WO2022242026A1 - Cross-linked polyethylene composite material, and preparation method therefor and application thereof - Google Patents

Cross-linked polyethylene composite material, and preparation method therefor and application thereof Download PDF

Info

Publication number
WO2022242026A1
WO2022242026A1 PCT/CN2021/125265 CN2021125265W WO2022242026A1 WO 2022242026 A1 WO2022242026 A1 WO 2022242026A1 CN 2021125265 W CN2021125265 W CN 2021125265W WO 2022242026 A1 WO2022242026 A1 WO 2022242026A1
Authority
WO
WIPO (PCT)
Prior art keywords
boron nitride
cross
composite material
linked polyethylene
polyethylene composite
Prior art date
Application number
PCT/CN2021/125265
Other languages
French (fr)
Chinese (zh)
Inventor
朱闻博
黎小林
傅明利
侯帅
惠宝军
冯宾
张逸凡
伍国兴
谢宏
徐曙
陈潇
Original Assignee
南方电网科学研究院有限责任公司
深圳供电局有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 南方电网科学研究院有限责任公司, 深圳供电局有限公司 filed Critical 南方电网科学研究院有限责任公司
Publication of WO2022242026A1 publication Critical patent/WO2022242026A1/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • 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
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
    • 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
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking

Definitions

  • the invention relates to the technical field of high-voltage AC cable insulation, in particular to a cross-linked polyethylene composite material and its preparation method and application.
  • cross-linked polyethylene Compared with polyethylene (PE), cross-linked polyethylene (XLPE) has a three-dimensional network macromolecular structure, its mechanical properties and environmental stress cracking resistance are significantly improved, and the long-term working temperature of the material is increased from 70°C to 90°C.
  • the formulation of high voltage cable insulation material is mainly composed of PE base resin, crosslinking agent and antioxidant.
  • cross-linked polyethylene insulating materials are inevitably exposed to high-temperature environments during production and use, and are prone to aging under the action of heat and oxygen, thereby affecting their electrical properties, mechanical properties and thermal stability, and reducing cable life.
  • Nano-polymers have excellent physical and chemical properties, which can improve the charge transport regulation ability and breakdown field strength of insulating media, and have become a hot spot in the research field of high-voltage insulating materials.
  • nanoparticles can bind the movement of surrounding polymer molecular chains through "entanglement” and other forms, and have a "pinning” effect that can inhibit the crack propagation process.
  • the interaction between the matrix and nanoparticles can change the arrangement of polymer molecular chains and regulate its glass transition temperature.
  • Functionalized nanoparticles such as cage-type silsesquioxane (POSS)
  • PES cage-type silsesquioxane
  • Blending thermally conductive and insulating inorganic fillers into the insulating matrix, and replacing the relatively disordered low thermal conductivity matrix with ordered lattice particles with high thermal conductivity, can significantly improve the thermal conductivity of the composite system, making the new composite material also have better insulation and thermal conductivity.
  • the commonly used inorganic heat-conducting particles mainly include boron nitride, aluminum nitride, silicon nitride and other nitrides.
  • the formation of thermal conduction paths inside the matrix is the decisive factor to improve the thermal conductivity of composite materials, and the distribution state of inorganic particles is very critical. Filling with particles of different types, particle sizes, and shapes, and treating the surface of the particles are all in order to form an effective heat conduction path in the matrix to the greatest extent and improve the thermal conductivity of the material.
  • the purpose of the present invention is to overcome the deficiencies of the prior art, improve the high-voltage AC breakdown resistance of the cross-linked polyethylene composite material, and propose a cross-linked polyethylene composite material and its preparation method and application. Experiments have proved that the composite material can Effectively increase the current carrying capacity and insulation breakdown field strength of high-voltage AC cables.
  • the technical solution adopted by the present invention is: a cross-linked polyethylene composite material, characterized in that it includes the following components in parts by mass: 100 parts of low-density polyethylene, 1.8-2 parts of cross-linking agent, 0.3 -0.5 parts of co-crosslinking agent, 2-4 parts of nano vinyl cage polysilsesquioxane and 30-40 parts of boron nitride; It is composed of nano-scale boron nitride, and the mass ratio of the micron-scale boron nitride to the nano-scale boronitride is 2-6:1.
  • the cross-linked polyethylene composite material of the invention uses nano vinyl cage polysilsesquioxane and boron nitride as additives, which can effectively improve the high-voltage AC breakdown resistance of the cross-linked polyethylene composite material.
  • Boron nitride is an insulator, and the addition of boron nitride will redistribute the space charge in the cross-linked polyethylene composite, which will lead to electric field homogenization and reduce the free volume of the cross-linked polyethylene composite. Boron has a certain blocking effect on the injection of charges and the transport of injected charges.
  • the content of boron nitride will also affect the breakdown field strength of cross-linked polyethylene composites. When the content is high, boron nitride is difficult to distribute uniformly in low-density polyethylene, thus affecting the breakdown performance of composites.
  • the mass ratio of the boron nitride with a micron-scale particle size to the boron nitride with a nano-scale particle size is 3 to 6:1.
  • the prepared cross-linked polyethylene composites have higher insulation breakdown field strength. More preferably, the particle size is that the mass ratio of micron-scale boron nitride and nano-scale boron nitride is 3:1, and the cross-linked polyethylene composite material prepared under the above ratio has the best insulation breakdown field strength.
  • the boron nitride is hexagonal boron nitride with a purity >99.1%.
  • the average median particle size of the micron-sized boron nitride is 5-15 ⁇ m; the particle size is nano-sized boron nitride.
  • the average median particle size is 40-60nm.
  • the distribution of boron nitride with different particle sizes in the cross-linked polyethylene composite material is different, and its arrangement is also different, and the blocking effect on charge injection and injected charge transport is different. Improve the breakdown field strength of composite materials.
  • the density of the low-density polyethylene is ⁇ 0.9230g/cm 3
  • the gel content is ⁇ 82%
  • the low-density polyethylene is 2.16kg at 190°C.
  • the melt mass flow rate under load was 0.9-2.1 g/10 min.
  • the cross-linking agent is dicumyl peroxide or ethylene peroxide.
  • the present invention uses dicumyl peroxide or ethylene peroxide as a cross-linking agent to form a three-dimensional network structure through cross-linking between polyethylene molecular chains and molecular chains.
  • the decomposition temperature is lower than the degradation temperature of polyethylene, thereby avoiding the degradation of polyethylene in the crosslinking process, and can effectively prevent the pre-crosslinking phenomenon of crosslinked polyethylene.
  • the auxiliary cross-linking agent is triallyl cyanurate, triallyl isocyanurate, trimethylolpropane three One of the methacrylates.
  • the melting point of the nano vinyl cage polysilsesquioxane is >350°C, and the flash point is >200°C.
  • the cross-linked polyethylene composite material further includes 0.2-0.3 parts by mass of an antioxidant.
  • the antioxidant is one of antioxidant 1010, antioxidant 1035, antioxidant 300, and antioxidant 1076.
  • the present invention also provides a kind of preparation method of cross-linked polyethylene composite material, comprises the following steps:
  • step (2) Add dried low-density polyethylene, antioxidant, crosslinking agent, co-crosslinking agent, nano vinyl cage polysilsesquioxane and surface-treated boron nitride obtained in step (1) In a mixer, mix thoroughly;
  • step (3) Preheat the mixture obtained in step (2) with a vulcanizer to fully melt the mixture, pressurize the vulcanizer to 30-50MPa, raise the temperature to 165-185°C, press the fully melted mixture for 30-60min, and then maintain the pressure Cool to room temperature without changing, and then dry to obtain the cross-linked polyethylene composite material.
