrafluoroethylene, 5.4 parts by weight of poly-diallyldimethylammonium chloride and 54 parts by weight of water, placing the mixture on a magnetic stirrer, and stirring the mixture for 5.5 hours at the temperature of between 20 and 25 ℃ at the stirring speed of 750r/min to obtain a mixture II;
4) adding the nano oxide powder obtained in the step 1) and the mixture I obtained in the step 2) into the mixture II obtained in the step 3), and placing the mixture I into an internal mixer for mixing for 14min, wherein the mixing temperature is 125 ℃, so as to obtain a primary mixed material;
5) adding 7.1 parts by weight of sodium methyl silicate, 9.4 parts by weight of polyaspartic acid, 4.6 parts by weight of styrene and 4.1 parts by weight of flame retardant DOPO into the primary mixed material obtained in the step 4), and continuously mixing for 55min in an internal mixer at the mixing temperature of 125 ℃ to obtain the flame-retardant modified polycarbonate resin.
Example eight
A corrosion-resistant insulating material for underground cables comprises the following components in percentage by weight: 28 parts of epoxy resin, 18 parts of polytetrafluoroethylene, 5.5 parts of 3-glycidyl ether oxypropyltrimethoxysilane, 17 parts of nano oxide, 5.6 parts of polydiallyl dimethyl ammonium chloride, 22 parts of polyvinylidene fluoride, 44 parts of N, N-dimethylacetamide, 7.2 parts of potassium methylsilicate, 9.6 parts of corrosion inhibitor, 4.7 parts of styrene, 4.2 parts of flame retardant, 26 parts of acetone and 55 parts of water.
The nano oxide is a mixture of nano magnesium oxide, nano silicon dioxide and nano titanium dioxide, and the weight ratio of the nano magnesium oxide to the nano silicon dioxide is as follows: nano silicon dioxide: the ratio of the nano titanium dioxide is 4:3: 3.
The corrosion-resistant agent is a mixture of polyaspartic acid and hexamethylenetetramine, and the weight ratio of polyaspartic acid: hexamethylenetetramine is 3: 7.
the flame retardant is flame retardant DDP, flame retardant DOPO and tricresyl phosphate, and the weight ratio of the flame retardant DDP: flame retardant DOPO: trimethylbenzene phosphate was 3:2: 5.
A method of making a corrosion resistant insulation for underground cables comprising the steps of:
1) placing 28 parts by weight of nano oxide in a vacuum drying oven at 80 ℃ for drying for 14 hours, mixing with 26 parts by weight of acetone, adding 5.5 parts by weight of 3-glycidyl ether oxypropyl trimethoxy silane, placing in a magnetic stirrer for stirring, carrying out suction filtration at 20-25 ℃ at the rotating speed of 400r/min for 4 hours, drying the filtrate in an oven at 80 ℃ for 8 hours, and grinding to obtain surface-modified nano oxide powder;
2) placing 22 parts by weight of polyvinylidene fluoride and 44 parts by weight of N, N-dimethylacetamide in a reaction kettle, introducing nitrogen, controlling the temperature of the reaction kettle at 120 ℃, and stirring for 3 hours at a stirring speed of 300r/min to obtain a first mixture;
3) mixing 28 parts by weight of epoxy resin, 18 parts by weight of polytetrafluoroethylene, 5.6 parts by weight of poly-diallyldimethylammonium chloride and 55 parts by weight of water, placing the mixture on a magnetic stirrer, and stirring for 6 hours at the temperature of 20-25 ℃ at the stirring speed of 800r/min to obtain a mixture II;
4) adding the nano oxide powder obtained in the step 1) and the mixture I obtained in the step 2) into the mixture II obtained in the step 3), and placing the mixture I into an internal mixer for mixing for 15min, wherein the mixing temperature is 130 ℃, so as to obtain a primary mixed material;
5) adding 7.2 parts by weight of potassium methylsilicate, 9.6 parts by weight of corrosion resistant agent, 4.7 parts by weight of styrene and 4.2 parts by weight of flame retardant DOPO into the primary mixed material obtained in the step 4), and continuously mixing for 60min in an internal mixer at the mixing temperature of 130 ℃ to obtain the flame-retardant modified polycarbonate resin.
Comparative example 1
A corrosion-resistant insulating material for underground cables, comprising the same components and amounts as in example two, but different from example two, in that polyvinylidene fluoride and N, N-dimethylacetamide were not added.
