CN115850834B - High-performance polyethylene/nano silicon dioxide composite cable insulating resin and preparation method and application thereof - Google Patents
High-performance polyethylene/nano silicon dioxide composite cable insulating resin and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of insulating resins, in particular to a high-performance polyethylene/nano silicon dioxide composite cable insulating resin, a preparation method and application thereof, wherein the polyethylene/nano silicon dioxide composite cable insulating resin comprises the following components in parts by weight: 65-80 parts of polyethylene resin, 15-25 parts of pre-irradiation polyethylene resin, 0.5-2 parts of modified nano silicon dioxide and 5-10 parts of reactive functional polystyrene resin, wherein the sum of the parts by weight of the polyethylene resin, the pre-irradiation polyethylene resin, the modified nano silicon dioxide and the reactive functional polystyrene resin is 100. The invention solves the problems that the voltage stabilizer is easy to migrate and separate out and the nano silicon dioxide is difficult to disperse, and improves the long-acting electric breakdown resistance of the polyethylene resin; the polyethylene nano composite insulating resin prepared by the invention has wide application prospect, can be directly used as an insulating layer, and can be used for preparing crosslinked polyethylene through radiation crosslinking or thermal crosslinking.
Description
Technical Field
The invention relates to the technical field of insulating resins, in particular to a high-performance polyethylene/nano silicon dioxide composite cable insulating resin and a preparation method and application thereof.
Background
The main insulating material used for the high-voltage and ultra-high-voltage plastic cable is crosslinked polyethylene. The crosslinked polyethylene has the advantages of low cost, easy obtainment, high electric insulation strength, low dielectric constant dielectric loss, high volume resistivity, low density, high temperature resistance and the like. However, crosslinked polyethylene also has problems such as space charge accumulation. With the increase of the load of the long-distance power transmission cable, the power transmission voltage level is increased, the working temperature is increased, the power cable insulating material needs higher voltage breakdown resistance level and better electrical aging resistance, so that the power transmission efficiency of the power cable is improved, and the energy consumption and loss are reduced.
The electric resistance level of the crosslinked polyethylene can be effectively improved by adding a small amount of voltage stabilizer, but the voltage stabilizer belongs to small molecules, has poor compatibility with polymers, is extremely easy to separate out from the polymers under the high temperature condition, and therefore reduces the use aging of the voltage stabilizer. In addition, the voltage stabilizer has larger polarity, and the addition of the voltage stabilizer with too high content can obviously improve the conductivity of the insulating material. Therefore, the migration of the voltage stabilizer is inhibited, the timeliness of the voltage stabilizer is improved, the electrical aging resistance time of the insulating material is prolonged, and the cable has positive effects on long-term stable operation. The long fatty chain grafted on the voltage stabilizer molecule can delay the precipitation of the small molecular voltage stabilizer, and can improve the compatibility of the voltage stabilizer and the resin, thereby improving the stability of the electric insulation material. However, this method cannot fundamentally solve the problems of migration and precipitation of the voltage stabilizer.
The electrical insulation property and the electrical aging resistance of the material can be effectively improved by adding inorganic nano-particles, and the selectable nano-particles comprise nano-silicon dioxide, nano-zinc oxide, nano-magnesium oxide, nano-boron nitride and the like, thereby being greatly helpful for improving the tree-lifting voltage, improving the electrical strength, reducing the electrical conductivity, inhibiting the space charge and the like of the polyethylene insulating material. However, the problem of the dispersibility of inorganic nano-particles in resins is the biggest obstacle to the development of nano-electrically insulating composites. The dispersibility of the inorganic nano particles can be partially improved by surface modification, but the inorganic nano particles cannot be caused to have strong interaction with the polyethylene resin, so that the performance of nano modification is limited.
Disclosure of Invention
Aiming at the problems, the invention provides a high-performance polyethylene/nano silicon dioxide composite cable insulating resin, a preparation method and application thereof, which are used for solving the problems that the existing voltage stabilizer is not compatible with polyethylene and is easy to separate out, and nano silicon dioxide is difficult to disperse in a polymer matrix, so that the long-acting electric breakdown resistance of the polyethylene resin is improved.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the high-performance polyethylene/nano silicon dioxide composite cable insulation resin comprises the following components in parts by weight:
polyethylene resin: 65-80 parts;
pre-irradiation polyethylene resin: 15-25 parts of a lubricant;
modified nano silicon dioxide: 0.5-2 parts;
reactive functional polystyrene resin: 5-10 parts;
and the sum of the weight parts of the polyethylene resin, the pre-irradiation polyethylene resin, the modified nano silicon dioxide and the reactive functional polystyrene resin is 100.