  • silane coupling agent in the present invention can effectively enhance the compatibility between boron nitride and low-density polyethylene, because the silane coupling agent can react with the hydroxyl groups on the surface of boron nitride, thereby covering a layer of silane layer on the surface of boron nitride, Effectively prevent the agglomeration of boron nitride and improve the dispersion of boron nitride. Drying at the end removes impurities from the cross-linked polyethylene composite.
  • the volume ratio of ethanol and water in the alcohol aqueous solution in the step (1) is 95:5; the mass of silane coupling agent and boron nitride The ratio is 1:100.
  • the present invention also provides an application of a cross-linked polyethylene composite material in a high-voltage AC cable.
  • the beneficial effects of the present invention are: the cross-linked polyethylene composite material of the present invention uses nano-vinyl cage polysilsesquioxane and boron nitride as additives, which can effectively improve the cross-linking efficiency.
  • the high-voltage AC breakdown resistance of polyethylene composite materials is of great significance for improving the operating voltage of domestic AC cable materials and the safe and stable operation of high-voltage AC cables.
  • Fig. 1 is the boron nitride surface treatment process
  • Fig. 2 is the Weibull distribution diagram of the exchange breakdown field strength of embodiment 1 ⁇ 7 gained cross-linked polyethylene composite material
  • Fig. 3 is a Weibull distribution diagram of the AC breakdown field strength of the cross-linked polyethylene composite material obtained in Example 9.
  • This embodiment provides a cross-linked polyethylene composite material, comprising the following components in parts by mass: 100 parts of low-density polyethylene, 1.8 parts of dicumyl peroxide, 0.4 parts of triallyl cyanurate, 0.2 parts of antioxidant 1010, 3 parts of nanometer vinyl cage polysilsesquioxane and 30 parts of boron nitride; Boron nitride composition, the mass ratio of boron nitride with a particle size of micron and boron nitride with a particle size of nanometer is 3:1.
  • boron nitride is hexagonal boron nitride, and the average median particle diameter of micron-scale boron nitride is 10 ⁇ m; the average median particle diameter of nanometer-scale boron nitride is 50 nm.
  • the purity is 99.1%; the density of low-density polyethylene is 0.9210g/cm 3 , the melt flow rate is 1.5g/10min, and the gel content is 86%; the melting point of nano vinyl cage polysilsesquioxane is 360 °C, the flash point is 210 °C.
  • This embodiment also provides a preparation method of cross-linked polyethylene composite material, comprising the following steps:
  • step (3) Weigh 50g of the mixture obtained in step (2), place it in a flat vulcanizer, preheat it at 120°C for 15 minutes, and fully melt the mixture; after that, pressurize the flat vulcanizer to 30MPa, and raise the temperature to 185°C at the same time, press 45min, then turn off the power supply of the flat vulcanizer, keep the pressure constant, let the sample cool down to room temperature naturally, then place the sample in a vacuum drying oven at 80°C, and dry it in vacuum for 48h to obtain the cross-linked polyethylene composite material , the obtained cross-linked polyethylene composite material has a side length of 80mm ⁇ 80mm and a thickness of 2mm.
  • This embodiment provides a cross-linked polyethylene composite material, comprising the following components by mass: 100 parts of low-density polyethylene, 1.9 parts of ethylene peroxide, 0.3 parts of triallyl isocyanurate, 0.25 parts Parts of antioxidant 1035, 2 parts of nano vinyl cage polysilsesquioxane and 35 parts of boron nitride;
  • the composition of boron, the mass ratio of boron nitride with a particle size of micron and boron nitride with a particle size of nanometer is 4:1.
  • boron nitride is hexagonal boron nitride, and the average median particle diameter of micrometer-sized boron nitride is 5 ⁇ m; the average median particle diameter of nanometer-sized boron nitride is 40 nm,
  • the purity is 99.1%; the density of low-density polyethylene is 0.9220g/cm 3 , the melt flow rate is 0.9g/10min, and the gel content is 84%; the melting point of nano vinyl cage polysilsesquioxane is 355 °C, the flash point is 205 °C.
  • This embodiment also provides a preparation method of cross-linked polyethylene composite material, comprising the following steps:
  • step (3) Weigh 50g of the mixture obtained in step (2), place it in a flat vulcanizer, preheat it at 120°C for 15 minutes, and fully melt the mixture; after that, pressurize the flat vulcanizer to 40MPa, and raise the temperature to 175°C at the same time, press 30min, then turn off the power supply of the flat vulcanizer, keep the pressure constant, let the sample cool down to room temperature naturally, then place the sample in a vacuum drying oven at 80°C, and dry it in vacuum for 48h to obtain the cross-linked polyethylene composite material , the side length of the obtained cross-linked polyethylene composite material is 80mm ⁇ 80mm, and the thickness is 2.2mm.
  • This embodiment provides a cross-linked polyethylene composite material, comprising the following components in parts by mass: 100 parts of low-density polyethylene, 2 parts of dicumyl peroxide, 0.5 part of trimethylolpropane trimethacrylate , 0.3 parts of antioxidant 300, 4 parts of nano vinyl cage polysilsesquioxane and 40 parts of boron nitride;
  • the composition of boron nitride, the mass ratio of boron nitride with a particle size of micron and boron nitride with a particle size of nanometer is 6:1.
  • boron nitride is hexagonal boron nitride, and the average median particle diameter of micron-scale boron nitride is 15 ⁇ m; the average median particle diameter of nanometer-scale boron nitride is 60 nm.
  • the purity is 99.1%; the density of low-density polyethylene is 0.9230g/cm 3 , the melt flow rate is 2.1g/10min, and the gel content is 82%; the melting point of nano vinyl cage polysilsesquioxane is 350 °C, and the flash point is 200 °C.
  • This embodiment also provides a preparation method of cross-linked polyethylene composite material, comprising the following steps:
  • step (3) Weigh 50g of the mixture obtained in step (2), place it in a flat vulcanizer, preheat it at 120°C for 15 minutes, and fully melt the mixture; after that, pressurize the flat vulcanizer to 50MPa, and simultaneously raise the temperature to 165°C, press 60min, then turn off the power supply of the flat vulcanizer, keep the pressure constant, let the sample cool down to room temperature naturally, then place the sample in a vacuum drying oven at 80°C, and vacuum dry for 48h to obtain the cross-linked polyethylene composite material , the side length of the obtained cross-linked polyethylene composite material is 80mm ⁇ 80mm, and the thickness is 1.8mm.
  • This embodiment provides a cross-linked polyethylene composite material, comprising the following components in parts by mass: 100 parts of low-density polyethylene, 1.8 parts of dicumyl peroxide, 0.4 parts of triallyl cyanurate, 0.2 parts of antioxidant 1076, 3 parts of nano vinyl cage polysilsesquioxane and 30 parts of boron nitride; Boron nitride composition, the mass ratio of boron nitride with a particle size of micron and boron nitride with a particle size of nanometer is 2:1.
  • boron nitride is hexagonal boron nitride, and the average median particle diameter of micron-scale boron nitride is 10 ⁇ m; the average median particle diameter of nanometer-scale boron nitride is 50 nm.