The corrosion-resistant insulation material for underground cables comprises the same steps as in example two, but differs from example two in that the comparative example lacks step 2), i.e., the mixing of polyvinylidene fluoride and N, N-dimethylacetamide.
Comparative example No. two
A corrosion-resistant insulating material for underground cables, comprising the same components and amounts as those in example three, except that a water repellent and an inhibitor were not added to the comparative example.
The corrosion-resistant insulating material for underground cables comprises the same steps as in example three, and the water repellent agent and the inhibitor are not added in the comparative example.
Comparative example No. three
A corrosion-resistant insulating material for underground cables, comprising the same components and amounts as those in example five, except that no corrosion-resistant agent was added to the comparative example.
The corrosion-resistant insulating material for underground cables comprises the same steps as the fifth embodiment, and the corrosion-resistant agent is not added in the fifth embodiment.
Comparative example No. four
A corrosion resistant insulation material for underground cables comprising the same components and amounts as in example seven, but different from example seven, the comparative example lacks a coupling agent.
The corrosion-resistant insulating material for underground cables comprises the same steps as those of the seventh example, but is different from the seventh example in that the comparative example lacks the step 1), i.e., the nano-oxide is not modified with a coupling agent.
And (3) performance testing:
1) mechanical Property test
And pouring the prepared mixed solution into the mold, and curing at room temperature to obtain a sample. The specification is as follows: a length of 30 mm, a width lO mm and a thickness of 100. mu.m. The paint layer was subjected to a stress-strain test using a U.S. Meits CMT5305 universal tester with a strain rate of 10 mm/min.
The tensile strength is the load per unit cross-sectional area of the specimen when the specimen is broken by tension in a tensile machine, and is N/mm2Expressed, the calculation formula is shown as 1-1:
P＝F/S (1-1)
in the formula: tensile Strength of P sample, N/mm2；
F-the force on the fracture section, N, at the time of fracture of the specimen;
s-area of fracture surface of specimen, mm2。
Wherein 1MPa = 1N/mm2
The elongation at break is the ratio of the elongation at which the specimen is pulled apart to the original length, expressed in percentage, and is calculated by the formula 1-2:
E=(L1-L0)/L0 （1-2）
in the formula: e-elongation at break,%;
L0the original length of a sample is mm;
L1the length of the stressed portion at break of the specimen, mm.
2) Water resistance test
And (3) taking 30g of the mixed solution in a glass culture dish, and drying in an oven to prepare a film. The water resistance of the film was characterized by the water absorption, the film was cut into square test specimens of 15mm × 15mm, and the mass of the test specimens was weighed (to the nearest 0.001 g). Placing the membrane into a culture dish filled with distilled water, soaking the membrane on the upper surface of the membrane for 24h at room temperature, and taking out the membrane. The surface of the film was gently wiped off with filter paper and immediately weighed. The water absorption of the film was calculated according to equation 2-1, and each sample was tested 3 times and averaged.
W=(m1-m0)/m0×100% （2-1）
In the formula, the water absorption of the W-film,%;
m0-initial mass of the sample, g;
m1mass after water absorption of the sample, g.
3) Insulation performance test
And pouring the prepared mixed solution into the mold, and curing at room temperature to obtain a sample. And (3) carrying out online test on the sample by adopting a capacitance measuring instrument, and calculating to obtain the insulated dielectric constant by using a capacitance calculation formula (3-1).
ε=Cx/Co （3-1）
In the formula: ε -the factor of increase in capacitance, i.e. the relative permittivity;
Cx-capacitance when the capacitor plates are filled with a medium;
Cothe capacitance of the capacitor when the two plates are under vacuum.
A ZC-36 type high-resistivity meter is used for carrying out volume resistivity test, the polyethylene nano composite material is prepared into a sample of 100 mm multiplied by 1 mm, an aluminum foil is attached to the sample, and the test voltage is 500V. By using three
And the electrode system measures the composite material by using a high-resistance meter, the measured value is volume resistance, and the volume resistivity of the sample can be calculated according to the formula (3-2). The formula is as follows:
ρv=Rvπ(D1+g)/4h （3-2）
in the formula: rhov-volume resistivity, Ω · m; rv-volume resistance, Ω;
D1-guard electrode diameter, m; g is the distance between the protected electrode and the protecting electrode, m;
h-thickness of the test specimen, m.
