WO2016206242A1 - Insulation composition for direct-current ultrahigh voltage, preparation method, and uses thereof - Google Patents

Insulation composition for direct-current ultrahigh voltage, preparation method, and uses thereof Download PDF

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WO2016206242A1
WO2016206242A1 PCT/CN2015/092063 CN2015092063W WO2016206242A1 WO 2016206242 A1 WO2016206242 A1 WO 2016206242A1 CN 2015092063 W CN2015092063 W CN 2015092063W WO 2016206242 A1 WO2016206242 A1 WO 2016206242A1
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graphene
insulating composition
ball mill
uhv
insulating
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PCT/CN2015/092063
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French (fr)
Chinese (zh)
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薛杨
钱西慧
王好盛
张冬海
陈运法
李欣欣
徐志磊
沈辉
韩世健
陈殿龙
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中国科学院过程工程研究所
江东金具设备有限公司
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Publication of WO2016206242A1 publication Critical patent/WO2016206242A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
    • H01B3/10—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances metallic oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes

Definitions

  • the present invention belongs to the field of materials, and in particular, the present invention relates to an insulating composition for a DC UHV, a preparation method and use thereof.
  • the insulating material of the polymer as the matrix is in a high-voltage electric field discharge environment for a long time, and the surface of the polymer is decomposed and ablated due to the arc discharge and the high temperature, thereby causing the insulation material to fail.
  • a large amount of aluminum hydroxide or aluminum oxide is added to improve the tracking resistance and electrical insulation performance of the insulating material, and the voltage applied to the transmission network is low, and cannot be applied to the DC UHV transmission network.
  • CN103787322A uses a water-soluble polymer chitosan-based material as a reducing agent and a stabilizer, and a layered silicate as a stabilizer and a template to prepare graphene to obtain a graphene-laden layered silicate nanocomposite.
  • the invention mainly solves the problem of strong toxicity in the preparation of graphene and difficulty in stable dispersion of the product, and it also does not involve the tracking resistance and the electric erosion resistance.
  • CN103143319A composites porous graphene and clay into a porous composite for adsorption of heavy metals and organic matter.
  • the invention mainly utilizes the strong adsorption capacity of graphene, which is also not related to leakage tracking and electrical erosion resistance.
  • a hydrotalcite-loaded graphene flame retardant is prepared by a coprecipitation method for modifying the flame retardant properties of a polymer.
  • the prior art mainly utilizes graphene to improve flame retardant performance, and does not mention leakage resistance. Electrical tracking and electrical erosion performance.
  • CN104392843A discloses a three-dimensional layered metal hydroxide nanosheet/graphene aerogel composite material and a preparation method thereof.
  • the layered metal hydroxide nanosheet/graphene aerogel material is composed of a three-dimensional graphene aerogel and a two-dimensional layered metal hydroxide nanosheet, and the ordered metal hydroxide nanosheets are orderedly distributed.
  • a three-dimensional network structure is formed between the surface and the layers of the graphene aerogel.
  • This prior art has formed a three-dimensional conductive path by adding a large amount of three-dimensional graphene, which cannot be directly used in an insulating material.
  • CN103275408A discloses a method for preparing graphene/layered double hydroxide composite flame retardant and polystyrene nano flame retardant composite material, which comprises dissolving carbon nanotubes in graphene oxide colloid, stirring and dispersing by ultrasonic wave. After dispersing uniformly, adding M 2+ salt and Al 3+ salt, adding urea, refluxing to obtain a graphene/carbon nanotube/layered double hydroxide composite assembly, and mixing the composite assembly with polystyrene resin After melt extrusion, a polystyrene nano flame retardant composite is obtained.
  • This prior art achieves its flame retardant effect by adding a large amount of graphene, which does not consider the influence of the large addition of graphene on the insulation properties.
  • the "UHV" to voltage is above 1000 kV.
  • An insulating composition for DC UHV comprising the following components:
  • the volume of the graphene nanosheet is 0.025 to 0.1 vol% of the volume of the layered composite metal hydroxide.
  • Graphene has a unique two-dimensional layered structure with excellent barrier flame retardancy and heat stability. It can form a barrier layer on the surface to prevent the polymer from decomposing under the action of arc, thus effectively improving the polymer as a matrix. Thermal insulation, tracking resistance and electrical erosion resistance of insulating materials.
  • the present invention overcomes the problem that graphene itself has strong electrical conductivity by selecting a content of graphene nanosheets which is much lower than the percolation threshold capable of forming a conductive network, so that the addition of graphene does not affect the insulation of the insulating material. Sex.
  • the layered composite metal hydroxide has excellent adsorption, barrier and heat resistance stability, and its layered structure of hydrotalcite is advantageous for recombination with graphene.
  • the invention combines a small amount of graphene with the layered composite metal hydroxide, and utilizes the synergistic effect between the two to improve the tracking resistance and the electric corrosion resistance of the insulating material without affecting the insulation performance.
  • the addition of graphene nanosheets can also improve the mechanical properties of the insulating material.
  • DC UHV insulation composition of the present invention may further comprise carbon nanotubes having a lower than penetration threshold content.
  • the volume of the graphene nanosheet is 0.025 to 0.1 vol.% of the volume of the layered composite metal hydroxide, for example, 0.03 vol.%, 0.035 vol.%, 0.04 vol.%, 0.045 vol.%. , 0.05 vol.%, 0.055 vol.%, 0.06 vol.%, 0.065 vol.%, 0.07 vol.%, 0.075 vol.%, 0.08 vol.%, 0.085 vol.%, 0.09 vol.% or 0.095 vol.% It is preferably 0.04 to 0.085 vol%, more preferably 0.045 to 0.07 vol%.
  • the graphene nanosheets are too large in size to easily form a conductive path and affect the insulating properties.
  • the graphene nanosheet has a thickness of 1 to 20 nm, preferably 5 to 10 nm; a length of 100 nm to 20 ⁇ m, preferably 300 nm to 5 ⁇ m; and a specific surface area of 30 to 1500 m 2 /g.
  • the layered double metal hydroxide has the following formula:
  • M1 and M2 are divalent metal cations
  • M1 includes, but is not limited to, any one of Ca 2+ , Mg 2+ , Zn 2+ , Cu 2+ , Co 2+ or Ni 2+ , preferably Ca 2+ , Mg Any one of 2+ or Zn 2+
  • M 2 includes, but is not limited to, any one of Ca 2+ , Mg 2+ , Zn 2+ , Cu 2+ , Co 2+ or Ni 2+ , preferably Co 2+ Any one of Ni 2+ or Cu 2+
  • M 3 and M 4 are trivalent metal cations
  • M 3 includes, but is not limited to, any one of Al 3+ , Cr 3+ , Fe 3+ or Ce 3+ , preferably Al 3+ or Fe 3+
  • M4 includes, but is not limited to, any one of Al 3+ , Cr 3+ , Fe 3+ or Ce 3+ , preferably Cr 3+ or Ce 3+ ;
  • a+b is equal to 1-x
  • c+d is equal to x, where x is the molar ratio of (M3 3+ +M4 3+ )/(M1 2+ +M2 2+ +M3 3+ +M4 3+ ), 0.1 to 0.9 (for example, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7 or 0.8), preferably 0.2 to 0.8, more preferably 0.5 to 0.7;
  • y is 1 to 6 (for example, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5 or 5.5), preferably 2 to 4;
  • a n- represents an anion exchangeable between layers, including but not limited to nitrate, sulfate, lactate, amino acid, chloride, carbonate, z is the molar number of anions, n is the anion valence, where zn is equal to [2 ( a+b)+3(c+d)-y]; v is the amount of water of crystallization between layers, which is 0.1 to 5 (for example, 0.2, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4 or 4.5), It is preferably 0.5 to 3.
  • a and b are not limited individually, and it is only necessary to satisfy the sum of a + b to be 1-x.
  • the layered composite metal hydroxide of the present invention contains at least one divalent metal cation and contains at least one trivalent metal cation.
  • the insulating composition further comprises (C) a coupling agent, and the component (C) coupling agent of the present invention is a common silane coupling agent, and different groups may be selected according to different polymer substrates.
  • a silane coupling agent is a common silane coupling agent, and different groups may be selected according to different polymer substrates.
  • the weight ratio of the (C) coupling agent to the (B) layered composite metal hydroxide is 1:5 to 1:70, for example 1:10, 1:20, 1:30, 1:40, 1 50 or 1:60, preferably 1:9 to 1:50, more preferably 1:12 to 1:45.
  • the insulating composition further comprises (D) a solvent.
  • the weight ratio of the component (D) solvent to the (B) layered composite metal hydroxide of the present invention is 1:1.25 to 1:3, for example, 1:1.5, 1:1.7, 1:1.9, 1:2.1, 1:2.3, 1:2.5, 1:2.7 or 1:2.9, preferably 1:1.5 to 1:2.5.
  • the solvent is deionized water.
  • Another object of the present invention is to provide a method for preparing an insulating composition for DC UHV, comprising the following steps:
  • the "divalent and trivalent metal salt or oxide” means “divalent metal salt or oxide” and “trivalent metal salt or oxide”.
  • the graphene nanosheet is first added to a solvent for ultrasonic dispersion, which is beneficial to the composite of the graphene nanosheet and the layered metal composite hydroxide, and has high dispersion, and can significantly improve various aspects of the product performance.
  • the temperature of the ultrasonic dispersion in the step (I) is 25 to 45 ° C, and the ultrasonic dispersion time is 20 to 90 min.
  • the rotation speed of the step (I) ball mill is 200 to 1000 r/min, preferably 350 r/min to 800 r/min, and the wet milling time is 200 min to 660 min, preferably 300 min to 450 min.
  • the step (II) ball mill rotation speed is 200-700 r/min, preferably 350 r/min to 600 r/min, and the dry grinding time is 20 min to 360 min, preferably 30 min to 240 min.