  • the purity is 99.1%; the density of low-density polyethylene is 0.9210g/cm 3 , the melt flow rate is 1.5g/10min, and the gel content is 86%; the melting point of nano vinyl cage polysilsesquioxane is 360 °C, the flash point is 210 °C.
  • This embodiment also provides a preparation method of cross-linked polyethylene composite material, comprising the following steps:
  • step (3) Weigh 50g of the mixture obtained in step (2), place it in a flat vulcanizer, preheat it at 120°C for 15 minutes, and fully melt the mixture; after that, pressurize the flat vulcanizer to 30MPa, and raise the temperature to 185°C at the same time, press 45min, then turn off the power supply of the flat vulcanizer, keep the pressure constant, let the sample cool down to room temperature naturally, then place the sample in a vacuum drying oven at 80°C, and dry it in vacuum for 48h to obtain the cross-linked polyethylene composite material , the obtained cross-linked polyethylene composite material has a side length of 80mm ⁇ 80mm and a thickness of 2.1mm.
  • This embodiment provides a cross-linked polyethylene composite material, comprising the following components in parts by mass: 100 parts of low-density polyethylene, 1.8 parts of dicumyl peroxide, 0.4 parts of triallyl cyanurate, 0.2 parts of antioxidant 1010, 1 part of nanometer vinyl cage polysilsesquioxane and 25 parts of boron nitride; Boron nitride composition, the mass ratio of boron nitride with a particle size of micron and boron nitride with a particle size of nanometer is 3:1.
  • boron nitride is hexagonal boron nitride, and the average median particle diameter of micron-scale boron nitride is 10 ⁇ m; the average median particle diameter of nanometer-scale boron nitride is 50 nm.
  • the purity is 99.1%; the density of low-density polyethylene is 0.9210g/cm 3 , the melt flow rate is 1.5g/10min, and the gel content is 86%; the melting point of nano vinyl cage polysilsesquioxane is 360 °C, the flash point is 210 °C.
  • This embodiment also provides a preparation method of cross-linked polyethylene composite material, comprising the following steps:
  • step (3) Weigh 50g of the mixture obtained in step (2), place it in a flat vulcanizer, preheat it at 120°C for 15 minutes, and fully melt the mixture; after that, pressurize the flat vulcanizer to 30MPa, and raise the temperature to 185°C at the same time, press 45min, then turn off the power supply of the flat vulcanizer, keep the pressure constant, let the sample cool down to room temperature naturally, then place the sample in a vacuum drying oven at 80°C, and dry it in vacuum for 48h to obtain the cross-linked polyethylene composite material , the obtained cross-linked polyethylene composite material has a side length of 80mm ⁇ 80mm and a thickness of 2mm.
  • This embodiment provides a cross-linked polyethylene composite material, comprising the following components in parts by mass: 100 parts of low-density polyethylene, 1.8 parts of dicumyl peroxide, 0.4 parts of triallyl cyanurate, 0.2 parts of antioxidant 1010, 5 parts of nanometer vinyl cage polysilsesquioxane and 45 parts of boron nitride; Boron nitride composition, the mass ratio of boron nitride with a particle size of micron and boron nitride with a particle size of nanometer is 3:1.
  • boron nitride is hexagonal boron nitride, and the average median particle diameter of micron-scale boron nitride is 10 ⁇ m; the average median particle diameter of nanometer-scale boron nitride is 50 nm.
  • the purity is 99.1%; the density of low-density polyethylene is 0.9210g/cm 3 , the melt flow rate is 1.5g/10min, and the gel content is 86%; the melting point of nano vinyl cage polysilsesquioxane is 360 °C, the flash point is 210 °C.
  • This embodiment also provides a preparation method of cross-linked polyethylene composite material, comprising the following steps:
  • step (3) Weigh 50g of the mixture obtained in step (2), place it in a flat vulcanizer, preheat it at 120°C for 15 minutes, and fully melt the mixture; after that, pressurize the flat vulcanizer to 30MPa, and raise the temperature to 185°C at the same time, press 45min, then turn off the power supply of the flat vulcanizer, keep the pressure constant, let the sample cool down to room temperature naturally, then place the sample in a vacuum drying oven at 80°C, and dry it in vacuum for 48h to obtain the cross-linked polyethylene composite material , the obtained cross-linked polyethylene composite material has a side length of 80mm ⁇ 80mm and a thickness of 2mm.
  • This embodiment provides a cross-linked polyethylene composite material, comprising the following components in parts by mass: 100 parts of low-density polyethylene, 1.8 parts of dicumyl peroxide, 0.4 parts of triallyl cyanurate, 0.2 parts Antioxidant 1010.
  • the low density polyethylene has a density of 0.9210g/cm 3 , a melt flow rate of 1.5g/10min and a gel content of 86%.
  • This embodiment also provides a preparation method of cross-linked polyethylene composite material, comprising the following steps:
  • step (2) Weigh 50g of the mixture obtained in step (1), place it in a flat vulcanizer, preheat it at 120°C for 15 minutes, and fully melt the mixture; after that, pressurize the flat vulcanizer to 30MPa, and raise the temperature to 185°C at the same time, press 45min, then turn off the power supply of the flat vulcanizer, keep the pressure constant, let the sample cool down to room temperature naturally, then place the sample in a vacuum drying oven at 80°C, and dry it in vacuum for 48h to obtain the cross-linked polyethylene composite material , the obtained cross-linked polyethylene composite material has a side length of 80mm ⁇ 80mm and a thickness of 2mm.
  • Test method test the breakdown voltage of the cross-linked polyethylene composite material obtained in Examples 1 to 7 at a boosting speed of 1 kV/s.
  • Fig. 2 is a Weibull distribution diagram of the AC breakdown field strength of the cross-linked polyethylene composite material obtained in Examples 1 to 7. It can be seen from Figure 2 that under the same probability, the breakdown field strengths of the composite materials obtained in Examples 1-4 are all above 49kV/mm, compared with the breakdown field strength of the pure cross-linked polyethylene material in Example 7 The field strength has been increased by 1.69 times. The changed additive content of Examples 5 and 6 is not within the scope of the present invention, resulting in a decrease in the breakdown field strength compared to Examples 1-4, which shows that the technical solution of the present invention can effectively improve the crossover field strength.
  • the breakdown field strength of linked polyethylene is not within the scope of the present invention, resulting in a decrease in the breakdown field strength compared to Examples 1-4, which shows that the technical solution of the present invention can effectively improve the crossover field strength.
  • the breakdown field strength of linked polyethylene is not within the scope of the present invention, resulting in a decrease in the breakdown field strength compared to Examples 1-4, which shows that the technical solution of
  • This embodiment further studies the mass ratio of boron nitride with micron-scale particle size and nano-scale boron nitride particle size in boron nitride to the high-voltage AC cable ampacity and insulation breakdown of the cross-linked polyethylene composite material of the present invention The influence of field strength.
  • the test method is as described in Example 8.
  • test groups a to g are set, and the formula of each group only changes the mass ratio of boron nitride with a particle size of micron scale and boron nitride with a particle size of nanoscale.
  • Table 1 the other components and preparation method of the cross-linked polyethylene composite material in this example are the same as those in Example 1.
  • the test results are shown in Figure 3.