4) Corrosion resistance test
30g of the mixed solution was placed in a glass petri dish and dried in an oven to prepare a thin film sample. Taking three clean beakers, respectively preparing 10% hydrochloric acid and 10% NaOH solutions, respectively immersing the samples in the prepared solutions, keeping the sealed environment for 45 days, and taking out the samples to observe the corrosion condition of the surface of the film.
The results of the test analyses of examples one to eight and comparative examples one to five are shown in table 1:
TABLE 1 test results of examples and comparative examples
| Tensile strength MPa | Elongation at break% | Water resistance | Dielectric constant | Volume resistivity (10)15Ω·m） | Acid resistance | Alkali resistance | |
| Example one | 23.5 | 520.7 | 41 | 1.5 | 4.2 | No wrinkle, bubble and peeling | No wrinkle, bubble and peeling |
| Example two | 24.2 | 527.6 | 40 | 1.5 | 4.4 | No wrinkle, bubble and peeling | No wrinkle, bubble and peeling |
| EXAMPLE III | 25.9 | 543.6 | 36 | 1.4 | 4.8 | No wrinkle, bubble and peeling | No wrinkle, bubble and peeling |
| Example four | 24.7 | 540.8 | 34 | 1.4 | 4.7 | No wrinkle, bubble and peeling | No wrinkle, bubble and peeling |
| EXAMPLE five | 29.4 | 589.3 | 32 | 1.2 | 5.5 | No wrinkle, bubble and peeling | No wrinkle, bubble and peeling |
| EXAMPLE six | 27.4 | 573.9 | 35 | 1.3 | 5.0 | No wrinkle, bubble and peeling | No wrinkle, bubble and peeling |
| EXAMPLE seven | 27.2 | 577.9 | 37 | 1.3 | 5.1 | No wrinkle, bubble and peeling | No wrinkle, bubble and peeling |
| Example eight | 28.3 | 580.3 | 35 | 1.3 | 5.4 | No wrinkle, bubble and peeling | No wrinkle, bubble and peeling |
| Comparative example 1 | 15.2 | 436.3 | 45 | 2.7 | 3.2 | Large amount of wrinkles, bubbles and peeling | Large amount of wrinkles, bubbles and peeling |
| Comparative example No. two | 17.3 | 440.5 | 58 | 2.5 | 2.6 | Large amount of wrinkles, bubbles and peeling | Large amount of wrinkles, bubbles and peeling |
| Comparative example No. three | 18.4 | 451.4 | 44 | 2.5 | 2.7 | Large amount of wrinkles, bubbles and peeling | Large amount of wrinkles, bubbles and peeling |
| Comparative example No. four | 17.6 | 427.3 | 50 | 2.8 | 3.0 | Small amount of wrinkles, bubbles and peeling-off | Small amount of wrinkles, bubbles and peeling-off |
As can be seen from table 1: 1) examples one to eight all show a good combination of properties: the cable has excellent mechanical properties, tensile strength of more than 23.5MPa, maximum tensile strength of 29.4MPa, elongation at break of more than 520%, water resistance, chemical corrosion resistance, excellent insulating property and dielectric constant of less than 1.5, and meets the technical requirements of underground cables. 2) The flame retardant and the corrosion resistant agent are both single substances, the flame retardant and the corrosion resistant agent are mixtures of two or three substances, and the comprehensive performance of the materials in the fifth to eighth examples is better than that of the materials in the first to fourth examples; compared with the three phases of the example, the composition and the content of the substances are the same, the technical parameters of the preparation method are different, and the performance of the three phase of the example is better than that of the four phase of the example. 3) Comparative example one compared to the example two, polyvinylidene fluoride and N, N-dimethylacetamide were absent; comparative example two lacks water repellent and inhibitor compared to example three; the third comparative example lacks corrosion resistance agent compared with the fifth example; comparative example four compared to example seven, the nano-oxide was not modified; the materials of comparative examples one to four had poorer performance than those of examples one to eight. The epoxy resin, the polytetrafluoroethylene and the polyvinylidene fluoride act together, the modified nano oxide increases the compatibility among molecules, and various auxiliary agents are organically combined with the components and interact to jointly enhance the comprehensive performance of the material while improving the performance of the material. The materials are complementary, and the performance of the insulating material is obviously reduced if any one of the materials is lacked.