Preferably, the polyethylene resin is low density polyethylene or linear low density polyethylene, and the linear low density polyethylene is one or more of ethylene-1-butene copolymer, ethylene-1-hexene copolymer and ethylene-1-octene copolymer.
Preferably, the pre-irradiated polyethylene resin is obtained by pre-irradiating a polyethylene resin; the irradiation source is an electron accelerator or 60 Co; the irradiation dose is 10-40kGy.
Preferably, the modified nano-silica is obtained via surface modification of gamma-methacryloxypropyl trimethoxysilane.
Preferably, the reactive functional polystyrene resin is obtained by random copolymerization of a reactive functional monomer, an active voltage stabilizer monomer, and a styrene monomer.
Preferably, the reactive functional monomer comprises one or more of allyl acrylate, allyl methacrylate and 10-undecylenic acid vinyl ester, and has the following structural formula:
the invention also provides a preparation method of the high-performance polyethylene/nano silicon dioxide composite cable insulation resin, which comprises the following steps:
step one, preparing pre-irradiation polyethylene resin:
by using 60 Co is used as an irradiation source, gamma rays are used for pre-irradiating the polyethylene resin in an air atmosphere, and the pre-irradiation dose is 10-40kGy, so that the pre-irradiated polyethylene resin is obtained; or electron accelerator is used as irradiation source, beta rays are used for pre-irradiating polyethylene resin in air atmosphere, and the pre-irradiation dose is 10-40kGy, thus obtainingPre-irradiating polyethylene resin;
step two, preparing modified nano silicon dioxide:
dispersing nano silicon dioxide particles in an absolute ethyl alcohol/deionized water solution with the volume ratio of 1:1, wherein the mass percentage of the nano silicon dioxide is 5%, and carrying out ultrasonic treatment for 0.5 hour; adding a silane coupling agent gamma-methacryloxypropyl trimethoxy silane with the same mass as nano silicon dioxide under the stirring condition, adjusting the pH value of the solution to 4, and stirring at 60 ℃ for 24 hours; after the reaction is finished, centrifugally collecting nano silicon dioxide, and washing with absolute ethyl alcohol for three times; vacuum drying at 60 deg.c for 24 hr to obtain modified nanometer silica;
step three, preparing reactive functional polystyrene resin:
adding deionized water, emulsifier sodium dodecyl sulfonate, styrene monomer, reactive functional monomer, active voltage stabilizer monomer and photoinitiator in a mass ratio of 100:0.2:15-25:0.16-1.16:0.63-2.91:0.15 into a reaction device, reacting for 3 hours under 365nm ultraviolet irradiation, precipitating the reaction product by absolute ethyl alcohol, filtering, and vacuum drying at 40 ℃ to obtain reactive functional polystyrene resin;
wherein the photoinitiator is 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone;
step four, preparing a polyethylene-nano silicon dioxide-reactive functional polystyrene graft:
adding the pre-irradiated polyethylene resin obtained in the first step, the modified nano silicon dioxide obtained in the second step and the reactive functional polystyrene resin obtained in the third step into an internal mixer according to a proportion, and banburying for 15 minutes at a reaction temperature of 200 ℃ and a rotation speed of 60r/min to obtain a polyethylene-nano silicon dioxide-reactive functional polystyrene graft;
fifthly, preparing insulating resin:
adding polyethylene resin and the polyethylene-nano silicon dioxide-reactive functional polystyrene graft obtained in the step four into a double-screw extruder according to the proportion, extruding at 130-230 ℃, drawing, cooling and granulating to obtain the insulating resin.
Preferably, in the second step, the nano silicon dioxide is spherical and has the particle size of 30-100 nanometers; in the third step, the reactive functional monomer mass percentage content in the prepared reactive functional polystyrene resin is 1-4%, and the active voltage stabilizer monomer mass percentage content is 4-10%.
The invention also provides an application of the high-performance polyethylene/nano silicon dioxide composite cable insulating resin prepared by the preparation method as an insulating material for a high-voltage direct-current transmission cable, which comprises the following specific steps:
the high-performance polyethylene/nano silicon dioxide composite cable insulating resin prepared by the invention can be directly coated on the surface of a conductor to prepare a cable, can be crosslinked by an irradiation method after being coated, can be blended with a proper amount of crosslinking agent master batch, and can be prepared into a crosslinked polyethylene cable by thermal crosslinking after being fused and coated.