  • the rotation speed of the ball mill in step (III) is from 200 r/min to 500 r/min, preferably from 350 r/min to 450 r/min, and the ball milling time is from 20 min to 360 min, preferably from 30 min to 240 min.
  • the invention prepares the graphene/layered hydroxide composition by ball milling by dry milling with a ball mill, which improves the material's resistance to tracking and electric erosion without affecting the insulation performance, and has a simple method and is convenient for industrialization. advantage.
  • a third object of the present invention is to provide an use of an insulating composition for a DC UHV as described above for the preparation of a DC UHV transmission line insulation device.
  • a fourth object of the present invention is to provide an insulating composite material for DC UHV containing the above-described insulating composition for DC UHV and a polymer matrix.
  • the quality of the insulating composition for DC UHV accounts for 5-30%, such as 6%, 10%, 15%, 20%, or the mass of the insulating composition of the DC UHV and the polymer matrix. 25%.
  • the content of the insulating composition for the DC UHV is too small to improve the electrical properties, and if the content is too large, the mechanical properties are remarkably lowered.
  • the polymer matrix is any one of silicone rubber, epoxy resin, polyethylene or polytetrafluoroethylene or a mixture of at least two.
  • the above-mentioned insulating composition for DC ultrahigh voltage containing graphene nanosheet/layered metal composite hydroxide is uniformly dispersed into the polymer matrix in a certain proportion, and the obtained insulating composite material is resistant to electric tracking and electric corrosion resistance.
  • the mechanical properties of the insulating composite material have also been significantly improved, and it can be used for the preparation of insulating devices for DC UHV transmission lines.
  • the present invention has the following beneficial effects:
  • the present invention selects graphene nanosheets that are lower than a percolation threshold capable of forming a conductive network
  • the content overcomes the problem that graphene itself has strong conductivity, so that the addition of graphene does not affect its insulation.
  • the layered metal composite hydroxide has excellent adsorption, barrier and heat resistance stability, and the layered structure of the hydrotalcite-like structure is favorable for compounding with graphene, and the invention combines a small amount of graphene with the layered metal.
  • the combination of hydroxides and the synergistic effect between the two can improve the insulation resistance and electrical erosion resistance of the insulating material without affecting the insulation performance;
  • the invention adopts ball mill dry-wet alternately ball milling to prepare DC high-voltage insulation composition, which improves the material's resistance to tracking and electric erosion without affecting the insulation performance, and has a simple method and is convenient for industrialization. The advantages.
  • the above-mentioned insulating composition for DC UHV is uniformly dispersed into the polymer matrix in a certain proportion, and the obtained insulating composite material has greatly improved resistance to tracking and electric corrosion resistance, and mechanical properties are also remarkably improved.
  • the test for electric leakage resistance and electric erosion is determined according to GB6553-2003.
  • the AC breakdown strength test is determined according to GBT 1695-2005.
  • the mechanical performance test is determined according to GB/T528-2009 and GB/T 529-2008.
  • the vulcanized film has been tested for tracking resistance up to 6.0kv 6h, corrosion depth 1.9mm, tensile strength 3.7MPa, elongation at break 679%, tear strength 6.8kN/m, AC breakdown strength 20kV/mm .
  • the vulcanized film has been tested for tracking resistance up to 6.0kv 9.5h, corrosion depth 2.2mm, tensile strength 6.3MPa, elongation at break 349%, tear strength 12.8kN/m, AC breakdown strength 31kV/ Mm.
  • the vulcanized film was tested to have a tracking resistance of up to 6.0 kv 10 h, an erosion depth of 2.4 mm, a tensile strength of 7.1 MPa, an elongation at break of 460%, a tear strength of 11.3 kN/m, and an AC breakdown strength of 28 kV/mm.
  • the vulcanized film has been tested for tracking resistance up to 6.0kv7.5h, corrosion depth 2.1mm, tensile strength 4.7MPa, elongation at break 589%, tear strength 8.1kN/m, AC breakdown strength 24kV/ Mm.
  • the vulcanized film was tested for tracking resistance up to 6.0kv7h, corrosion depth 1.6mm, tensile strength 6.2MPa, elongation at break 465%, tear strength 11.4kN/m, and AC breakdown strength 26kV/mm.
  • the vulcanized film was tested for tracking resistance up to 6.0kv8h, corrosion depth 2.5mm, tensile strength 5.7MPa, elongation at break 510%, tear strength 10.7kN/m, and AC breakdown strength 25kV/mm.
  • the vulcanized film has been tested for tracking resistance up to 6.0kv 7h, corrosion depth 1.8mm, tensile strength 4.5MPa, elongation at break 690%, tear strength 7.3kN/m, AC breakdown strength 23kV/mm .
  • Example 7 achieves a technical effect significantly superior to that of Example 1 by further optimizing the content of the graphene nanosheet.
  • Example 2 The rest was the same as in Example 2 except that the content of graphene nanosheets was 0.0143 g.
  • the vulcanized film has been tested for tracking resistance up to 6.0kv 11h, corrosion depth 1.6mm, tensile strength 7.2MPa, elongation at break 459%, tear strength 14.1kN/m, AC breakdown strength 32kV/mm .
  • Example 8 achieved a technical effect significantly superior to that of Example 2 by further optimizing the content of the graphene nanosheet.
  • the film after vulcanization has been tested for tracking resistance. It can only pass 2h under DC 6.0kv, the depth of erosion is 3.6mm, the tensile strength is 2.9MPa, the elongation at break is 610%, the tear strength is 5.3kN/m. Wearing strength 17kV/mm.
  • Example 1 and Comparative Example 1 It can be found from Example 1 and Comparative Example 1 that the performance of all aspects of the product of Example 1 is significantly better than that of Comparative Example 1, which indicates that in the present invention, the addition of graphene nanosheets in the layered composite metal hydroxide On the basis of the material, the performance of all aspects of the product is significantly improved.
  • the vulcanized film has been tested for tracking resistance. It can only pass 4h under DC 6.0kv, the erosion depth reaches 3.2mm, the tensile strength is 3.1MPa, the elongation at break is 604%, the tear strength is 5.9kN/m. Wear strength 18kV/mm.
  • Example 1 It can be found from Example 1 and Comparative Example 2 that the amount of graphene nanosheets added is too small, which is insufficient to significantly improve various aspects of the product.
  • the rest was the same as in Example 1, except that the graphene nanosheets were added in an amount of 2 g.
  • Example 1 It can be found from Example 1 and Comparative Example 3 that the amount of graphene nanosheets added is too large, which significantly cracks its insulating properties, making it unusable for the preparation of DC UHV transmission line insulation devices.
  • the tracking resistance was destroyed after 40 min at DC 6.0 kv, the corrosion depth reached 3.8 mm, the tensile strength was 3.8 MPa, the elongation at break was 647,%, and the tear strength was 7.5 kN/m. Wear strength 12kV/mm.
  • the vulcanized film has been tested for tracking resistance up to 6.0kV for 6h, corrosion depth of 2.2mm, tensile strength of 2.5MPa, elongation at break of 604%, tear strength of 4.98kN/m, and AC breakdown strength of 20kV/ Mm.
  • Comparing Example 1 and Comparative Example 4 it was found that the performance of each aspect of the product obtained by the alternate ball milling method of the present invention was remarkably superior to that of Comparative Example 4.

Abstract

The present invention relates to an insulation composition for a direct-current ultrahigh voltage, a preparation method, and uses thereof. The composition comprises the following components: (A) graphene nanosheets; (B) layered metal double hydroxides; (C) a coupling agent; and (D) deionized water. The volume of the graphene nanosheets is 0.025vol% to 0.1vol% of that of the layered metal double hydroxides. The preparation method comprises: wet-milling graphene nanosheets and layered metal double hydroxides in a ball-milling machine, adding a coupling agent, and then dry-milling the mixture. The composite material of the present invention has excellent tracking resistance, electric corrosion resistance and flame retardance performance; mechanical performance of the material can be effectively improved; and the composite material can be used for preparing an insulation material for a direct-current ultrahigh-voltage power transmission line.

Description

一种用于直流特高压的绝缘组合物、制备方法及其用途Insulation composition for DC UHV, preparation method and use thereof 技术领域Technical field
本发明属于材料领域，具体地，本发明涉及一种用于直流特高压的绝缘组合物、制备方法及其用途。The present invention belongs to the field of materials, and in particular, the present invention relates to an insulating composition for a DC UHV, a preparation method and use thereof.
背景技术Background technique
在高压输电网络中，高分子聚合物为基体的绝缘材料长期处于高电压电场放电环境下，其表面由于电弧放电及引起的高温而导致高分子聚合物分解烧蚀，从而造成绝缘材料失效。一般情况下通过大量添加氢氧化铝或氧化铝来提高绝缘材料耐漏电起痕和电绝缘性能，其应用输电网络的电压低，无法应用于直流特高压输电网络。In the high-voltage transmission network, the insulating material of the polymer as the matrix is in a high-voltage electric field discharge environment for a long time, and the surface of the polymer is decomposed and ablated due to the arc discharge and the high temperature, thereby causing the insulation material to fail. Under normal circumstances, a large amount of aluminum hydroxide or aluminum oxide is added to improve the tracking resistance and electrical insulation performance of the insulating material, and the voltage applied to the transmission network is low, and cannot be applied to the DC UHV transmission network.
CN104327456A将极少量的金属纳米颗粒加入聚合物体系中，由于产生库伦阻塞效应提高了材料的体积电阻率和击穿强度。但是，该已有技术仅公开了将金属纳米颗粒的加入可以提高材料的体积电阻率和击穿强度，并未涉及耐漏电起痕和电蚀损性能。CN104327456A The addition of very small amounts of metal nanoparticles to a polymer system increases the volume resistivity and breakdown strength of the material due to the Coulomb blockage effect. However, this prior art only discloses that the addition of metal nanoparticles can increase the volume resistivity and breakdown strength of the material, and does not involve tracking resistance and electrical erosion resistance.