  • Fig. 2 is a Weibull distribution diagram of the AC breakdown field strength of the cross-linked polyethylene composite material obtained in Examples 1 to 7. It can be seen from Fig. 3 that among the 7 test groups, the breakdown field strength of composite materials in groups c to f is the highest, all above 50kV/mm, while groups a, b and g are not within the scope of the present invention due to changes in the mass ratio. As a result, the breakdown field strength decreased compared with groups c to f, indicating that the technical solution of the present invention can effectively improve the breakdown field strength of cross-linked polyethylene.

Abstract

A cross-linked polyethylene composite material, and a preparation method therefor and an application thereof, relating to the technical field of high-voltage alternating-current cable insulation. The cross-linked polyethylene composite material comprises the following components in parts by mass: 100 parts of low-density polyethylene, 1.8 to 2 parts of a cross-linking agent, 0.3 to 0.5 parts of an auxiliary cross-linking agent, 0.2 to 0.3 parts of an antioxidant, 2 to 4 parts of nano vinyl polyhedral oligomeric silsesquioxane, and 30 to 40 parts of boron nitride; the boron nitride consists of boron nitride having a micron-scale particle size and boron nitride having a nano-scale particle size, and the mass ratio of the boron nitride having a micron-scale particle size to the boron nitride having a nano-scale particle size is 2 to 6:1.In the cross-linked polyethylene composite material, nano vinyl polyhedral oligomeric silsesquioxane and boron nitride are used as additives, so that the insulation and high-voltage alternating-current breakdown resistance capability of the cross-linked polyethylene composite material can be effectively improved.

Description

一种交联聚乙烯复合材料及其制备方法与应用A kind of cross-linked polyethylene composite material and its preparation method and application 技术领域technical field
本发明涉及高压交流电缆绝缘技术领域，尤其涉及一种交联聚乙烯复合材料及其制备方法与应用。The invention relates to the technical field of high-voltage AC cable insulation, in particular to a cross-linked polyethylene composite material and its preparation method and application.
背景技术Background technique
近年来，我国城市化进程不断推进，城市用电需求不断增加，电缆输电电压等级由110kV、220kV向500kV发展，高压电缆输电线路年平均增长率高达13％，电缆行业发展前景广阔。交联聚乙烯(XLPE)相比油纸绝缘在电力电缆中应用具有显著优势。目前国际上从35kV中低压电缆到110kV以上高压电缆都倾向于用XLPE作为主绝缘。相比于聚乙烯(PE)，交联聚乙烯(XLPE)具有三维网状大分子结构，其机械性能和耐环境应力开裂性显著提高，材料长期工作温度由70℃提高到90℃。高压电缆绝缘料配方主要由PE基础树脂、交联剂和抗氧剂构成。此外，交联聚乙烯绝缘材料在生产和使用过程中均不可避免地处于高温环境中，极易在热和氧的作用下发生老化，从而影响其电学性能、力学性能和热稳定性，并降低电缆使用寿命。In recent years, my country's urbanization process has continued to advance, urban electricity demand has continued to increase, cable transmission voltage levels have developed from 110kV, 220kV to 500kV, and the average annual growth rate of high-voltage cable transmission lines has reached 13%. The cable industry has broad prospects for development. Compared with oil-paper insulation, cross-linked polyethylene (XLPE) has significant advantages in the application of power cables. At present, XLPE tends to be used as the main insulation in the world from 35kV medium and low voltage cables to 110kV and above high voltage cables. Compared with polyethylene (PE), cross-linked polyethylene (XLPE) has a three-dimensional network macromolecular structure, its mechanical properties and environmental stress cracking resistance are significantly improved, and the long-term working temperature of the material is increased from 70°C to 90°C. The formulation of high voltage cable insulation material is mainly composed of PE base resin, crosslinking agent and antioxidant. In addition, cross-linked polyethylene insulating materials are inevitably exposed to high-temperature environments during production and use, and are prone to aging under the action of heat and oxygen, thereby affecting their electrical properties, mechanical properties and thermal stability, and reducing cable life.
纳米聚合物具有优异的物理、化学性能，可以提高绝缘介质电荷输运调控能力和击穿场强，已成为高电压绝缘材料研究领域的关注热点。一方面，纳米粒子可以通过“缠结”等形式束缚周围聚合物分子链运动，具有“钉扎”作用能够抑制裂纹扩展过程。另一方面，基体与纳米粒子相互作用可以改变聚合物分子链的排列方式，调控其玻璃态转化温度。功能化纳米粒子例如笼型倍半硅氧烷(POSS)等，既能发挥“纳米效应”，又可提高分散性、相容性等，实现纳米粒子功能化，进而大幅提高聚合物的机械性能、热稳定性、电气性能等。Nano-polymers have excellent physical and chemical properties, which can improve the charge transport regulation ability and breakdown field strength of insulating media, and have become a hot spot in the research field of high-voltage insulating materials. On the one hand, nanoparticles can bind the movement of surrounding polymer molecular chains through "entanglement" and other forms, and have a "pinning" effect that can inhibit the crack propagation process. On the other hand, the interaction between the matrix and nanoparticles can change the arrangement of polymer molecular chains and regulate its glass transition temperature. Functionalized nanoparticles, such as cage-type silsesquioxane (POSS), can not only exert the "nano effect", but also improve dispersion, compatibility, etc., realize the functionalization of nanoparticles, and greatly improve the mechanical properties of polymers , thermal stability, electrical properties, etc.
将导热绝缘无机填料掺混到绝缘基体中，用高热导率有序晶格颗粒替代相对无序低热导率基体，可显著改善复合体系的导热性能，使新型的复合材料同时具有较好的绝缘和导热性能。目前常用的无机导热颗粒主要有氮化硼、氮化 铝、氮化硅等氮化物。在基体内部形成导热通路是提高复合材料热导率的决定性因素，无机颗粒的分布状态非常关键。使用不同种类、粒径、形状的颗粒填充，对颗粒表面进行处理处理等手段都是为了最大程度的在基体内形成有效的导热通路而提高材料热导率。Blending thermally conductive and insulating inorganic fillers into the insulating matrix, and replacing the relatively disordered low thermal conductivity matrix with ordered lattice particles with high thermal conductivity, can significantly improve the thermal conductivity of the composite system, making the new composite material also have better insulation and thermal conductivity. At present, the commonly used inorganic heat-conducting particles mainly include boron nitride, aluminum nitride, silicon nitride and other nitrides. The formation of thermal conduction paths inside the matrix is the decisive factor to improve the thermal conductivity of composite materials, and the distribution state of inorganic particles is very critical. Filling with particles of different types, particle sizes, and shapes, and treating the surface of the particles are all in order to form an effective heat conduction path in the matrix to the greatest extent and improve the thermal conductivity of the material.
发明内容Contents of the invention
本发明的目的在于克服现有技术的不足，改善交联聚乙烯复合材料的耐高压交流击穿能力，提出一种交联聚乙烯复合材料及其制备方法与应用，实验证明，该复合材料可以有效提升高压交流电缆的载流量和绝缘击穿场强。The purpose of the present invention is to overcome the deficiencies of the prior art, improve the high-voltage AC breakdown resistance of the cross-linked polyethylene composite material, and propose a cross-linked polyethylene composite material and its preparation method and application. Experiments have proved that the composite material can Effectively increase the current carrying capacity and insulation breakdown field strength of high-voltage AC cables.