The invention has the beneficial effects that:
1. the invention adopts the voltage stabilizer monomer to form a macromolecular chain through copolymerization with styrene, inhibits migration and precipitation in the resin when the voltage stabilizer is taken as a small molecule, ensures that the voltage stabilizer is always remained in the polymer, and further ensures that the polyethylene has the characteristic of permanent high voltage breakdown resistance.
2. The invention adopts the monomer with two unequal active double bonds to copolymerize with styrene and voltage stabilizer monomer, and when the polymerization is initiated by low temperature light, the high active acrylic ester double bonds participate in the reaction, and the low active propenyl and vinyl double bonds remain in the copolymer. The method comprises the steps of pre-irradiating polyethylene resin in an air atmosphere to generate peroxide on a polyethylene molecular chain after pre-irradiation, wherein the peroxide generates free radicals through thermal decomposition, and reactive functional polystyrene with low-activity double bonds can be grafted on the polyethylene molecular chain in a high-temperature banburying process to form grafts, so that the problem of compatibility between the polyethylene and the functional polystyrene does not exist, and the voltage stabilizer can play a role better.
3. According to the invention, the nano silicon dioxide is modified by the silane coupling agent with carbon-carbon double bonds, and the modified nano silicon dioxide with the carbon-carbon double bonds on the surface is easy to react with peroxide on the pre-irradiation polyethylene during high-temperature banburying, so that grafting of the nano silicon dioxide and the polyethylene is formed, and the strong interaction of the nano silicon dioxide and the polyethylene grafting during melt blending further improves the dispersion effect of the nano silicon dioxide in the polyethylene. On one hand, the dispersibility of the nano silicon dioxide in polyethylene is improved by dispersion grafting modification; on the other hand, the direct grafting of the nano silicon dioxide and the polyethylene strengthens the interface structure of the nano silicon dioxide and the polyethylene, so that the compatibility of the nano silicon dioxide and the polyethylene is improved. The combination of multiple factors keeps the electrical aging resistance of the nano silicon dioxide to the polyethylene resin, and the reduction of the electrical breakdown strength caused by difficult dispersion and incompatibility with the polyethylene resin is overcome, so that the polyethylene resin with high electrical breakdown resistance is obtained.
Detailed Description
The technical scheme of the present invention is further illustrated and described below by means of specific embodiments, but the embodiments of the present invention are not limited thereto.
The high-performance polyethylene/nano silicon dioxide composite cable insulation resin comprises the following components in parts by weight: 65-80 parts of polyethylene resin, 15-25 parts of pre-irradiation polyethylene resin and 0.5-2 parts of modified nano silicon dioxide; 5-10 parts of reactive functional polystyrene resin; and the sum of the weight parts of the polyethylene resin, the pre-irradiation polyethylene resin, the modified nano silicon dioxide and the reactive functional polystyrene resin is 100.
Wherein the pre-irradiated polyethylene resin is obtained by pre-irradiating polyethylene, the polyethylene is low density polyethylene or linear low density polyethylene, the pre-irradiation dose is 10-40kGy, and the irradiation source is 60 Co or electron accelerator.
The modified nano silicon dioxide is obtained by surface modification of a silane coupling agent gamma-methacryloxypropyl trimethoxy silane; the reactive functional polystyrene is prepared by the free radical copolymerization of reactive functional monomers, voltage stabilizer monomers and styrene.
The preparation method of the high-performance polyethylene/nano silicon dioxide composite cable insulating resin comprises the following specific steps:
step one, preparing pre-irradiation polyethylene resin:
by using 60 Co is used as an irradiation source, gamma rays are used for pre-irradiating the polyethylene resin in an air atmosphere, and the pre-irradiation dose is 10-40kGy, so that the pre-irradiated polyethylene resin is obtained; or adopting an electron accelerator as an irradiation source, and pre-irradiating the polyethylene resin in an air atmosphere by using beta rays, wherein the pre-irradiation dose is 10-40kGy, so as to obtain pre-irradiated polyethylene resin;
the polyethylene resin is low-density polyethylene or linear low-density polyethylene, and the linear low-density polyethylene is one or more of ethylene-1-butene copolymer, ethylene-1-hexene copolymer and ethylene-1-octene copolymer.