CN103787322A采用水溶性高分子壳聚糖基材料作为还原剂和稳定剂，层状硅酸盐作为稳定剂和模板来制备石墨烯，获得一种担载石墨烯层状硅酸盐纳米复合材料。该发明主要解决的为石墨烯制备过程中的强毒性和产物难以稳定分散的问题，其同样并未涉及耐漏电起痕和电蚀损性能。CN103787322A uses a water-soluble polymer chitosan-based material as a reducing agent and a stabilizer, and a layered silicate as a stabilizer and a template to prepare graphene to obtain a graphene-laden layered silicate nanocomposite. The invention mainly solves the problem of strong toxicity in the preparation of graphene and difficulty in stable dispersion of the product, and it also does not involve the tracking resistance and the electric erosion resistance.
CN103143319A将多孔石墨烯和粘土复合成多孔的复合材料，用于重金属和有机物的吸附。该发明主要利用的是石墨烯的强吸附能力，其同样并未涉及耐漏电起痕和电蚀损性能。CN103143319A composites porous graphene and clay into a porous composite for adsorption of heavy metals and organic matter. The invention mainly utilizes the strong adsorption capacity of graphene, which is also not related to leakage tracking and electrical erosion resistance.
CN104371144A通过共沉淀法制备水滑石负载石墨烯阻燃剂，用于改性聚合物阻燃性能。该已有技术主要是利用石墨烯来提高阻燃性能，并未提及耐漏 电起痕和电蚀损性能。CN104371144A A hydrotalcite-loaded graphene flame retardant is prepared by a coprecipitation method for modifying the flame retardant properties of a polymer. The prior art mainly utilizes graphene to improve flame retardant performance, and does not mention leakage resistance. Electrical tracking and electrical erosion performance.
CN104392843A公开一种三维层状金属氢氧化物纳米片/石墨烯气凝胶复合材料及制备方法。所述层状金属氢氧化物纳米片/石墨烯气凝胶材料是由三维石墨烯气凝胶与二维层状金属氢氧化物纳米片组成，层状金属氢氧化物纳米片有序的分布在石墨烯气凝胶表面和层间，形成一种三维网状结构。该已有技术均是通过添加大量的三维石墨烯来形成三维导电通路，其无法直接用于绝缘材料中。CN104392843A discloses a three-dimensional layered metal hydroxide nanosheet/graphene aerogel composite material and a preparation method thereof. The layered metal hydroxide nanosheet/graphene aerogel material is composed of a three-dimensional graphene aerogel and a two-dimensional layered metal hydroxide nanosheet, and the ordered metal hydroxide nanosheets are orderedly distributed. A three-dimensional network structure is formed between the surface and the layers of the graphene aerogel. This prior art has formed a three-dimensional conductive path by adding a large amount of three-dimensional graphene, which cannot be directly used in an insulating material.
CN103275408A公开了一种石墨烯/层状双氢氧化物复合型阻燃剂及聚苯乙烯纳米阻燃复合材料的制备方法：包括将碳纳米管溶于氧化石墨烯胶体中，搅拌并利用超声波分散使其分散均匀后加入M2+盐与Al3+盐后加入尿素，回流反应后得到石墨烯/碳纳米管/层状双氢氧化物复合组装体，将复合组装体与聚苯乙烯树脂混合后熔融挤出得到聚苯乙烯纳米阻燃复合材料。该已有技术通过加入大量的石墨烯以实现其阻燃作用，其并未考虑石墨烯的大量加入对绝缘性能的影响。CN103275408A discloses a method for preparing graphene/layered double hydroxide composite flame retardant and polystyrene nano flame retardant composite material, which comprises dissolving carbon nanotubes in graphene oxide colloid, stirring and dispersing by ultrasonic wave. After dispersing uniformly, adding M 2+ salt and Al 3+ salt, adding urea, refluxing to obtain a graphene/carbon nanotube/layered double hydroxide composite assembly, and mixing the composite assembly with polystyrene resin After melt extrusion, a polystyrene nano flame retardant composite is obtained. This prior art achieves its flame retardant effect by adding a large amount of graphene, which does not consider the influence of the large addition of graphene on the insulation properties.
发明内容Summary of the invention
针对现有技术的不足，本发明目的在于提供一种用于直流特高压的绝缘组合物及其制备方法。In view of the deficiencies of the prior art, it is an object of the present invention to provide an insulating composition for DC UHV and a method of preparing the same.
在本发明中，所述“特高压”至电压在1000kV以上。In the present invention, the "UHV" to voltage is above 1000 kV.
为了达到上述目的，本发明采用了如下技术方案：In order to achieve the above object, the present invention adopts the following technical solutions:
一种用于直流特高压的绝缘组合物，其包括如下组分：An insulating composition for DC UHV, comprising the following components:
(A)石墨烯纳米片；(A) graphene nanosheets;
(B)层状复合金属氢氧化物；(B) a layered composite metal hydroxide;
所述石墨烯纳米片的体积是层状复合金属氢氧化物体积的0.025～0.1vol％。 The volume of the graphene nanosheet is 0.025 to 0.1 vol% of the volume of the layered composite metal hydroxide.
石墨烯具有独特的二维层状结构，具有优异的阻隔阻燃性能和耐热稳定性，能够在表面形成隔离层，防止电弧作用下聚合物的继续分解，从而可以有效的提高聚合物为基体的绝缘材料的耐热稳定性、耐漏电起痕和电蚀损性能。此外，本发明通过选择远低于能够形成导电网络的逾渗阈值的石墨烯纳米片的含量，克服了石墨烯本身具有很强的导电性的问题，使得石墨烯的加入不影响绝缘材料的绝缘性。Graphene has a unique two-dimensional layered structure with excellent barrier flame retardancy and heat stability. It can form a barrier layer on the surface to prevent the polymer from decomposing under the action of arc, thus effectively improving the polymer as a matrix. Thermal insulation, tracking resistance and electrical erosion resistance of insulating materials. In addition, the present invention overcomes the problem that graphene itself has strong electrical conductivity by selecting a content of graphene nanosheets which is much lower than the percolation threshold capable of forming a conductive network, so that the addition of graphene does not affect the insulation of the insulating material. Sex.
层状复合金属氢氧化物具有优异的吸附、阻隔和耐热稳定性，其类水滑石的层状结构有利于与石墨烯进行复合。本发明将少量的石墨烯与层状复合金属氢氧化物结合，利用两者之间的复配协同效应，在提高绝缘材料耐漏电起痕和电蚀损性能的同时不影响其绝缘性能。此外，石墨烯纳米片的加入还可以提高绝缘材料的机械性能。The layered composite metal hydroxide has excellent adsorption, barrier and heat resistance stability, and its layered structure of hydrotalcite is advantageous for recombination with graphene. The invention combines a small amount of graphene with the layered composite metal hydroxide, and utilizes the synergistic effect between the two to improve the tracking resistance and the electric corrosion resistance of the insulating material without affecting the insulation performance. In addition, the addition of graphene nanosheets can also improve the mechanical properties of the insulating material.
本发明所述的“包括”，意指其除所述组分外，还可以包括其他组分，这些其他组分赋予所述绝缘组合物不同的特性。除此之外，本发明所述的“包括”，还可以替换为封闭式的“为”或“由……组成”。示例性的如，本发明所述用于直流特高压绝缘组合物还可以包括低于渗透阈值含量的碳纳米管。"Comprising" as used herein means that in addition to the components, it may include other components which impart different characteristics to the insulating composition. In addition, the "include" of the present invention may also be replaced by a closed "for" or "consisting of". Illustratively, the DC UHV insulation composition of the present invention may further comprise carbon nanotubes having a lower than penetration threshold content.
在本发明中，所述石墨烯纳米片的体积是层状复合金属氢氧化物体积的0.025～0.1vol.％，例如0.03vol.％、0.035vol.％、0.04vol.％、0.045vol.％、0.05vol.％、0.055vol.％、0.06vol.％、0.065vol.％、0.07vol.％、0.075vol.％、0.08vol.％、0.085vol.％、0.09vol.％或0.095vol.％，优选0.04～0.085vol％，进一步优选0.045～0.07vol％。In the present invention, the volume of the graphene nanosheet is 0.025 to 0.1 vol.% of the volume of the layered composite metal hydroxide, for example, 0.03 vol.%, 0.035 vol.%, 0.04 vol.%, 0.045 vol.%. , 0.05 vol.%, 0.055 vol.%, 0.06 vol.%, 0.065 vol.%, 0.07 vol.%, 0.075 vol.%, 0.08 vol.%, 0.085 vol.%, 0.09 vol.% or 0.095 vol.% It is preferably 0.04 to 0.085 vol%, more preferably 0.045 to 0.07 vol%.
在本发明中，石墨烯纳米片尺寸太大，容易形成导电通路，影响绝缘性能。优选地，所述石墨烯纳米片的厚度为1～20nm，优选5～10nm；长度为100nm～20μm，优选300nm～5μm；比表面积为30～1500m2/g。 In the present invention, the graphene nanosheets are too large in size to easily form a conductive path and affect the insulating properties. Preferably, the graphene nanosheet has a thickness of 1 to 20 nm, preferably 5 to 10 nm; a length of 100 nm to 20 μm, preferably 300 nm to 5 μm; and a specific surface area of 30 to 1500 m 2 /g.