为实现上述目的，本发明采取的技术方案为：一种交联聚乙烯复合材料，其特征在于，包括以下质量份的组分：100份低密度聚乙烯、1.8-2份交联剂、0.3-0.5份助交联剂、2-4份纳米乙烯基笼型聚倍半硅氧烷和30-40份氮化硼；所述氮化硼由粒径为微米级的氮化硼和粒径为纳米级的氮化硼组成，所述粒径为微米级的氮化硼和粒径为纳米级的氮化硼的质量比为2～6:1。In order to achieve the above object, the technical solution adopted by the present invention is: a cross-linked polyethylene composite material, characterized in that it includes the following components in parts by mass: 100 parts of low-density polyethylene, 1.8-2 parts of cross-linking agent, 0.3 -0.5 parts of co-crosslinking agent, 2-4 parts of nano vinyl cage polysilsesquioxane and 30-40 parts of boron nitride; It is composed of nano-scale boron nitride, and the mass ratio of the micron-scale boron nitride to the nano-scale boron nitride is 2-6:1.
本发明所述一种交联聚乙烯复合材料以纳米乙烯基笼型聚倍半硅氧烷和氮化硼为添加剂，可以有效提高交联聚乙烯复合材料的耐高压交流击穿能力。氮化硼是一种绝缘体，添加氮化硼会使交联聚乙烯复合材料中的空间电荷重新分布，从而会导致电场均化，并且降低了交联聚乙烯复合材料的自由体积，同时氮化硼对电荷的注入和注入电荷的传输具有一定的阻挡作用。氮化硼的含量也会对交联聚乙烯复合材料的击穿场强有影响，含量较高时，氮化硼难以均匀分布在低密度聚乙烯中，从而影响了复合材料的击穿性能。The cross-linked polyethylene composite material of the invention uses nano vinyl cage polysilsesquioxane and boron nitride as additives, which can effectively improve the high-voltage AC breakdown resistance of the cross-linked polyethylene composite material. Boron nitride is an insulator, and the addition of boron nitride will redistribute the space charge in the cross-linked polyethylene composite, which will lead to electric field homogenization and reduce the free volume of the cross-linked polyethylene composite. Boron has a certain blocking effect on the injection of charges and the transport of injected charges. The content of boron nitride will also affect the breakdown field strength of cross-linked polyethylene composites. When the content is high, boron nitride is difficult to distribute uniformly in low-density polyethylene, thus affecting the breakdown performance of composites.
作为本发明所述交联聚乙烯复合材料的优选实施方式，所述粒径为微米级的氮化硼和粒径为纳米级的氮化硼的质量比为3～6:1，上述比例下制备的交联聚乙烯复合材料具有更高的绝缘击穿场强。更优选的，所述粒径为微米级的氮化硼和粒径为纳米级的氮化硼的质量比为3:1，在上述比例下制备的交联聚乙烯复合材料具有最佳的绝缘击穿场强。As a preferred embodiment of the cross-linked polyethylene composite material of the present invention, the mass ratio of the boron nitride with a micron-scale particle size to the boron nitride with a nano-scale particle size is 3 to 6:1. The prepared cross-linked polyethylene composites have higher insulation breakdown field strength. More preferably, the particle size is that the mass ratio of micron-scale boron nitride and nano-scale boron nitride is 3:1, and the cross-linked polyethylene composite material prepared under the above ratio has the best insulation breakdown field strength.
作为本发明所述交联聚乙烯复合材料的优选实施方式，所述氮化硼为六方氮化硼，纯度>99.1％。As a preferred embodiment of the cross-linked polyethylene composite material in the present invention, the boron nitride is hexagonal boron nitride with a purity >99.1%.
作为本发明所述交联聚乙烯复合材料的优选实施方式，所述粒径为微米级的氮化硼的平均中位粒径为5～15μm；所述粒径为纳米级的氮化硼的平均中位粒径为40～60nm。As a preferred embodiment of the cross-linked polyethylene composite material in the present invention, the average median particle size of the micron-sized boron nitride is 5-15 μm; the particle size is nano-sized boron nitride. The average median particle size is 40-60nm.
不同粒径的氮化硼在交联聚乙烯复合材料的分布不同，其排列方式也不同，对电荷的注入和注入电荷传输的阻挡作用不同，发明人发现上述粒径的氮化硼能够较好的提高复合材料的击穿场强。The distribution of boron nitride with different particle sizes in the cross-linked polyethylene composite material is different, and its arrangement is also different, and the blocking effect on charge injection and injected charge transport is different. Improve the breakdown field strength of composite materials.
作为本发明所述交联聚乙烯复合材料的优选实施方式，所述低密度聚乙烯的密度<0.9230g/cm 3，凝胶含量≥82％，所述低密度聚乙烯在190℃，2.16kg负荷下的熔体质量流动速率为0.9-2.1g/10min。 As a preferred embodiment of the cross-linked polyethylene composite material of the present invention, the density of the low-density polyethylene is <0.9230g/cm 3 , the gel content is ≥82%, and the low-density polyethylene is 2.16kg at 190°C. The melt mass flow rate under load was 0.9-2.1 g/10 min.
作为本发明所述交联聚乙烯复合材料的优选实施方式，所述交联剂为过氧化二异丙苯或过氧化乙烷。As a preferred embodiment of the cross-linked polyethylene composite material in the present invention, the cross-linking agent is dicumyl peroxide or ethylene peroxide.
本发明使用过氧化二异丙苯或过氧化乙烷作为交联剂，使聚乙烯分子链与分子链之间通过交联形成三维网状结构，过氧化二异丙苯或过氧化乙烷的分解温度低于聚乙烯的降解温度，从而避免了聚乙烯交联过程中降解的情况，并且能够有效的防止交联聚乙烯的预交联现象。The present invention uses dicumyl peroxide or ethylene peroxide as a cross-linking agent to form a three-dimensional network structure through cross-linking between polyethylene molecular chains and molecular chains. The decomposition temperature is lower than the degradation temperature of polyethylene, thereby avoiding the degradation of polyethylene in the crosslinking process, and can effectively prevent the pre-crosslinking phenomenon of crosslinked polyethylene.
作为本发明所述交联聚乙烯复合材料的优选实施方式，所述助交联剂为三烯丙基三聚氰酸酯、三烯丙基异三聚氰酸酯、三羟甲基丙烷三甲基丙烯酸酯中的一种。As a preferred embodiment of the cross-linked polyethylene composite material of the present invention, the auxiliary cross-linking agent is triallyl cyanurate, triallyl isocyanurate, trimethylolpropane three One of the methacrylates.
作为本发明所述交联聚乙烯复合材料的优选实施方式，所述纳米乙烯基笼型聚倍半硅氧烷的熔点>350℃，闪点>200℃。As a preferred embodiment of the cross-linked polyethylene composite material of the present invention, the melting point of the nano vinyl cage polysilsesquioxane is >350°C, and the flash point is >200°C.
作为本发明所述交联聚乙烯复合材料的优选实施方式，所述交联聚乙烯复合材料还包括0.2-0.3质量份抗氧剂。As a preferred embodiment of the cross-linked polyethylene composite material in the present invention, the cross-linked polyethylene composite material further includes 0.2-0.3 parts by mass of an antioxidant.
作为本发明所述交联聚乙烯复合材料的优选实施方式，所述抗氧剂为抗氧剂1010、抗氧剂1035、抗氧剂300、抗氧剂1076的一种。As a preferred embodiment of the cross-linked polyethylene composite material of the present invention, the antioxidant is one of antioxidant 1010, antioxidant 1035, antioxidant 300, and antioxidant 1076.