Step two, preparing modified nano silicon dioxide:
dispersing nano silicon dioxide particles in an absolute ethyl alcohol/deionized water solution with the volume ratio of 1:1, wherein the mass percentage of the nano silicon dioxide is 5%, and carrying out ultrasonic treatment for 0.5 hour; adding a silane coupling agent gamma-methacryloxypropyl trimethoxy silane with the same mass as nano silicon dioxide under the stirring condition, adjusting the pH value of the solution to 4, and stirring at 60 ℃ for 24 hours; after the reaction is finished, centrifugally collecting nano silicon dioxide, and washing with absolute ethyl alcohol for three times; vacuum drying at 60 deg.c for 24 hr to obtain modified nanometer silica.
Wherein the nano silicon dioxide is spherical, and the diameter is 30-100nm.
Step three, preparing reactive functional polystyrene resin:
deionized water, emulsifier sodium dodecyl sulfonate, styrene monomer, reactive functional monomer, active voltage stabilizer monomer and photoinitiator are added into a reaction device according to the mass ratio of 100:0.2:15-25:0.16-1.16:0.63-2.91:0.15, reacted for 3 hours under 365nm ultraviolet irradiation, and the reaction product is subjected to absolute ethanol precipitation, suction filtration and vacuum drying at 40 ℃ to obtain the reactive functional polystyrene resin.
Wherein the photoinitiator is 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone.
The reactive functional polystyrene contains 1-4% of reactive functional monomer and 4-10% of active voltage stabilizer monomer.
The reactive functional monomer is one or more of propyl acrylate, propyl methacrylate and 10-undecylenic acid vinyl ester, and has the following structural formula:
the active voltage stabilizer monomer is 4-acryloxyacetophenone, and the structural formula is as follows:
step four, preparing a polyethylene-nano silicon dioxide-reactive functional polystyrene graft:
adding the pre-irradiated polyethylene resin obtained in the first step, the modified nano silicon dioxide obtained in the second step and the reactive functional polystyrene resin obtained in the third step into an internal mixer according to a proportion, banburying at a reaction temperature of 200 ℃ at a rotation speed of 60r/min for 15 minutes to obtain the polyethylene-nano silicon dioxide-reactive functional polystyrene graft.
Fifthly, preparing insulating resin:
adding polyethylene resin and the polyethylene-nano silicon dioxide-reactive functional polystyrene graft obtained in the step four into a double-screw extruder according to the proportion, extruding at 130-230 ℃, drawing, cooling and granulating to obtain the insulating resin.
The application of the high-performance polyethylene/nano silicon dioxide composite cable insulating resin prepared by the invention as the insulating material for the high-voltage direct-current transmission cable is as follows:
the high-performance polyethylene/nano silicon dioxide composite cable insulating resin prepared by the invention can be directly coated on the surface of a conductor to prepare a cable, can be crosslinked by an irradiation method after being coated, can be blended with a proper amount of crosslinking agent master batch, and can be prepared into a crosslinked polyethylene cable by thermal crosslinking after being fused and coated.
Example 1:
by using 60 Co is used as an irradiation source, gamma rays are used for pre-irradiating the linear low-density polyethylene resin in an air atmosphere, and the pre-irradiation dose range is 25kGy, so that the pre-irradiated polyethylene resin is obtained;
5g of nano-silica particles with the particle size of 50nm are dispersed in 100g of absolute ethyl alcohol/deionized water solution with the volume ratio of 1:1, and are subjected to ultrasonic treatment for 0.5 hour. 5g of the silane coupling agent gamma-methacryloxypropyl trimethoxysilane were added with stirring, the pH of the solution was adjusted to 4 and stirred at 60℃for 24 hours. After the reaction, the nano silica was collected by centrifugation and washed three times with absolute ethanol. Vacuum drying at 60 deg.c for 24 hr to obtain modified nanometer silica.
15g of styrene monomer, 0.16g of reactive functional monomer allyl acrylate, 0.63g of active voltage stabilizer monomer 4-acryloxyacetophenone and 0.15g of photoinitiator are dispersed in 100g of deionized water dissolved with 0.2g of sodium dodecyl sulfonate, reacted for 3 hours under the irradiation of 365nm ultraviolet lamp, ethanol precipitation is carried out, vacuum drying is carried out at the temperature of 40 ℃ by suction filtration, and the reactive functional polystyrene resin is obtained.