优选地，所述层状双金属氢氧化物具有如下通式：Preferably, the layered double metal hydroxide has the following formula:
[M1a 2+M2b 2+M3c 3+M4d 3+(OH)y]x+(zAn-)·vH2O[M1 a 2+ M2 b 2+ M3 c 3+ M4 d 3+ (OH) y ] x+ (zA n- )·vH 2 O
其中M1和M2为二价金属阳离子，M1包括但不限于Ca2+、Mg2+、Zn2+、Cu2+、Co2+或Ni2+中的任意一种，优选Ca2+、Mg2+或Zn2+中的任意一种；M2包括但不限于Ca2+、Mg2+、Zn2+、Cu2+、Co2+或Ni2+中的任意一种，优选Co2+、Ni2+或Cu2+中的任意一种；M3和M4为三价金属阳离子，M3包括但不限于Al3+、Cr3+、Fe3+或Ce3+中的任意一种，优选Al3+或Fe3+；M4包括但不限于Al3+、Cr3+、Fe3+或Ce3+中的任意一种，优选Cr3+或Ce3+；Wherein M1 and M2 are divalent metal cations, and M1 includes, but is not limited to, any one of Ca 2+ , Mg 2+ , Zn 2+ , Cu 2+ , Co 2+ or Ni 2+ , preferably Ca 2+ , Mg Any one of 2+ or Zn 2+ ; M 2 includes, but is not limited to, any one of Ca 2+ , Mg 2+ , Zn 2+ , Cu 2+ , Co 2+ or Ni 2+ , preferably Co 2+ Any one of Ni 2+ or Cu 2+ ; M 3 and M 4 are trivalent metal cations, and M 3 includes, but is not limited to, any one of Al 3+ , Cr 3+ , Fe 3+ or Ce 3+ , preferably Al 3+ or Fe 3+ ; M4 includes, but is not limited to, any one of Al 3+ , Cr 3+ , Fe 3+ or Ce 3+ , preferably Cr 3+ or Ce 3+ ;
a+b等于1-x；c+d等于x，其中，x为(M33++M43+)/(M12++M22++M33++M43+)的摩尔比值，为0.1～0.9(例如0.2、0.3、0.4、0.5、0.6、0.7或0.8)，优选0.2～0.8，更优选0.5～0.7；y为1～6(例如1.5、2、2.5、3、3.5、4、4.5、5或5.5)，优选2～4；a+b is equal to 1-x; c+d is equal to x, where x is the molar ratio of (M3 3+ +M4 3+ )/(M1 2+ +M2 2+ +M3 3+ +M4 3+ ), 0.1 to 0.9 (for example, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7 or 0.8), preferably 0.2 to 0.8, more preferably 0.5 to 0.7; y is 1 to 6 (for example, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5 or 5.5), preferably 2 to 4;
An-代表层间可交换的阴离子，包括但不限于硝酸根、硫酸根、乳酸根、氨基酸、氯离子、碳酸根，z为阴离子摩尔数量，n为阴离子价数，其中zn等于[2(a+b)+3(c+d)-y]；v为层间结晶水数量，为0.1～5(例如0.2、0.5、1、1.5、2、2.5、3、3.5、4或4.5)，优选0.5～3。A n- represents an anion exchangeable between layers, including but not limited to nitrate, sulfate, lactate, amino acid, chloride, carbonate, z is the molar number of anions, n is the anion valence, where zn is equal to [2 ( a+b)+3(c+d)-y]; v is the amount of water of crystallization between layers, which is 0.1 to 5 (for example, 0.2, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4 or 4.5), It is preferably 0.5 to 3.
在上述通式中，对a和b单独不作限定，其只需要满足a+b的和为1-x即可。In the above formula, a and b are not limited individually, and it is only necessary to satisfy the sum of a + b to be 1-x.
本发明的层状复合金属氢氧化物，其含至少一种二价金属阳离子，且含至少一种三价金属阳离子。The layered composite metal hydroxide of the present invention contains at least one divalent metal cation and contains at least one trivalent metal cation.
优选地，所述绝缘组合物还包括(C)偶联剂，本发明所述组份(C)偶联剂为常见的硅烷偶联剂，可根据不同的聚合物基体选用含有不同基团的硅烷偶联剂。 Preferably, the insulating composition further comprises (C) a coupling agent, and the component (C) coupling agent of the present invention is a common silane coupling agent, and different groups may be selected according to different polymer substrates. A silane coupling agent.
优选地，(C)偶联剂与(B)层状复合金属氢氧化物的重量比为1∶5～1∶70，例如1∶10、1∶20、1∶30、1∶40、1∶50或1∶60，优选1∶9～1∶50，更优选1∶12～1∶45。Preferably, the weight ratio of the (C) coupling agent to the (B) layered composite metal hydroxide is 1:5 to 1:70, for example 1:10, 1:20, 1:30, 1:40, 1 50 or 1:60, preferably 1:9 to 1:50, more preferably 1:12 to 1:45.
优选地，所述绝缘组合物还包括(D)溶剂。Preferably, the insulating composition further comprises (D) a solvent.
优选地，本发明所述的组分(D)溶剂与(B)层状复合金属氢氧化物的重量比为1∶1.25～1∶3，例如1∶1.5、1∶1.7、1∶1.9、1∶2.1、1∶2.3、1∶2.5、1∶2.7或1∶2.9，优选1∶1.5～1∶2.5。Preferably, the weight ratio of the component (D) solvent to the (B) layered composite metal hydroxide of the present invention is 1:1.25 to 1:3, for example, 1:1.5, 1:1.7, 1:1.9, 1:2.1, 1:2.3, 1:2.5, 1:2.7 or 1:2.9, preferably 1:1.5 to 1:2.5.
优选地，所述溶剂为去离子水。Preferably, the solvent is deionized water.
本发明的目的之二在于提供一种用于直流特高压的绝缘组合物的制备方法，包括如下步骤：Another object of the present invention is to provide a method for preparing an insulating composition for DC UHV, comprising the following steps:
(I)将石墨烯纳米片加入溶剂中超声分散，然后加入制备层状复合金属氢氧化物的二价和三价金属盐或氧化物，搅拌均匀，然后放入球磨机中湿磨，而后烘干；(I) ultrasonically dispersing the graphene nanosheets in a solvent, then adding the divalent and trivalent metal salts or oxides of the layered composite metal hydroxide, stirring uniformly, then placing them in a ball mill for wet grinding, and then drying ;
(II)将烘干后得到的物料再放入球磨机中干磨；(II) the material obtained after drying is placed in a ball mill for dry grinding;
任选地，进行步骤(III)：Optionally, proceeding to step (III):
(III)加入偶联剂干磨。(III) Drying by adding a coupling agent.
在本发明中，所述“二价和三价金属盐或氧化物”即，“二价金属盐或氧化物”与“三价金属盐或氧化物”。In the present invention, the "divalent and trivalent metal salt or oxide" means "divalent metal salt or oxide" and "trivalent metal salt or oxide".
本发明中，将石墨烯纳米片首先加入溶剂中进行超声分散，有利于石墨烯纳米片和层状金属复合氢氧化物的复合，分散度高，可显著提高产品的各方面性能。In the present invention, the graphene nanosheet is first added to a solvent for ultrasonic dispersion, which is beneficial to the composite of the graphene nanosheet and the layered metal composite hydroxide, and has high dispersion, and can significantly improve various aspects of the product performance.
优选地，步骤(I)超声分散的温度为25～45℃，超声分散的时间为20～90min。Preferably, the temperature of the ultrasonic dispersion in the step (I) is 25 to 45 ° C, and the ultrasonic dispersion time is 20 to 90 min.
优选地，步骤(I)球磨机的转速为200～1000r/min，优选350r/min～800r/min，湿磨时间为200min～660min，优选300min～450min。 Preferably, the rotation speed of the step (I) ball mill is 200 to 1000 r/min, preferably 350 r/min to 800 r/min, and the wet milling time is 200 min to 660 min, preferably 300 min to 450 min.
优选地，步骤(II)球磨机转速为200～700r/min，优选350r/min～600r/min，干磨时间为20min～360min，优选30min～240min。Preferably, the step (II) ball mill rotation speed is 200-700 r/min, preferably 350 r/min to 600 r/min, and the dry grinding time is 20 min to 360 min, preferably 30 min to 240 min.
优选地，步骤(III)球磨机转速为200r/min～500r/min，优选350r/min～450r/min，球磨时间为20min～360min，优选30min～240min。Preferably, the rotation speed of the ball mill in step (III) is from 200 r/min to 500 r/min, preferably from 350 r/min to 450 r/min, and the ball milling time is from 20 min to 360 min, preferably from 30 min to 240 min.
本发明通过采用球磨机干湿交替进行球磨制备石墨烯/层状氢氧化物组合物，在提高材料耐漏电起痕和电蚀损性能的同时不影响其绝缘性能，同时具有方法简单，便于工业化的优点。The invention prepares the graphene/layered hydroxide composition by ball milling by dry milling with a ball mill, which improves the material's resistance to tracking and electric erosion without affecting the insulation performance, and has a simple method and is convenient for industrialization. advantage.
本发明的目的之三在于提供一种如上所述的用于直流特高压的绝缘组合物的用途，其用于直流特高压输电线路绝缘器件的制备。A third object of the present invention is to provide an use of an insulating composition for a DC UHV as described above for the preparation of a DC UHV transmission line insulation device.
本发明的目的之四在于提供一种用于直流特高压的绝缘复合材料，其含有如上所述的用于直流特高压的绝缘组合物以及聚合物基体。A fourth object of the present invention is to provide an insulating composite material for DC UHV containing the above-described insulating composition for DC UHV and a polymer matrix.
优选地，所述用于直流特高压的绝缘组合物的质量占用于直流特高压的绝缘组合物和聚合物基体质量总和的5～30％，例如6％、10％、15％、20％或25％。用于直流特高压的绝缘组合物的含量太少，无法实现电性能的提高，含量太多，则会显著降低力学性能。Preferably, the quality of the insulating composition for DC UHV accounts for 5-30%, such as 6%, 10%, 15%, 20%, or the mass of the insulating composition of the DC UHV and the polymer matrix. 25%. The content of the insulating composition for the DC UHV is too small to improve the electrical properties, and if the content is too large, the mechanical properties are remarkably lowered.
优选地，所述聚合物基体为硅橡胶、环氧树脂、聚乙烯或聚四氟乙烯中的任意一种或者至少两种的混合物。Preferably, the polymer matrix is any one of silicone rubber, epoxy resin, polyethylene or polytetrafluoroethylene or a mixture of at least two.