第二方面，本发明还提供了一种交联聚乙烯复合材料的制备方法，包括以 下步骤：Second aspect, the present invention also provides a kind of preparation method of cross-linked polyethylene composite material, comprises the following steps:
(1)将硅烷偶联剂加入到醇水溶液中，搅拌均匀后，加入干燥后的氮化硼，得到混合液，用超声波分散混合液，然后在水浴中搅拌，最后烘干研磨筛选得到表面处理后的氮化硼；(1) Add the silane coupling agent to the alcohol aqueous solution, stir evenly, add the dried boron nitride to obtain the mixed solution, disperse the mixed solution with ultrasonic waves, then stir in the water bath, and finally dry, grind and screen to obtain the surface treatment After boron nitride;
(2)将干燥后的低密度聚乙烯、抗氧剂、交联剂、助交联剂、纳米乙烯基笼型聚倍半硅氧烷和步骤(1)所得表面处理后的氮化硼加入密炼机中，充分混合；(2) Add dried low-density polyethylene, antioxidant, crosslinking agent, co-crosslinking agent, nano vinyl cage polysilsesquioxane and surface-treated boron nitride obtained in step (1) In a mixer, mix thoroughly;
(3)将步骤(2)所得混合物用硫化机预热使混合物充分熔融后，将硫化机加压至30～50MPa、升温至165～185℃，压制充分熔融的混合物30-60min，然后维持压力不变冷却至室温，之后进行干燥得到所述交联聚乙烯复合材料。(3) Preheat the mixture obtained in step (2) with a vulcanizer to fully melt the mixture, pressurize the vulcanizer to 30-50MPa, raise the temperature to 165-185°C, press the fully melted mixture for 30-60min, and then maintain the pressure Cool to room temperature without changing, and then dry to obtain the cross-linked polyethylene composite material.
本发明使用硅烷偶联剂可以有效增强氮化硼和低密度聚乙烯的相容性，因为硅烷偶联剂可以与氮化硼表面的羟基反应，从而在氮化硼表面覆盖一层硅烷层，有效防止氮化硼的团聚，提高氮化硼的分散性。在最后进行干燥能够排除交联聚乙烯复合材料中的杂质。The use of silane coupling agent in the present invention can effectively enhance the compatibility between boron nitride and low-density polyethylene, because the silane coupling agent can react with the hydroxyl groups on the surface of boron nitride, thereby covering a layer of silane layer on the surface of boron nitride, Effectively prevent the agglomeration of boron nitride and improve the dispersion of boron nitride. Drying at the end removes impurities from the cross-linked polyethylene composite.
作为本发明所述交联聚乙烯复合材料的制备方法的优选实施方式，所述步骤(1)中醇水溶液中乙醇和水的体积比为95：5；硅烷偶联剂与氮化硼的质量比为1:100。As a preferred embodiment of the preparation method of the crosslinked polyethylene composite material of the present invention, the volume ratio of ethanol and water in the alcohol aqueous solution in the step (1) is 95:5; the mass of silane coupling agent and boron nitride The ratio is 1:100.
第三方面，本发明还提供了一种交联聚乙烯复合材料在高压交流电缆中的应用。In the third aspect, the present invention also provides an application of a cross-linked polyethylene composite material in a high-voltage AC cable.
与现有技术相比，本发明的有益效果为：本发明所述一种交联聚乙烯复合材料以纳米乙烯基笼型聚倍半硅氧烷和氮化硼为添加剂，可以有效提高交联聚乙烯复合材料的耐高压交流击穿能力，这对提高国内交流电缆料运行电压及高压交流电缆的安全稳定运行具有重要意义。Compared with the prior art, the beneficial effects of the present invention are: the cross-linked polyethylene composite material of the present invention uses nano-vinyl cage polysilsesquioxane and boron nitride as additives, which can effectively improve the cross-linking efficiency. The high-voltage AC breakdown resistance of polyethylene composite materials is of great significance for improving the operating voltage of domestic AC cable materials and the safe and stable operation of high-voltage AC cables.
附图说明Description of drawings
图1是氮化硼表面处理工序；Fig. 1 is the boron nitride surface treatment process;
图2是实施例1～7所得交联聚乙烯复合材料的交流击穿场强威布尔分布图；Fig. 2 is the Weibull distribution diagram of the exchange breakdown field strength of embodiment 1～7 gained cross-linked polyethylene composite material;
图3是实施例9所得交联聚乙烯复合材料的交流击穿场强威布尔分布图。Fig. 3 is a Weibull distribution diagram of the AC breakdown field strength of the cross-linked polyethylene composite material obtained in Example 9.
具体实施方式Detailed ways
为更好的说明本发明的目的、技术方案和优点，下面将结合具体实施例和附图对本发明作进一步的说明。In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments and accompanying drawings.
实施例1Example 1
本实施例提供了一种交联聚乙烯复合材料，包括以下质量份的组分：100份低密度聚乙烯、1.8份过氧化二异丙苯、0.4份三烯丙基三聚氰酸酯、0.2份抗氧剂1010、3份纳米乙烯基笼型聚倍半硅氧烷和30份氮化硼；所述氮化硼由粒径为微米级的氮化硼和粒径为纳米级的氮化硼组成，所述粒径为微米级的氮化硼和粒径为纳米级的氮化硼的质量比为3:1。This embodiment provides a cross-linked polyethylene composite material, comprising the following components in parts by mass: 100 parts of low-density polyethylene, 1.8 parts of dicumyl peroxide, 0.4 parts of triallyl cyanurate, 0.2 parts of antioxidant 1010, 3 parts of nanometer vinyl cage polysilsesquioxane and 30 parts of boron nitride; Boron nitride composition, the mass ratio of boron nitride with a particle size of micron and boron nitride with a particle size of nanometer is 3:1.
其中氮化硼为六方氮化硼，所述粒径为微米级的氮化硼的平均中位粒径为10μm；所述粒径为纳米级的氮化硼的平均中位粒径为50nm，纯度为99.1％；低密度聚乙烯的密度为0.9210g/cm 3，熔体流动速率为1.5g/10min，凝胶含量为86％；纳米乙烯基笼型聚倍半硅氧烷的熔点为360℃，闪点为210℃。 Wherein boron nitride is hexagonal boron nitride, and the average median particle diameter of micron-scale boron nitride is 10 μm; the average median particle diameter of nanometer-scale boron nitride is 50 nm. The purity is 99.1%; the density of low-density polyethylene is 0.9210g/cm 3 , the melt flow rate is 1.5g/10min, and the gel content is 86%; the melting point of nano vinyl cage polysilsesquioxane is 360 °C, the flash point is 210 °C.