Taking pre-irradiation polyethylene resin, modifying nano silicon dioxide and banburying reactive functional polystyrene resin in an internal mixer according to the mass fraction ratio of 15:0.5:10, wherein the internal mixer is at the temperature of 200 ℃ and the rotating speed is 60r/min, and the banburying time is 15 minutes, so as to obtain the polyethylene-nano silicon dioxide-reactive functional polystyrene graft.
Adding the polyethylene-nano silicon dioxide-reactive functional polystyrene graft and polyethylene resin into a double screw extruder according to the mass ratio of 25.5:74.5, extruding at 130-230 ℃, drawing, cooling and granulating to obtain the insulating resin.
A linearly increasing AC/DC voltage was applied to the insulating material (film sample having a thickness of 75 μm) until the samples broke down, resulting in average breakdown strengths of 10 samples, respectively. The electrical breakdown strength was measured at 60 degrees celsius for different times and the results are shown in table 1.
Table 1:
| Time | for 1 day | For 5 days | For 10 days |
| AC breakdown (kV/mm) | 102 | 101 | 101 |
| DC breakdown (kV/mm) | 390 | 395 | 394 |
Example 2:
by using 60 Co is used as an irradiation source, gamma rays are used for pre-irradiating the linear low-density polyethylene resin in an air atmosphere, and the pre-irradiation dosage range is 15kGy, so that the pre-irradiated polyethylene resin is obtained;
5g of nano-silica particles with the particle size of 30nm are dispersed in 100g of absolute ethyl alcohol/deionized water solution with the volume ratio of 1:1, and are subjected to ultrasonic treatment for 0.5 hour. 5g of the silane coupling agent gamma-methacryloxypropyl trimethoxysilane were added with stirring, the pH of the solution was adjusted to 4 and stirred at 60℃for 24 hours. After the reaction, the nano silica was collected by centrifugation and washed three times with absolute ethanol. Vacuum drying at 60 deg.c for 24 hr to obtain modified nanometer silica.
20g of styrene monomer, 1.16g of reactive functional monomer allyl methacrylate, 2.91g of active voltage stabilizer monomer 4-acryloxyacetophenone and 0.15g of photoinitiator are dispersed in 100g of deionized water dissolved with 0.2g of sodium dodecyl sulfonate, reacted for 3 hours under the irradiation of 365nm ultraviolet lamp, precipitated by ethanol, filtered by suction and dried in vacuum at 40 ℃ to obtain the reactive functional polystyrene resin.
Taking pre-irradiation polyethylene resin, modifying nano silicon dioxide and banburying reactive functional polystyrene resin in an internal mixer according to the mass fraction ratio of 23:2:10, wherein the rotation speed of the internal mixer is 60r/min at 200 ℃ and the banburying time is 15 minutes, so as to obtain the polyethylene-nano silicon dioxide-reactive functional polystyrene graft.
Adding the polyethylene-nano silicon dioxide-reactive functional polystyrene graft and polyethylene resin into a double-screw extruder according to the mass ratio of 35:65, extruding at 130-230 ℃, drawing, cooling and granulating to obtain the insulating resin.
A linearly increasing AC/DC voltage was applied to the insulating material (film sample having a thickness of 75 μm) until the samples broke down, resulting in average breakdown strengths of 10 samples, respectively. The electrical breakdown strength was measured at 60 degrees celsius for different times and the results are shown in table 2.
Table 2:
| Time | for 1 day | For 5 days | For 10 days |
| AC breakdown (kV/mm) | 120 | 118 | 119 |
| DC breakdown (kV/mm) | 450 | 445 | 445 |
Example 3:
using an electron accelerator as an irradiation source, and pre-irradiating the low-density polyethylene resin in an air atmosphere by using beta rays, wherein the pre-irradiation dose range is 40kGy, so as to obtain pre-irradiated polyethylene resin;
5g of nano-silica particles with the particle size of 100nm are dispersed in 100g of absolute ethyl alcohol/deionized water solution with the volume ratio of 1:1, and are subjected to ultrasonic treatment for 0.5 hour. 5g of the silane coupling agent gamma-methacryloxypropyl trimethoxysilane were added with stirring, the pH of the solution was adjusted to 4 and stirred at 60℃for 24 hours. After the reaction, the nano silica was collected by centrifugation and washed three times with absolute ethanol. Vacuum drying at 60 deg.c for 24 hr to obtain modified nanometer silica.