Finally, the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting, and other modifications or equivalent substitutions made by the technical solutions of the present invention by those of ordinary skill in the art should be covered within the scope of the claims of the present invention as long as they do not depart from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. A corrosion resistant insulation material for underground cables, characterized by: the raw materials comprise the following components in percentage by weight: 20-28 parts of epoxy resin, 12-18 parts of polytetrafluoroethylene, 3.8-5.5 parts of coupling agent, 12-17 parts of nano oxide, 4.5-5.6 parts of polydiallyl propyl dimethyl ammonium chloride, 17-22 parts of polyvinylidene fluoride, 35-44 parts of N, N-dimethylacetamide, 6.7-7.2 parts of waterproof agent, 8.9-9.6 parts of corrosion inhibitor, 3.4-4.7 parts of inhibitor, 3.3-4.2 parts of flame retardant, 20-26 parts of acetone and 40-55 parts of water;
the nano oxide is a mixture of nano magnesium oxide, nano silicon dioxide and nano titanium dioxide, and the weight ratio of the nano magnesium oxide to the nano silicon dioxide is as follows: nano silicon dioxide: the ratio of the nano titanium dioxide is 4:3: 3;
the preparation method of the corrosion-resistant insulating material for the underground cable comprises the following steps:
1) placing 12-17 parts by weight of nano oxide in a vacuum drying oven at 80 ℃ for drying for 13-14h, mixing with 20-26 parts by weight of acetone, adding 3.8-5.5 parts by weight of coupling agent, placing in a magnetic stirrer for stirring at the rotation speed of 300-400r/min and the stirring time of 2-4h at 20-25 ℃, performing suction filtration, drying the filtrate in an oven at 75-80 ℃ for 6-8h, and grinding to obtain surface-modified nano oxide powder;
2) placing 17-22 parts by weight of polyvinylidene fluoride and 35-44 parts by weight of N, N-dimethylacetamide into a reaction kettle, introducing nitrogen, controlling the temperature of the reaction kettle at 90-120 ℃, stirring at the rotation speed of 200-300r/min, and stirring for 2-3h to obtain a first mixture;
3) mixing 20-28 parts by weight of epoxy resin, 12-18 parts by weight of polytetrafluoroethylene, 4.5-5.6 parts by weight of poly-diallyldimethylammonium chloride and 40-55 parts by weight of water, placing the mixture on a magnetic stirrer, and stirring for 4-6 hours at the temperature of 20-25 ℃ at the stirring speed of 600-800r/min to obtain a second mixture;
4) adding the nano oxide powder obtained in the step 1) and the mixture I obtained in the step 2) into the mixture II obtained in the step 3), and placing the mixture I into an internal mixer for mixing for 10-15min at the mixing temperature of 115 ℃ and 130 ℃ to obtain a primary mixed material;
5) adding 6.7-7.2 parts by weight of a waterproof agent, 8.9-9.6 parts by weight of an anticorrosion agent, 3.4-4.7 parts by weight of an inhibitor and 3.3-4.2 parts by weight of a flame retardant into the primary mixed material obtained in the step 4), and continuously mixing for 40-60min in an internal mixer at the mixing temperature of 115 ℃ and 130 ℃ to obtain the finished product.
2. A corrosion resistant insulation material for underground cables according to claim 1 wherein: the coupling agent is 3-aminopropyl triethoxysilane or 3-glycidyl ether oxypropyl trimethoxysilane.
3. A corrosion resistant insulation material for underground cables according to claim 1 wherein: the waterproof agent is sodium methyl silicate or potassium methyl silicate.
4. A corrosion resistant insulation material for underground cables according to claim 1 wherein: the corrosion-resistant agent is one or two of polyaspartic acid and hexamethylenetetramine.
5. A corrosion resistant insulation material for underground cables according to claim 4, wherein: the corrosion-resistant agent is a mixture of polyaspartic acid and hexamethylenetetramine, and the weight ratio of polyaspartic acid: hexamethylenetetramine is 3: 7.
6. a corrosion resistant insulation material for underground cables according to claim 1 wherein: the inhibitor is styrene or hydroquinone.
7. A corrosion resistant insulation material for underground cables according to claim 1 wherein: the flame retardant is one or more of a flame retardant DDP, a flame retardant DOPO and tricresyl phosphate.
8. A corrosion resistant insulation material for underground cables according to claim 7 wherein: the flame retardant is a mixture of a flame retardant DDP, a flame retardant DOPO and tricresyl phosphate, and the weight ratio of the flame retardant DDP: flame retardant DOPO: trimethylbenzene phosphate was 3:2: 5.
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