本实施例还提供了一种交联聚乙烯复合材料的制备方法，包括以下步骤：This embodiment also provides a preparation method of cross-linked polyethylene composite material, comprising the following steps:
(1)将氮化硼置于干燥箱中在110℃下烘干12h，制备醇水溶液(乙醇和水的体积比为95ml：5ml)，将硅烷偶联剂γ-氨丙基三乙氧基硅烷加入到醇水溶液中溶解，硅烷偶联剂质量为氮化硼质量的1％，搅拌20分钟后将烘干的氮化硼加入到溶液中。用超声波将混合液分散1h后，继续在80℃水浴中搅拌3h。将经超声分散的溶液置于干燥箱中在110℃下烘干24h，烘干后仔细研磨筛选后即得到表面处理的氮化硼颗粒，制备过程示意图如图1所示；(1) Put the boron nitride in a drying oven and dry it at 110°C for 12 hours to prepare an aqueous alcohol solution (the volume ratio of ethanol to water is 95ml:5ml), and the silane coupling agent γ-aminopropyltriethoxy The silane is added into the aqueous alcohol solution to dissolve, the mass of the silane coupling agent is 1% of the mass of the boron nitride, and the dried boron nitride is added into the solution after stirring for 20 minutes. After the mixture was dispersed for 1 h by ultrasonic waves, it was stirred in a water bath at 80° C. for 3 h. Place the ultrasonically dispersed solution in a drying oven and dry at 110°C for 24 hours. After drying, carefully grind and screen to obtain surface-treated boron nitride particles. The schematic diagram of the preparation process is shown in Figure 1;
(2)将低密度聚乙烯、过氧化二异丙苯、三烯丙基三聚氰酸酯、抗氧剂1010和纳米乙烯基笼型聚倍半硅氧烷及氮化硼置于干燥箱中在110℃下烘干12h，然后在密炼机中充分混合30min得到混合物，密炼机的温度为110℃，密炼机的转 速为100r/min；(2) Place low-density polyethylene, dicumyl peroxide, triallyl cyanurate, antioxidant 1010, and nano-vinyl cage polysilsesquioxane and boron nitride in a drying oven Dry at 110°C for 12 hours, then fully mix in an internal mixer for 30 minutes to obtain the mixture, the temperature of the internal mixer is 110°C, and the rotational speed of the internal mixer is 100r/min;
(3)称取步骤(2)所得混合物50g，置于平板硫化机中，120℃预热15min，使混合物充分熔融；之后，平板硫化机加压至30MPa，同时温度升高至185℃，压制45min，然后关闭平板硫化机电源，维持压力不变，使试样自然冷却至室温，然后将试样置于80℃的真空干燥箱内，真空干燥48h，即得所述交联聚乙烯复合材料，所得交联聚乙烯复合材料的边长为80mm×80mm，厚度2mm。(3) Weigh 50g of the mixture obtained in step (2), place it in a flat vulcanizer, preheat it at 120°C for 15 minutes, and fully melt the mixture; after that, pressurize the flat vulcanizer to 30MPa, and raise the temperature to 185°C at the same time, press 45min, then turn off the power supply of the flat vulcanizer, keep the pressure constant, let the sample cool down to room temperature naturally, then place the sample in a vacuum drying oven at 80°C, and dry it in vacuum for 48h to obtain the cross-linked polyethylene composite material , the obtained cross-linked polyethylene composite material has a side length of 80mm×80mm and a thickness of 2mm.
实施例2Example 2
本实施例提供了一种交联聚乙烯复合材料，包括以下质量份的组分：100份低密度聚乙烯、1.9份过氧化乙烷、0.3份三烯丙基异三聚氰酸酯、0.25份抗氧剂1035、2份纳米乙烯基笼型聚倍半硅氧烷和35份氮化硼；所述氮化硼由粒径为微米级的氮化硼和粒径为纳米级的氮化硼组成，所述粒径为微米级的氮化硼和粒径为纳米级的氮化硼的质量比为4:1。This embodiment provides a cross-linked polyethylene composite material, comprising the following components by mass: 100 parts of low-density polyethylene, 1.9 parts of ethylene peroxide, 0.3 parts of triallyl isocyanurate, 0.25 parts Parts of antioxidant 1035, 2 parts of nano vinyl cage polysilsesquioxane and 35 parts of boron nitride; The composition of boron, the mass ratio of boron nitride with a particle size of micron and boron nitride with a particle size of nanometer is 4:1.
其中氮化硼为六方氮化硼，所述粒径为微米级的氮化硼的平均中位粒径为5μm；所述粒径为纳米级的氮化硼的平均中位粒径为40nm，纯度为99.1％；低密度聚乙烯的密度为0.9220g/cm 3，熔体流动速率为0.9g/10min，凝胶含量为84％；纳米乙烯基笼型聚倍半硅氧烷的熔点为355℃，闪点为205℃。 Wherein boron nitride is hexagonal boron nitride, and the average median particle diameter of micrometer-sized boron nitride is 5 μm; the average median particle diameter of nanometer-sized boron nitride is 40 nm, The purity is 99.1%; the density of low-density polyethylene is 0.9220g/cm 3 , the melt flow rate is 0.9g/10min, and the gel content is 84%; the melting point of nano vinyl cage polysilsesquioxane is 355 °C, the flash point is 205 °C.
本实施例还提供了一种交联聚乙烯复合材料的制备方法，包括以下步骤：This embodiment also provides a preparation method of cross-linked polyethylene composite material, comprising the following steps:
(1)将氮化硼置于干燥箱中在110℃下烘干12h，制备醇水溶液(乙醇和水的体积比为95ml：5ml)，将硅烷偶联剂γ-氨丙基三乙氧基硅烷加入到醇水溶液中溶解，硅烷偶联剂质量为氮化硼质量的1％，搅拌20分钟后将烘干的氮化硼加入到溶液中。用超声波将混合液分散1h后，继续在80℃水浴中搅拌3h。将经超声分散的溶液置于干燥箱中在110℃下烘干24h，烘干后仔细研磨筛选后即得到表面处理的氮化硼颗粒；(1) Put the boron nitride in a drying oven and dry it at 110°C for 12 hours to prepare an aqueous alcohol solution (the volume ratio of ethanol to water is 95ml:5ml), and the silane coupling agent γ-aminopropyltriethoxy The silane is added into the aqueous alcohol solution to dissolve, the mass of the silane coupling agent is 1% of the mass of the boron nitride, and the dried boron nitride is added into the solution after stirring for 20 minutes. After the mixture was dispersed for 1 h by ultrasonic waves, it was stirred in a water bath at 80° C. for 3 h. Place the ultrasonically dispersed solution in a drying oven and dry at 110°C for 24 hours. After drying, carefully grind and screen to obtain surface-treated boron nitride particles;
(2)将低密度聚乙烯、过氧化二异丙苯、三烯丙基三聚氰酸酯、抗氧剂1010和纳米乙烯基笼型聚倍半硅氧烷及氮化硼置于干燥箱中在110℃下烘干12h，然后在密炼机中充分混合30min得到混合物，密炼机的温度为110℃，密炼机的转 速为100r/min；(2) Place low-density polyethylene, dicumyl peroxide, triallyl cyanurate, antioxidant 1010, and nano-vinyl cage polysilsesquioxane and boron nitride in a drying oven Dry at 110°C for 12 hours, then fully mix in an internal mixer for 30 minutes to obtain the mixture, the temperature of the internal mixer is 110°C, and the rotational speed of the internal mixer is 100r/min;
(3)称取步骤(2)所得混合物50g，置于平板硫化机中，120℃预热15min，使混合物充分熔融；之后，平板硫化机加压至40MPa，同时温度升高至175℃，压制30min，然后关闭平板硫化机电源，维持压力不变，使试样自然冷却至室温，然后将试样置于80℃的真空干燥箱内，真空干燥48h，即得所述交联聚乙烯复合材料，所得交联聚乙烯复合材料的边长80mm×80mm，厚度2.2mm。(3) Weigh 50g of the mixture obtained in step (2), place it in a flat vulcanizer, preheat it at 120°C for 15 minutes, and fully melt the mixture; after that, pressurize the flat vulcanizer to 40MPa, and raise the temperature to 175°C at the same time, press 30min, then turn off the power supply of the flat vulcanizer, keep the pressure constant, let the sample cool down to room temperature naturally, then place the sample in a vacuum drying oven at 80°C, and dry it in vacuum for 48h to obtain the cross-linked polyethylene composite material , the side length of the obtained cross-linked polyethylene composite material is 80mm×80mm, and the thickness is 2.2mm.