将上述含有石墨烯纳米片/层状金属复合氢氧化物的用于直流特高压的绝缘组合物按一定比例均匀分散到聚合物基体中，所得的绝缘复合材料耐漏电起痕和电蚀损性能有大幅度提高，此外，绝缘复合材料的机械性能也得到了显著提高，可用于直流特高压输电线路绝缘器件的制备。The above-mentioned insulating composition for DC ultrahigh voltage containing graphene nanosheet/layered metal composite hydroxide is uniformly dispersed into the polymer matrix in a certain proportion, and the obtained insulating composite material is resistant to electric tracking and electric corrosion resistance. The mechanical properties of the insulating composite material have also been significantly improved, and it can be used for the preparation of insulating devices for DC UHV transmission lines.
与已有技术相比，本发明具有如下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
(1)本发明通过选择低于能够形成导电网络的逾渗阈值的石墨烯纳米片的 含量，克服了石墨烯本身具有很强的导电性的问题，使得石墨烯的加入不影响其绝缘性。(1) The present invention selects graphene nanosheets that are lower than a percolation threshold capable of forming a conductive network The content overcomes the problem that graphene itself has strong conductivity, so that the addition of graphene does not affect its insulation.
(2)层状金属复合氢氧化物具有优异的吸附、阻隔和耐热稳定性，其类水滑石的层状结构有利于与石墨烯进行复合，本发明将少量的石墨烯与层状金属复合氢氧化物结合，利用两者之间的复配协同效应，在提高绝缘材料耐漏电起痕和电蚀损性能的同时不影响其绝缘性能；(2) The layered metal composite hydroxide has excellent adsorption, barrier and heat resistance stability, and the layered structure of the hydrotalcite-like structure is favorable for compounding with graphene, and the invention combines a small amount of graphene with the layered metal. The combination of hydroxides and the synergistic effect between the two can improve the insulation resistance and electrical erosion resistance of the insulating material without affecting the insulation performance;
(3)本发明通过采用球磨机干湿交替进行球磨制备用于直流特高压绝缘组合物，在提高材料耐漏电起痕和电蚀损性能的同时不影响其绝缘性能，同时具有方法简单，便于工业化的优点。(3) The invention adopts ball mill dry-wet alternately ball milling to prepare DC high-voltage insulation composition, which improves the material's resistance to tracking and electric erosion without affecting the insulation performance, and has a simple method and is convenient for industrialization. The advantages.
(4)将上述用于直流特高压的绝缘组合物按一定比例均匀分散到聚合物基体中，所得的绝缘复合材料耐漏电起痕和电蚀损性能有大幅度提高，机械性能也显著提高。(4) The above-mentioned insulating composition for DC UHV is uniformly dispersed into the polymer matrix in a certain proportion, and the obtained insulating composite material has greatly improved resistance to tracking and electric corrosion resistance, and mechanical properties are also remarkably improved.
具体实施方式detailed description
下面通过具体实施方式来进一步说明本发明的技术方案。The technical solution of the present invention will be further described below by way of specific embodiments.
其耐漏电起痕和电蚀损测试按GB6553-2003测定，交流击穿强度测试按照GBT 1695-2005测定，机械性能测试按照GB/T528-2009和GB/T 529-2008测定。The test for electric leakage resistance and electric erosion is determined according to GB6553-2003. The AC breakdown strength test is determined according to GBT 1695-2005. The mechanical performance test is determined according to GB/T528-2009 and GB/T 529-2008.
实施例1Example 1
将0.0063g石墨烯纳米片(厚度为1nm，长度为100nm，比表面积为1500m2/g)加入20ml去离子水中，常温超声60min，加入8.97g氧化钙，13.74g硝酸铁和2.6g硝酸铈，搅拌均匀，放入球磨机中湿磨，球磨机转速为200r/min，球磨时间为660min，然后放入烘箱中烘干，再放入球磨机干磨，球磨机转速为700r/min，球磨时间为20min，得到石墨烯/[Ca0.8Fe0.17Ce0.03(OH)2](NO3)0.2·0.1H2O组合物。然后加入5.1g乙烯基三乙氧基硅烷球磨，球磨机转速为200r/min，球 磨时间为360min，得到改性的石墨烯/[Ca0.8Fe0.17Ce0.03(OH)2](NO3)0.2·0.1H2O组合物。取其5g加入到95g高温硫化硅橡胶中，并加入2，5-二甲基-2，5-双(叔丁基过氧基)己烷1.5g以及羟基硅油3.5g，混炼出片。0.0063 g of graphene nanosheets (thickness: 1 nm, length: 100 nm, specific surface area: 1500 m 2 /g) were added to 20 ml of deionized water, sonicated at room temperature for 60 min, and 8.97 g of calcium oxide, 13.74 g of ferric nitrate and 2.6 g of lanthanum nitrate were added. Stir well, put into the ball mill for wet grinding, the ball mill speed is 200r/min, the ball milling time is 660min, then put it into the oven for drying, then put it into the ball mill dry grinding, the ball mill speed is 700r/min, the ball milling time is 20min, get Graphene/[Ca 0.8 Fe 0.17 Ce 0.03 (OH) 2 ](NO 3 ) 0.2 ·0.1H 2 O composition. Then, 5.1 g of vinyltriethoxysilane was ball milled, the ball mill was rotated at 200 r/min, and the milling time was 360 min to obtain modified graphene/[Ca 0.8 Fe 0.17 Ce 0.03 (OH) 2 ](NO 3 ) 0.2 · 0.1H 2 O composition. 5 g of this was added to 95 g of high-temperature vulcanized silicone rubber, and 1.5 g of 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane and 3.5 g of hydroxysilicone oil were added, and the mixture was kneaded.
硫化后的胶片经测试耐漏电起痕达到直流6.0kv 6h，蚀损深度1.9mm，拉伸强度3.7MPa，断裂伸长率679％，撕裂强度6.8kN/m，交流击穿强度20kV/mm。The vulcanized film has been tested for tracking resistance up to 6.0kv 6h, corrosion depth 1.9mm, tensile strength 3.7MPa, elongation at break 679%, tear strength 6.8kN/m, AC breakdown strength 20kV/mm .
实施例2Example 2
将0.02g石墨烯纳米片(厚度为20nm，长度为20μm，比表面积为30m2/g)加入6.8ml去离子水中，常温超声60min，加入7.5g氧化钙，6.5g氯化铜和6.4g氯化铝，搅拌均匀，放入球磨机中湿磨，球磨机转速为1000r/min，球磨时间为300min，然后放入烘箱中烘干，再放入球磨机干磨，球磨机转速为200r/min，球磨时间为360min，得到石墨烯/[Ca0.67Cu0.19Al0.24(OH)2](Cl)0.44·3H2O组合物。然后加入0.3g乙烯基三乙氧基硅烷球磨，球磨机转速为700r/min，球磨时间为20min，得到改性的石墨烯/[Ca0.67Cu0.19Al0.24(OH)2](Cl)0.44·3H2O组合物。取其30g加入到70g高温硫化硅橡胶中，并加入2，5-二甲基-2，5-双(叔丁基过氧基)己烷2.5g以及羟基硅油4.5g，混炼出片。0.02 g of graphene nanosheets (thickness 20 nm, length 20 μm, specific surface area 30 m 2 /g) were added to 6.8 ml of deionized water, sonicated at room temperature for 60 min, 7.5 g of calcium oxide, 6.5 g of copper chloride and 6.4 g of chlorine were added. Aluminum, stir evenly, put into the ball mill, wet grinding, ball mill speed is 1000r/min, ball milling time is 300min, then put it in the oven to dry, then put it into the ball mill dry grinding, the ball mill speed is 200r/min, the ball milling time is At 360 min, a graphene/[Ca 0.67 Cu 0.19 Al 0.24 (OH) 2 ](Cl) 0.44 ·3H 2 O composition was obtained. Then, 0.3 g of vinyltriethoxysilane was ball-milled, the ball mill was rotated at 700 r/min, and the ball milling time was 20 min to obtain modified graphene/[Ca 0.67 Cu 0.19 Al 0.24 (OH) 2 ](Cl) 0.44 ·3H. 2 O composition. 30 g of this was added to 70 g of high-temperature vulcanized silicone rubber, and 2.5 g of 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane and 4.5 g of hydroxysilicone oil were added, and the mixture was kneaded.
硫化后的胶片经测试耐漏电起痕达到直流6.0kv 9.5h，蚀损深度2.2mm，拉伸强度6.3MPa，断裂伸长率349％，撕裂强度12.8kN/m，交流击穿强度31kV/mm。The vulcanized film has been tested for tracking resistance up to 6.0kv 9.5h, corrosion depth 2.2mm, tensile strength 6.3MPa, elongation at break 349%, tear strength 12.8kN/m, AC breakdown strength 31kV/ Mm.
实施例3Example 3
将0.023g石墨烯纳米片(厚度为5nm，长度为300nm，比表面积为750m2/g)加入23ml去离子水中，常温超声60min，加入16.84g硫酸镁，7.45g硫酸镍，13.32g硫酸铝和20.2g硫酸铁，搅拌均匀，放入球磨机中湿磨，球磨机转速为800r/min，球磨时间为300min，然后放入烘箱中烘干，再放入球磨机干磨，球磨机转速为600r/min，球磨时间为30min，得到石墨烯 /[Mg0.41Ni0.17Al0.12Fe0.3(OH)2](SO4)0.21·0.8H2O组合物。然后加入1.16g乙烯基三(β-甲氧基乙氧基)硅烷球磨，球磨机转速为450r/min，球磨时间为30min，得到改性的石墨烯/[Mg0.41Ni0.17Al0.12Fe0.3(OH)2](SO4)0.21·0.8H2O组合物。取其26g加入到74g室温硫化硅橡胶中，并加入2，5-二甲基-2，5-双(叔丁基过氧基)己烷2.5g以及羟基硅油3.5g，混炼出片。0.023 g of graphene nanosheet (thickness 5 nm, length 300 nm, specific surface area 750 m 2 /g) was added to 23 ml of deionized water, sonicated at room temperature for 60 min, 16.84 g of magnesium sulfate, 7.45 g of nickel sulfate, 13.32 g of aluminum sulfate and 20.2g ferric sulfate, stir evenly, put into the ball mill for wet grinding, the ball mill speed is 800r/min, the ball milling time is 300min, then put it into the oven for drying, then put it into the ball mill for dry grinding, the ball mill speed is 600r/min, ball mill The time was 30 min, and a graphene/[Mg 0.41 Ni 0.17 Al 0.12 Fe 0.3 (OH) 2 ](SO 4 ) 0.21 ·0.8H 2 O composition was obtained. Then, 1.16 g of vinyltris(β-methoxyethoxy)silane was ball-milled, the ball mill was rotated at 450 r/min, and the ball milling time was 30 min to obtain modified graphene/[Mg 0.41 Ni 0.17 Al 0.12 Fe 0.3 (OH). 2 ] (SO 4 ) 0.21 · 0.8H 2 O composition. 26 g of this was added to 74 g of room temperature vulcanized silicone rubber, and 2.5 g of 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane and 3.5 g of hydroxysilicone oil were added, and the mixture was kneaded.