25g of styrene monomer, 0.8g of reactive functional monomer allyl methacrylate, 2g of active voltage stabilizer monomer 4-acryloxyacetophenone and 0.15g of photoinitiator are dispersed in 100g of deionized water dissolved with 0.2g of sodium dodecyl sulfonate, reacted for 3 hours under the irradiation of an ultraviolet lamp of 365nm, ethanol precipitation is carried out, vacuum drying is carried out at the temperature of 40 ℃ by suction filtration, and the reactive functional polystyrene resin is obtained.
Taking pre-irradiation polyethylene resin, modifying nano silicon dioxide and banburying reactive functional polystyrene resin in an internal mixer according to the mass fraction ratio of 23:2:10, wherein the rotation speed of the internal mixer is 60r/min at 200 ℃ and the banburying time is 15 minutes, so as to obtain the polyethylene-nano silicon dioxide-reactive functional polystyrene graft.
Adding the polyethylene-nano silicon dioxide-reactive functional polystyrene graft and polyethylene resin into a double-screw extruder according to the mass ratio of 35:65, extruding at 130-230 ℃, drawing, cooling and granulating to obtain the insulating resin.
A linearly increasing AC/DC voltage was applied to the insulating material (film sample having a thickness of 75 μm) until the samples broke down, resulting in average breakdown strengths of 10 samples, respectively. The electrical breakdown strength was measured at 60 degrees celsius for different times and the results are shown in table 3.
Table 3:
| Time | for 1 day | For 5 days | For 10 days |
| AC breakdown (kV/mm) | 115 | 115 | 114 |
| DC breakdown (kV/mm) | 420 | 421 | 425 |
Example 4:
using an electron accelerator as an irradiation source, and pre-irradiating the low-density polyethylene resin in an air atmosphere by using beta rays, wherein the pre-irradiation dose range is 10kGy, so as to obtain pre-irradiated polyethylene resin;
5g of nanosilica particles having a particle size of 30nm were dispersed in 100g of an absolute ethanol/deionized water solution in a volume ratio of 1:1 for 0.5 hour by sonication. 5g of the silane coupling agent gamma-methacryloxypropyl trimethoxysilane were added with stirring, the pH of the solution was adjusted to 4 and stirred at 60℃for 24 hours. After the reaction, the nano silica was collected by centrifugation and washed three times with absolute ethanol. Vacuum drying at 60 deg.c for 24 hr to obtain modified nanometer silica.
20g of styrene monomer, 0.5g of reactive functional monomer allyl methacrylate, 1.5g of active voltage stabilizer monomer 4-acryloxyacetophenone and 0.15g of photoinitiator are dispersed in 100g of deionized water dissolved with 0.2g of sodium dodecyl sulfonate, reacted for 3 hours under the irradiation of 365nm ultraviolet lamp, precipitated by ethanol, filtered by suction and dried in vacuum at 40 ℃ to obtain the reactive functional polystyrene resin.
Taking pre-irradiation polyethylene resin, modified nano silicon dioxide and reactive functional polystyrene resin, banburying the pre-irradiation polyethylene resin and the modified nano silicon dioxide in an internal mixer according to the mass fraction ratio of 20:1:5, wherein the rotating speed of the internal mixer at 200 ℃ is 60r/min, and the banburying time is 15 minutes, so as to obtain the polyethylene-nano silicon dioxide-reactive functional polystyrene graft.
Adding the polyethylene-nano silicon dioxide-reactive functional polystyrene graft and polyethylene resin into a double-screw extruder according to the mass ratio of 26:84, extruding at 130-230 ℃, drawing, cooling and granulating to obtain the insulating resin.
A linearly increasing AC/DC voltage was applied to the insulating material (film sample having a thickness of 75 μm) until the samples broke down, resulting in average breakdown strengths of 10 samples, respectively. The electrical breakdown strength was measured at 60 degrees celsius for different times and the results are shown in table 4.
Table 4:
| Time | for 1 day | For 5 days | For 10 days |
| AC breakdown (kV/mm) | 110 | 111 | 109 |
| DC breakdown (kV/mm) | 405 | 410 | 412 |
Comparative example 1:
in comparison with example 4, the polyethylene resin was not irradiated, and the other steps were the same.
A linearly increasing AC/DC voltage was applied to the insulating material (film sample having a thickness of 75 μm) until the samples broke down, resulting in average breakdown strengths of 10 samples, respectively. The electrical breakdown strength was measured at 60 degrees celsius for different times and the results are shown in table 5.