硫化后的胶片经测试耐漏电起痕达到直流6.0kv10h，蚀损深度2.4mm，拉伸强度7.1MPa，断裂伸长率460％，撕裂强度11.3kN/m，交流击穿强度28kV/mm。The vulcanized film was tested to have a tracking resistance of up to 6.0 kv 10 h, an erosion depth of 2.4 mm, a tensile strength of 7.1 MPa, an elongation at break of 460%, a tear strength of 11.3 kN/m, and an AC breakdown strength of 28 kV/mm.
实施例4Example 4
将0.026g石墨烯纳米片(厚度为10nm，长度为5μm，比表面积为47m2/g)加入20ml去离子水中，常温超声60min，加入2.5g氧化钙，5.13g硝酸镁和23g硝酸铝，搅拌均匀，放入球磨机中湿磨，球磨机转速为350r/min，球磨时间为450min，然后放入烘箱中烘干，再放入球磨机干磨，球磨机转速为350r/min，球磨时间为240min，得到石墨烯/[Ca0.35Mg0.16Al0.49(OH)2](NO3)0.49·0.5H2O组合物。然后加入3.4g乙烯基三乙氧基硅烷球磨，球磨机转速为500r/min，球磨时间为200min，得到改性的石墨烯/[Ca0.35Mg0.16Al0.49(OH)2](NO3)0.49·0.5H2O组合物。取其10g加入到90g高温硫化硅橡胶中，并加入2，5-二甲基-2，5-双(叔丁基过氧基)己烷2.5g以及羟基硅油3.5g，混炼出片。0.026 g of graphene nanosheet (thickness 10 nm, length 5 μm, specific surface area 47 m 2 /g) was added to 20 ml of deionized water, sonicated at room temperature for 60 min, 2.5 g of calcium oxide, 5.13 g of magnesium nitrate and 23 g of aluminum nitrate were added and stirred. Uniform, put into the ball mill for wet grinding, the ball mill speed is 350r/min, the ball milling time is 450min, then put it into the oven for drying, then put it into the ball mill dry grinding, the ball mill speed is 350r/min, the ball milling time is 240min, get the graphite Alkene/[Ca 0.35 Mg 0.16 Al 0.49 (OH) 2 ](NO 3 ) 0.49 ·0.5H 2 O composition. Then, 3.4 g of vinyltriethoxysilane was ball-milled, the ball mill was rotated at 500 r/min, and the ball milling time was 200 min to obtain modified graphene/[Ca 0.35 Mg 0.16 Al 0.49 (OH) 2 ](NO 3 ) 0.49 · 0.5H 2 O composition. 10 g of this was added to 90 g of a high-temperature vulcanized silicone rubber, and 2.5 g of 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane and 3.5 g of a hydroxy silicone oil were added, and the mixture was kneaded.
硫化后的胶片经测试耐漏电起痕达到直流6.0kv7.5h，蚀损深度2.1mm，拉伸强度4.7MPa，断裂伸长率589％，撕裂强度8.1kN/m，交流击穿强度24kV/mm。The vulcanized film has been tested for tracking resistance up to 6.0kv7.5h, corrosion depth 2.1mm, tensile strength 4.7MPa, elongation at break 589%, tear strength 8.1kN/m, AC breakdown strength 24kV/ Mm.
实施例5Example 5
将0.023g石墨烯纳米片(厚度为8nm，长度为600nm，比表面积为643m2/g)加入26ml去离子水中，常温超声60min，加入5.27g氧化钙，6.41g硫酸镁，17.32g 硫酸铝和2.17g硫酸铁，搅拌均匀，放入球磨机中湿磨，球磨机转速为600r/min，球磨时间为380min，然后放入烘箱中烘干，再放入球磨机干磨，球磨机转速为550r/min，球磨时间为160min，得到石墨烯/[Ca0.47Mg0.13Al0.13Fe0.27(OH)2](SO4)0.2·2.5H2O组合物。然后加入4.2g乙烯基三乙氧基硅烷球磨，球磨机转速为400r/min，球磨时间为80min，得到改性的石墨烯/[Ca0.47Mg0.13Al0.13Fe0.27(OH)2](SO4)0.2·2.5H2O组合物。取其24g加入到76g高温硫化硅橡胶中，并加入2，5-二甲基-2，5-双(叔丁基过氧基)己烷1.5g以及羟基硅油5g，混炼出片。0.023 g of graphene nanosheet (thickness 8 nm, length 600 nm, specific surface area 643 m 2 /g) was added to 26 ml of deionized water, sonicated at room temperature for 60 min, 5.27 g of calcium oxide, 6.41 g of magnesium sulfate, and 17.32 g of aluminum sulfate and 2.17g iron sulphate, stir evenly, put into the ball mill for wet grinding, the ball mill speed is 600r/min, the ball milling time is 380min, then put it into the oven to dry, then put it into the ball mill dry grinding, the ball mill speed is 550r/min, ball mill The time was 160 min, and a graphene/[Ca 0.47 Mg 0.13 Al 0.13 Fe 0.27 (OH) 2 ](SO 4 ) 0.2 ·2.5H 2 O composition was obtained. Then, 4.2 g of vinyltriethoxysilane was ball-milled, the ball mill was rotated at 400 r/min, and the ball milling time was 80 min to obtain modified graphene/[Ca 0.47 Mg 0.13 Al 0.13 Fe 0.27 (OH) 2 ](SO 4 ). 0.2 · 2.5H 2 O composition. 24 g of this was added to 76 g of high-temperature vulcanized silicone rubber, and 1.5 g of 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane and 5 g of hydroxysilicone oil were added, and the mixture was kneaded.
硫化后的胶片经测试耐漏电起痕达到直流6.0kv7h，蚀损深度1.6mm，拉伸强度6.2MPa，断裂伸长率465％，撕裂强度11.4kN/m，交流击穿强度26kV/mm。The vulcanized film was tested for tracking resistance up to 6.0kv7h, corrosion depth 1.6mm, tensile strength 6.2MPa, elongation at break 465%, tear strength 11.4kN/m, and AC breakdown strength 26kV/mm.
实施例6Example 6
将0.039g石墨烯纳米片(厚度为15nm，长度为1μm，比表面积为478m2/g)加入34ml去离子水中，常温超声60min，加入17.95g硝酸镁，28.76g硝酸铝，4.71g硝酸铁和3.62g硝酸铈，搅拌均匀，放入球磨机中湿磨，球磨机转速为750r/min，球磨时间为350min，然后放入烘箱中烘干，再放入球磨机干磨，球磨机转速为420r/min，球磨时间为130min，得到石墨烯/[Mg0.42Al0.46Fe0.07Ce0.05(OH)2](NO3)0.58·1.6H2O组合物。然后加入1.22g乙烯基三叔丁基过氧硅烷球磨，球磨机转速为500r/min，球磨时间为200min，得到改性的石墨烯/[Mg0.42Al0.46Fe0.07Ce0.05(OH)2](NO3)0.58·1.6H2O组合物。取其19g加入到91g高温硫化硅橡胶中，并加入2，5-二甲基-2，5-双(叔丁基过氧基)己烷0.5g以及羟基硅油2.5g，混炼出片。0.039 g of graphene nanosheet (thickness 15 nm, length 1 μm, specific surface area 478 m 2 /g) was added to 34 ml of deionized water, sonicated at room temperature for 60 min, 17.95 g of magnesium nitrate, 28.76 g of aluminum nitrate, 4.71 g of ferric nitrate and 3.62g lanthanum nitrate, stir evenly, put it into the ball mill for wet grinding, the ball mill speed is 750r/min, the ball milling time is 350min, then put it into the oven to dry, then put it into the ball mill dry grinding, the ball mill speed is 420r/min, ball mill The time was 130 min, and a graphene/[Mg 0.42 Al 0.46 Fe 0.07 Ce 0.05 (OH) 2 ](NO 3 ) 0.58 ·1.6H 2 O composition was obtained. Then, 1.22 g of vinyltri-tert-butylperoxysilane was ball-milled, the ball mill was rotated at 500 r/min, and the ball milling time was 200 min to obtain modified graphene/[Mg 0.42 Al 0.46 Fe 0.07 Ce 0.05 (OH) 2 ] (NO 3 ) 0.58 · 1.6H 2 O composition. 19 g of this was added to 91 g of a high-temperature vulcanized silicone rubber, and 0.5 g of 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane and 2.5 g of a hydroxysilicone oil were added, and the mixture was kneaded.
硫化后的胶片经测试耐漏电起痕达到直流6.0kv8h，蚀损深度2.5mm，拉伸强度5.7MPa，断裂伸长率510％，撕裂强度10.7kN/m，交流击穿强度25kV/mm。 The vulcanized film was tested for tracking resistance up to 6.0kv8h, corrosion depth 2.5mm, tensile strength 5.7MPa, elongation at break 510%, tear strength 10.7kN/m, and AC breakdown strength 25kV/mm.