Table 5:
| Time | for 1 day | For 5 days | For 10 days |
| AC breakdown (kV/mm) | 102 | 100 | 101 |
| DC breakdown (kV/mm) | 385 | 390 | 390 |
Since polyethylene is not irradiated, there is no strong interaction between the modified nano silicon dioxide and the reactive polystyrene and the polyethylene resin, so the electrical breakdown performance of the material is reduced, but since the voltage stabilizer does not migrate after copolymerization with styrene, the breakdown strength does not change with time.
Comparative example 2:
in contrast to example 4, the nanosilica was not modified, the other steps being the same.
A linearly increasing AC/DC voltage was applied to the insulating material (film sample having a thickness of 75 μm) until the samples broke down, resulting in average breakdown strengths of 10 samples, respectively. The electrical breakdown strength was measured at 60 degrees celsius for different times and the results are shown in table 6.
Table 6:
| Time | for 1 day | For 5 days | For 10 days |
| AC breakdown (kV/mm) | 85 | 84 | 81 |
| DC breakdown (kV/mm) | 344 | 339 | 342 |
Because the nano silicon dioxide is not modified, the nano silicon dioxide is easy to agglomerate in the composite material, and the electrical property of the nano composite material is directly reduced.
Comparative example 3:
the other steps were the same as in example 4 except that no voltage stabilizer monomer was added at the time of polymerization of the reactive functional polystyrene resin, and the voltage stabilizer monomer was added at the time of blending the polyethylene-nanosilicon dioxide-reactive functional polystyrene graft with the polyethylene tree so that the voltage stabilizer was not grafted with the polyethylene resin and the voltage stabilizer content was the same as in the insulating resin prepared in comparative example 4.
A linearly increasing AC/DC voltage was applied to the insulating material (film sample having a thickness of 75 μm) until the samples broke down, resulting in average breakdown strengths of 10 samples, respectively. The electrical breakdown strength was measured at 60 degrees celsius for different times and the results are shown in table 7.
Table 7:
| Time | for 1 day | For 5 days | For 10 days |
| AC breakdown (kV/mm) | 110 | 92 | 80 |
| DC breakdown (kV/mm) | 410 | 370 | 350 |
The voltage stabilizer of comparative example 3 was not grafted with polyethylene, and was initially consistent with the electrical strength of example 4, and the small molecule voltage stabilizer monomer gradually precipitated over time, and the electrical breakdown strength of the resin prepared in comparative example 3 was reduced.
In conclusion, the high-performance polyethylene/nano silicon dioxide composite cable insulation resin prepared by the invention solves the problems that the voltage stabilizer is easy to migrate and separate out and the nano silicon dioxide is difficult to disperse, and improves the long-acting electric breakdown resistance of the polyethylene resin; the prepared polyethylene nano composite insulating resin has wide application prospect, can be directly used as an insulating layer, and can be used for preparing crosslinked polyethylene through radiation crosslinking or thermal crosslinking.
It should be noted that, not described in detail, the present invention is well known to those skilled in the art.
The above embodiments are only for further illustrating the embodiments of the present invention, but the present invention is not limited to the above embodiments, and all the equivalent changes and modifications made in the above embodiments are included in the scope of the present invention according to the technical spirit of the present invention.
Claims (7)
1. The high-performance polyethylene/nano silicon dioxide composite cable insulation resin is characterized by comprising the following components in parts by weight: polyethylene resin: 65-80 parts;
pre-irradiation polyethylene resin: 15-25 parts of a lubricant;
modified nano silicon dioxide: 0.5-2 parts;
reactive functional polystyrene resin: 5-10 parts;
and the sum of the weight parts of the polyethylene resin, the pre-irradiation polyethylene resin, the modified nano silicon dioxide and the reactive functional polystyrene resin is 100;
the reactive functional polystyrene resin is obtained by random copolymerization of a reactive functional monomer, an active voltage stabilizer monomer and a styrene monomer;
the reactive functional monomer comprises one or more of allyl acrylate, allyl methacrylate and 10-undecylenic acid vinyl ester, and the structural formula is as follows:
the active voltage stabilizer monomer is 4-acryloyloxy acetophenone and has the following structural formula:
the preparation method of the reactive functional polystyrene resin comprises the following steps:
adding deionized water, emulsifier sodium dodecyl sulfonate, styrene monomer, reactive functional monomer, active voltage stabilizer monomer and photoinitiator in a mass ratio of 100:0.2:15-25:0.16-1.16:0.63-2.91:0.15 into a reaction device, reacting for 3 hours under 365nm ultraviolet irradiation, precipitating the reaction product by absolute ethyl alcohol, filtering, and vacuum drying at 40 ℃ to obtain reactive functional polystyrene resin;
wherein the photoinitiator is 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone.