实施例7Example 7
其余与实施例1相同，除石墨烯纳米片的含量为0.0115g。The rest was the same as in Example 1, except that the content of graphene nanosheets was 0.0115 g.
硫化后的胶片经测试耐漏电起痕达到直流6.0kv 7h，蚀损深度1.8mm，拉伸强度4.5MPa，断裂伸长率690％，撕裂强度7.3kN/m，交流击穿强度23kV/mm。The vulcanized film has been tested for tracking resistance up to 6.0kv 7h, corrosion depth 1.8mm, tensile strength 4.5MPa, elongation at break 690%, tear strength 7.3kN/m, AC breakdown strength 23kV/mm .
通过实施例1与实施例7的对比可以发现，实施例7通过对石墨烯纳米片含量的进一步优选，实现了显著优于实施例1的技术效果。From the comparison of Example 1 with Example 7, it can be found that Example 7 achieves a technical effect significantly superior to that of Example 1 by further optimizing the content of the graphene nanosheet.
实施例8Example 8
其余与实施例2相同，除石墨烯纳米片的含量为0.0143g。The rest was the same as in Example 2 except that the content of graphene nanosheets was 0.0143 g.
硫化后的胶片经测试耐漏电起痕达到直流6.0kv 11h，蚀损深度1.6mm，拉伸强度7.2MPa，断裂伸长率459％，撕裂强度14.1kN/m，交流击穿强度32kV/mm。The vulcanized film has been tested for tracking resistance up to 6.0kv 11h, corrosion depth 1.6mm, tensile strength 7.2MPa, elongation at break 459%, tear strength 14.1kN/m, AC breakdown strength 32kV/mm .
通过实施例8与实施例2的对比可以发现，实施例8通过对石墨烯纳米片含量的进一步优选，实现了显著优于实施例2的技术效果。From the comparison of Example 8 with Example 2, it was found that Example 8 achieved a technical effect significantly superior to that of Example 2 by further optimizing the content of the graphene nanosheet.
对比例1Comparative example 1
在球磨机中加入8.97g氧化钙，13.74g硝酸铁和2.6g硝酸铈，搅拌均匀，放入球磨机中湿磨，球磨机转速为200r/min，球磨时间为660min，然后放入烘箱中烘干，再放入球磨机干磨，球磨机转速为700r/min，球磨时间为20min，得到[Ca0.8Fe0.17Ce0.03(OH)2](NO3)0.2·0.1H2O层状氢氧化物。然后加入5.1g乙烯基三乙氧基硅烷球磨，球磨机转速为200r/min，球磨时间为360min，得到改性的[Ca0.8Fe0.17Ce0.03(OH)2](NO3)0.2·0.1H2O层状氢氧化物。取其5g加入到95g高温硫化硅橡胶中，并加入2，5-二甲基-2，5-双(叔丁基过氧基)己烷1.5g以及羟基硅油3.5g，混炼出片。Add 8.97g calcium oxide, 13.74g ferric nitrate and 2.6g lanthanum nitrate to the ball mill, stir evenly, put it into the ball mill for wet grinding, the ball mill speed is 200r/min, the ball milling time is 660min, then put it in the oven to dry, then The ball mill was dry-milled, the ball mill was rotated at 700 r/min, and the ball milling time was 20 min to obtain a layered hydroxide of [Ca 0.8 Fe 0.17 Ce 0.03 (OH) 2 ](NO 3 ) 0.2 ·0.1H 2 O. Then, 5.1 g of vinyltriethoxysilane was ball-milled, the ball mill was rotated at 200 r/min, and the ball milling time was 360 min to obtain modified [Ca 0.8 Fe 0.17 Ce 0.03 (OH) 2 ](NO 3 ) 0.2 ·0.1H 2 O layered hydroxide. 5 g of this was added to 95 g of high-temperature vulcanized silicone rubber, and 1.5 g of 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane and 3.5 g of hydroxysilicone oil were added, and the mixture was kneaded.
硫化后的胶片经测试耐漏电起痕在直流6.0kv下只能通过2h，蚀损深度达到3.6mm，拉伸强度2.9MPa，断裂伸长率610％，撕裂强度5.3kN/m，交流击 穿强度17kV/mm。The film after vulcanization has been tested for tracking resistance. It can only pass 2h under DC 6.0kv, the depth of erosion is 3.6mm, the tensile strength is 2.9MPa, the elongation at break is 610%, the tear strength is 5.3kN/m. Wearing strength 17kV/mm.
通过实施例1与对比例1可以发现，实施例1的产品各方面性能均显著地优于对比例1，这说明，在本发明中，石墨烯纳米片的加入，在层状复合金属氢氧化物的基础上，显著地提升了产品的各方面性能。It can be found from Example 1 and Comparative Example 1 that the performance of all aspects of the product of Example 1 is significantly better than that of Comparative Example 1, which indicates that in the present invention, the addition of graphene nanosheets in the layered composite metal hydroxide On the basis of the material, the performance of all aspects of the product is significantly improved.
对比例2Comparative example 2
其余与实施例1相同，除石墨烯纳米片的含量为0.003g。The rest was the same as in Example 1, except that the content of graphene nanosheets was 0.003 g.
硫化后的胶片经测试耐漏电起痕在直流6.0kv下只能通过4h，蚀损深度达到3.2mm，拉伸强度3.1MPa，断裂伸长率604％，撕裂强度5.9kN/m，交流击穿强度18kV/mm。The vulcanized film has been tested for tracking resistance. It can only pass 4h under DC 6.0kv, the erosion depth reaches 3.2mm, the tensile strength is 3.1MPa, the elongation at break is 604%, the tear strength is 5.9kN/m. Wear strength 18kV/mm.
通过实施例1和对比例2可以发现，石墨烯纳米片的加入量太少，其不足以显著提升产品的各方面性能。It can be found from Example 1 and Comparative Example 2 that the amount of graphene nanosheets added is too small, which is insufficient to significantly improve various aspects of the product.
对比例3Comparative example 3
其余与实施例1相同，除石墨烯纳米片的加入量为2g。The rest was the same as in Example 1, except that the graphene nanosheets were added in an amount of 2 g.
通过实施例1和对比例3可以发现，石墨烯纳米片的加入量太多，其显著地裂化了其绝缘性能，导致其无法用于直流特高压输电线路绝缘器件的制备。It can be found from Example 1 and Comparative Example 3 that the amount of graphene nanosheets added is too large, which significantly cracks its insulating properties, making it unusable for the preparation of DC UHV transmission line insulation devices.
硫化后的胶片经测试耐漏电起痕在直流6.0kv下40min后就破坏，蚀损深度达到3.8mm，拉伸强度3.8MPa，断裂伸长率647％，撕裂强度7.5kN/m，交流击穿强度12kV/mm。After the vulcanized film was tested, the tracking resistance was destroyed after 40 min at DC 6.0 kv, the corrosion depth reached 3.8 mm, the tensile strength was 3.8 MPa, the elongation at break was 647,%, and the tear strength was 7.5 kN/m. Wear strength 12kV/mm.
对比例4Comparative example 4
配比与实施例1相同，但采用如下所述方法制备：The ratio was the same as in Example 1, but was prepared as follows:
将0.0063g石墨烯纳米片(厚度为1nm，长度为100nm，比表面积为1500m2/g)加入20ml去离子水中，常温超声60min，得到分散液；向上述分散液中加入8.97g氧化钙，13.74g硝酸铁和2.6g硝酸铈，均匀搅拌10～30分钟后加入 尿素，回流，将得到的悬浮液用蒸馏水和乙醇反复洗涤，烘干。然后加入5.1g乙烯基三乙氧基硅烷球磨，球磨机转速为200r/min，球磨时间为360min，得到改性的石墨烯/[Ca0.8Fe0.17Ce0.03(OH)2](NO3)0.2·0.1H2O组合物。取其5g加入到95g高温硫化硅橡胶中，并加入2，5-二甲基-2，5-双(叔丁基过氧基)己烷1.5g以及羟基硅油3.5g，混炼出片。0.0063 g of graphene nanosheet (thickness: 1 nm, length: 100 nm, specific surface area: 1500 m 2 /g) was added to 20 ml of deionized water, and ultrasonicated at room temperature for 60 min to obtain a dispersion; 8.97 g of calcium oxide was added to the above dispersion, 13.74 g ferric nitrate and 2.6 g of cerium nitrate, uniformly stirred for 10 to 30 minutes, then added urea, refluxed, and the obtained suspension was repeatedly washed with distilled water and ethanol, and dried. Then, 5.1 g of vinyltriethoxysilane was ball-milled, the ball mill was rotated at 200 r/min, and the ball milling time was 360 min to obtain modified graphene/[Ca 0.8 Fe 0.17 Ce 0.03 (OH) 2 ](NO 3 ) 0.2 · 0.1H 2 O composition. 5 g of this was added to 95 g of high-temperature vulcanized silicone rubber, and 1.5 g of 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane and 3.5 g of hydroxysilicone oil were added, and the mixture was kneaded.
硫化后的胶片经测试耐漏电起痕达到直流6.0kV 6h，蚀损深度2.2mm，拉伸强度2.5MPa，断裂伸长率604％，撕裂强度4.98kN/m，，交流击穿强度20kV/mm。The vulcanized film has been tested for tracking resistance up to 6.0kV for 6h, corrosion depth of 2.2mm, tensile strength of 2.5MPa, elongation at break of 604%, tear strength of 4.98kN/m, and AC breakdown strength of 20kV/ Mm.
对比实施例1和对比例4可以发现，采用本发明的交替球磨的方法得到的产品的各方面的性能均显著地优于采用对比例4的方法。Comparing Example 1 and Comparative Example 4, it was found that the performance of each aspect of the product obtained by the alternate ball milling method of the present invention was remarkably superior to that of Comparative Example 4.
申请人声明，本发明通过上述实施例来说明本发明的详细方法，但本发明并不局限于上述详细方法，即不意味着本发明必须依赖上述详细方法才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。 The Applicant declares that the present invention is described by the above-described embodiments, but the present invention is not limited to the above detailed methods, that is, it does not mean that the present invention must be implemented by the above detailed methods. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitution of the various materials of the products of the present invention, addition of auxiliary components, selection of specific means, and the like, are all within the scope of the present invention.

Claims (10)

  1. 一种用于直流特高压的绝缘组合物，其包括如下组分：An insulating composition for DC UHV, comprising the following components:
    (A)石墨烯纳米片；(A) graphene nanosheets;
    (B)层状复合金属氢氧化物；(B) a layered composite metal hydroxide;
    所述石墨烯纳米片的体积是层状复合金属氢氧化物体积的0.025～0.1vol％。The volume of the graphene nanosheet is 0.025 to 0.1 vol% of the volume of the layered composite metal hydroxide.
  2. 如权利要求1所述的绝缘组合物，其特征在于，所述石墨烯纳米片的体积百分比为0.04～0.085vol％，优选0.045～0.07vol％；The insulating composition according to claim 1, wherein the graphene nanosheet has a volume percentage of 0.04 to 0.085 vol%, preferably 0.045 to 0.07 vol%;
    优选地，所述石墨烯纳米片的厚度为1～20nm，优选5～10nm；长度为100nm～20μm，优选300nm～5μm；比表面积为30～1500m2/g。Preferably, the graphene nanosheet has a thickness of 1 to 20 nm, preferably 5 to 10 nm; a length of 100 nm to 20 μm, preferably 300 nm to 5 μm; and a specific surface area of 30 to 1500 m 2 /g.
  3. 如权利要求1或2所述的绝缘组合物，其特征在于，所述层状复合金属氢氧化物具有如下通式：The insulating composition according to claim 1 or 2, wherein the layered composite metal hydroxide has the following formula:
    [M1a 2+M2b 2+M3c 3+M4d 3+(OH)y]x+(zAn-)·vH2O[M1 a 2+ M2 b 2+ M3 c 3+ M4 d 3+ (OH) y ] x+ (zA n- )·vH 2 O
    其中M1和M2为二价金属阳离子，M1包括Ca2+、Mg2+、Zn2+、Cu2+、Co2+或Ni2+中的任意一种，优选Ca2+、Mg2+或Zn2+中的任意一种；M2包括Ca2+、Mg2+、Zn2+、Cu2+、Co2+或Ni2+中的任意一种，优选Co2+、Ni2+或Cu2+中的任意一种；M3和M4为三价金属阳离子，M3包括Al3+、Cr3+、Fe3+或Ce3+中的任意一种，优选Al3+或Fe3+；M4包括Al3+、Cr3+、Fe3+或Ce3+中的任意一种，优选Cr3+或Ce3+；Wherein M1 and M2 are divalent metal cations, and M1 includes any one of Ca 2+ , Mg 2+ , Zn 2+ , Cu 2+ , Co 2+ or Ni 2+ , preferably Ca 2+ , Mg 2+ or Any one of Zn 2+ ; M2 includes any one of Ca 2+ , Mg 2+ , Zn 2+ , Cu 2+ , Co 2+ or Ni 2+ , preferably Co 2+ , Ni 2+ or Cu Any one of 2+ ; M3 and M4 are trivalent metal cations, and M3 includes any one of Al 3+ , Cr 3+ , Fe 3+ or Ce 3+ , preferably Al 3+ or Fe 3+ ; M4 Including any one of Al 3+ , Cr 3+ , Fe 3+ or Ce 3+ , preferably Cr 3+ or Ce 3+ ;
    a+b等于1-x；c+d等于x，其中，x为(M33++M43+)/(M12++M22++M33++M43+)的摩尔比值，为0.1～0.9，优选0.2～0.8，更优选0.5～0.7；y为1～6，优选2～4；a+b is equal to 1-x; c+d is equal to x, where x is the molar ratio of (M3 3+ +M4 3+ )/(M1 2+ +M2 2+ +M3 3+ +M4 3+ ), 0.1 to 0.9, preferably 0.2 to 0.8, more preferably 0.5 to 0.7; y is 1 to 6, preferably 2 to 4;
    An-代表层间可交换的阴离子，包括硝酸根、硫酸根、乳酸根、氨基酸、氯离子、碳酸根，z为阴离子摩尔数量，n为阴离子价数，其中zn等于[2(a+b)+3(c+d)-y]；v为层间结晶水数量，为0.1～5，优选0.5～3。A n- represents an anion exchangeable between layers, including nitrate, sulfate, lactate, amino acid, chloride, carbonate, z is the molar number of anions, n is the valence of anion, where zn is equal to [2 (a+b) +3(c+d)-y]; v is the amount of water of crystallization between layers, and is 0.1 to 5, preferably 0.5 to 3.
  4. 如权利要求1-3之一所述的绝缘组合物，其特征在于，所述绝缘组合物 还包括(C)偶联剂；The insulating composition according to any one of claims 1 to 3, wherein the insulating composition Also included is (C) a coupling agent;
    优选地，所述偶联剂为硅烷偶联剂；Preferably, the coupling agent is a silane coupling agent;
    优选地，(C)偶联剂与(B)层状复合金属氢氧化物的重量比为1∶5～1∶70，优选1∶9～1∶50，更优选1∶12～1∶45。Preferably, the weight ratio of the (C) coupling agent to the (B) layered composite metal hydroxide is from 1:5 to 1:70, preferably from 1:9 to 1:50, more preferably from 1:12 to 1:45. .
  5. 如权利要求1-4之一所述的绝缘组合物，其特征在于，所述绝缘组合物还包括(D)溶剂；The insulating composition according to any one of claims 1 to 4, wherein the insulating composition further comprises (D) a solvent;
    优选地，本发明所述的(D)溶剂与(B)层状复合金属氢氧化物的重量比为1∶1.25～1∶3，优选1∶1.5～1∶2.5；Preferably, the weight ratio of the (D) solvent to the (B) layered composite metal hydroxide of the present invention is from 1:1.25 to 1:3, preferably from 1:1.5 to 1:2.5;
    优选地，所述溶剂为去离子水。Preferably, the solvent is deionized water.
  6. 一种如权利要求1-5之一所述的用于直流特高压的绝缘组合物的制备方法，包括如下步骤：A method of preparing an insulating composition for DC UHV according to any one of claims 1 to 5, comprising the steps of:
    (I)将石墨烯纳米片加入溶剂中超声分散，然后加入制备层状复合金属氢氧化物的二价和三价金属盐或氧化物，搅拌均匀，然后放入球磨机中湿磨，而后烘干；(I) ultrasonically dispersing the graphene nanosheets in a solvent, then adding the divalent and trivalent metal salts or oxides of the layered composite metal hydroxide, stirring uniformly, then placing them in a ball mill for wet grinding, and then drying ;
    (II)将烘干后得到的物料再放入球磨机中干磨；(II) the material obtained after drying is placed in a ball mill for dry grinding;
    任选地，进行步骤(III)：Optionally, proceeding to step (III):
    (III)加入偶联剂干磨。(III) Drying by adding a coupling agent.
  7. 如权利要求6所述的方法，其特征在于，步骤(I)超声分散的温度为25～45℃，超声分散的时间为20～90min；The method according to claim 6, wherein the step (I) ultrasonic dispersion temperature is 25 to 45 ° C, and the ultrasonic dispersion time is 20 to 90 min;
    优选地，步骤(I)球磨机的转速为200～1000r/min，优选350r/min～800r/min，湿磨时间为200min～660min，优选300min～450min；Preferably, the rotation speed of the step (I) ball mill is 200-1000r/min, preferably 350r/min-800r/min, and the wet-grinding time is 200min-660min, preferably 300min-450min;
    优选地，步骤(II)球磨机转速为200～700r/min，优选350r/min～600r/min，干磨时间为20min～360min，优选30min～240min； Preferably, the step (II) ball mill rotation speed is 200 ~ 700r / min, preferably 350r / min ~ 600r / min, dry grinding time is 20min ~ 360min, preferably 30min ~ 240min;
    优选地，步骤(III)球磨机转速为200r/min～500r/min，优选350r/min～450r/min，球磨时间为20min～360min，优选30min～240min。Preferably, the rotation speed of the ball mill in step (III) is from 200 r/min to 500 r/min, preferably from 350 r/min to 450 r/min, and the ball milling time is from 20 min to 360 min, preferably from 30 min to 240 min.
  8. 一种如权利要求1-5之一所述的用于直流特高压的绝缘组合物的用途，其用于直流特高压输电线路绝缘器件的制备。Use of an insulating composition for DC UHV according to any one of claims 1 to 5 for the preparation of a DC UHV transmission line insulation device.
  9. 一种用于直流特高压的绝缘复合材料，其含有如权利要求1-5之一所述的用于直流特高压的绝缘组合物以及聚合物基体。An insulating composite material for a DC UHV, comprising the insulating composition for DC UHV according to any one of claims 1 to 5 and a polymer matrix.
  10. 如权利要求9所述的绝缘复合材料，其特征在于，所述用于直流特高压的绝缘组合物的质量占用于直流特高压的绝缘组合物和聚合物基体质量总和的5～30％；The insulating composite material according to claim 9, wherein the insulating composition for DC ultrahigh voltage accounts for 5 to 30% of the total mass of the insulating composition for the DC UHV and the polymer matrix;
    优选地，所述聚合物基体为硅橡胶、环氧树脂、聚乙烯或聚四氟乙烯中的任意一种或者至少两种的混合物。 Preferably, the polymer matrix is any one of silicone rubber, epoxy resin, polyethylene or polytetrafluoroethylene or a mixture of at least two.
PCT/CN2015/092063 2015-06-24 2015-10-16 Insulation composition for direct-current ultrahigh voltage, preparation method, and uses thereof WO2016206242A1 (en)

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