2. The high performance polyethylene/nano silica composite cable insulation resin of claim 1, wherein the polyethylene resin is a low density polyethylene or a linear low density polyethylene, the linear low density polyethylene being one or more of ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer.
3. The high performance polyethylene/nano silica composite cable insulation resin according to claim 1, wherein the pre-irradiated polyethylene resin is obtained by pre-irradiating a polyethylene resin; the irradiation source is an electron accelerator or 60 Co; the irradiation dose is 10-40kGy.
4. The high performance polyethylene/nano silica composite cable insulation resin according to claim 1, wherein the modified nano silica is obtained via surface modification of γ -methacryloxypropyl trimethoxysilane.
5. A method for preparing the high-performance polyethylene/nano silicon dioxide composite cable insulation resin according to claim 1, which comprises the following steps:
step one, preparing pre-irradiation polyethylene resin:
by using 60 Co is used as an irradiation source, gamma rays are used for pre-irradiating the polyethylene resin in an air atmosphere, and the pre-irradiation dose is 10-40kGy, so that the pre-irradiated polyethylene resin is obtained; or adopting an electron accelerator as an irradiation source, and pre-irradiating the polyethylene resin in an air atmosphere by using beta rays, wherein the pre-irradiation dose is 10-40kGy, so as to obtain pre-irradiated polyethylene resin;
step two, preparing modified nano silicon dioxide:
dispersing nano silicon dioxide particles in an absolute ethyl alcohol/deionized water solution with the volume ratio of 1:1, wherein the mass percentage of the nano silicon dioxide is 5%, and carrying out ultrasonic treatment for 0.5 hour; adding a silane coupling agent gamma-methacryloxypropyl trimethoxy silane with the same mass as nano silicon dioxide under the stirring condition, adjusting the pH value of the solution to 4, and stirring at 60 ℃ for 24 hours; after the reaction is finished, centrifugally collecting nano silicon dioxide, and washing with absolute ethyl alcohol for three times; vacuum drying at 60 deg.c for 24 hr to obtain modified nanometer silica;
step three, preparing reactive functional polystyrene resin:
adding deionized water, emulsifier sodium dodecyl sulfonate, styrene monomer, reactive functional monomer, active voltage stabilizer monomer and photoinitiator in a mass ratio of 100:0.2:15-25:0.16-1.16:0.63-2.91:0.15 into a reaction device, reacting for 3 hours under 365nm ultraviolet irradiation, precipitating the reaction product by absolute ethyl alcohol, filtering, and vacuum drying at 40 ℃ to obtain reactive functional polystyrene resin;
wherein the photoinitiator is 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone;
step four, preparing a polyethylene-nano silicon dioxide-reactive functional polystyrene graft:
adding the pre-irradiated polyethylene resin obtained in the first step, the modified nano silicon dioxide obtained in the second step and the reactive functional polystyrene resin obtained in the third step into an internal mixer according to a proportion, and banburying for 15 minutes at a reaction temperature of 200 ℃ and a rotation speed of 60r/min to obtain a polyethylene-nano silicon dioxide-reactive functional polystyrene graft;
fifthly, preparing insulating resin:
adding polyethylene resin and the polyethylene-nano silicon dioxide-reactive functional polystyrene graft obtained in the step four into a double-screw extruder according to the proportion, extruding at the temperature of 130-230 ℃, and obtaining the insulating resin through drawing, cooling and granulating.
6. The method for preparing high-performance polyethylene/nano silicon dioxide composite cable insulation resin according to claim 5, wherein in the second step, the nano silicon dioxide is spherical and has a particle size of 30-100 nm; in the third step, the reactive functional monomer mass percentage content in the prepared reactive functional polystyrene resin is 1-4%, and the active voltage stabilizer monomer mass percentage content is 4-10%.
7. Use of the high-performance polyethylene/nano silicon dioxide composite cable insulation resin prepared by the preparation method of claim 5 as an insulation material for high-voltage direct-current transmission cables.
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