实施例3Example 3
本实施例提供了一种交联聚乙烯复合材料，包括以下质量份的组分：100份低密度聚乙烯、2份过氧化二异丙苯、0.5份三羟甲基丙烷三甲基丙烯酸酯、0.3份抗氧剂300、4份纳米乙烯基笼型聚倍半硅氧烷和40份氮化硼；所述氮化硼由粒径为微米级的氮化硼和粒径为纳米级的氮化硼组成，所述粒径为微米级的氮化硼和粒径为纳米级的氮化硼的质量比为6:1。This embodiment provides a cross-linked polyethylene composite material, comprising the following components in parts by mass: 100 parts of low-density polyethylene, 2 parts of dicumyl peroxide, 0.5 part of trimethylolpropane trimethacrylate , 0.3 parts of antioxidant 300, 4 parts of nano vinyl cage polysilsesquioxane and 40 parts of boron nitride; The composition of boron nitride, the mass ratio of boron nitride with a particle size of micron and boron nitride with a particle size of nanometer is 6:1.
其中氮化硼为六方氮化硼，所述粒径为微米级的氮化硼的平均中位粒径为15μm；所述粒径为纳米级的氮化硼的平均中位粒径为60nm，纯度为99.1％；低密度聚乙烯的密度为0.9230g/cm 3，熔体流动速率为2.1g/10min，凝胶含量为82％；纳米乙烯基笼型聚倍半硅氧烷的熔点为350℃，闪点为200℃。 Wherein boron nitride is hexagonal boron nitride, and the average median particle diameter of micron-scale boron nitride is 15 μm; the average median particle diameter of nanometer-scale boron nitride is 60 nm. The purity is 99.1%; the density of low-density polyethylene is 0.9230g/cm 3 , the melt flow rate is 2.1g/10min, and the gel content is 82%; the melting point of nano vinyl cage polysilsesquioxane is 350 °C, and the flash point is 200 °C.
本实施例还提供了一种交联聚乙烯复合材料的制备方法，包括以下步骤：This embodiment also provides a preparation method of cross-linked polyethylene composite material, comprising the following steps:
(1)将氮化硼置于干燥箱中在110℃下烘干12h，制备醇水溶液(乙醇和水的体积比为95ml:5ml)，将硅烷偶联剂γ-氨丙基三乙氧基硅烷加入到醇水溶液中溶解，硅烷偶联剂质量为氮化硼质量的1％，搅拌20分钟后将烘干的氮化硼加入到溶液中。用超声波将混合液分散1h后，继续在80℃水浴中搅拌3h。将经超声分散的溶液置于干燥箱中在110℃下烘干24h，烘干后仔细研磨筛选后即得到表面处理的氮化硼颗粒；(1) Put the boron nitride in a drying oven and dry it at 110°C for 12 hours to prepare an aqueous alcohol solution (the volume ratio of ethanol and water is 95ml:5ml), and the silane coupling agent γ-aminopropyltriethoxy The silane is added into the aqueous alcohol solution to dissolve, the mass of the silane coupling agent is 1% of the mass of the boron nitride, and the dried boron nitride is added into the solution after stirring for 20 minutes. After the mixture was dispersed for 1 h by ultrasonic waves, it was stirred in a water bath at 80° C. for 3 h. Place the ultrasonically dispersed solution in a drying oven and dry at 110°C for 24 hours. After drying, carefully grind and screen to obtain surface-treated boron nitride particles;
(2)将低密度聚乙烯(LDPE)、过氧化二异丙苯(DCP)、三烯丙基三聚氰酸酯、抗氧剂1010和纳米乙烯基笼型聚倍半硅氧烷及氮化硼置于干燥箱中在110℃下烘干12h，然后在密炼机中充分混合30min得到混合物，密炼机的温度 为110℃，密炼机的转速为100r/min；(2) Low density polyethylene (LDPE), dicumyl peroxide (DCP), triallyl cyanurate, antioxidant 1010 and nano vinyl cage polysilsesquioxane and nitrogen Put the boron in a drying oven and dry at 110°C for 12 hours, then fully mix in the internal mixer for 30 minutes to obtain the mixture, the temperature of the internal mixer is 110°C, and the speed of the internal mixer is 100r/min;
(3)称取步骤(2)所得混合物50g，置于平板硫化机中，120℃预热15min，使混合物充分熔融；之后，平板硫化机加压至50MPa，同时温度升高至165℃，压制60min，然后关闭平板硫化机电源，维持压力不变，使试样自然冷却至室温，然后将试样置于80℃的真空干燥箱内，真空干燥48h，即得所述交联聚乙烯复合材料，所得交联聚乙烯复合材料的边长80mm×80mm，厚度1.8mm。(3) Weigh 50g of the mixture obtained in step (2), place it in a flat vulcanizer, preheat it at 120°C for 15 minutes, and fully melt the mixture; after that, pressurize the flat vulcanizer to 50MPa, and simultaneously raise the temperature to 165°C, press 60min, then turn off the power supply of the flat vulcanizer, keep the pressure constant, let the sample cool down to room temperature naturally, then place the sample in a vacuum drying oven at 80°C, and vacuum dry for 48h to obtain the cross-linked polyethylene composite material , the side length of the obtained cross-linked polyethylene composite material is 80mm×80mm, and the thickness is 1.8mm.
实施例4Example 4
本实施例提供了一种交联聚乙烯复合材料，包括以下质量份的组分：100份低密度聚乙烯、1.8份过氧化二异丙苯、0.4份三烯丙基三聚氰酸酯、0.2份抗氧剂1076、3份纳米乙烯基笼型聚倍半硅氧烷和30份氮化硼；所述氮化硼由粒径为微米级的氮化硼和粒径为纳米级的氮化硼组成，所述粒径为微米级的氮化硼和粒径为纳米级的氮化硼的质量比为2:1。This embodiment provides a cross-linked polyethylene composite material, comprising the following components in parts by mass: 100 parts of low-density polyethylene, 1.8 parts of dicumyl peroxide, 0.4 parts of triallyl cyanurate, 0.2 parts of antioxidant 1076, 3 parts of nano vinyl cage polysilsesquioxane and 30 parts of boron nitride; Boron nitride composition, the mass ratio of boron nitride with a particle size of micron and boron nitride with a particle size of nanometer is 2:1.
其中氮化硼为六方氮化硼，所述粒径为微米级的氮化硼的平均中位粒径为10μm；所述粒径为纳米级的氮化硼的平均中位粒径为50nm，纯度为99.1％；低密度聚乙烯的密度为0.9210g/cm 3，熔体流动速率为1.5g/10min，凝胶含量为86％；纳米乙烯基笼型聚倍半硅氧烷的熔点为360℃，闪点为210℃。 Wherein boron nitride is hexagonal boron nitride, and the average median particle diameter of micron-scale boron nitride is 10 μm; the average median particle diameter of nanometer-scale boron nitride is 50 nm. The purity is 99.1%; the density of low-density polyethylene is 0.9210g/cm 3 , the melt flow rate is 1.5g/10min, and the gel content is 86%; the melting point of nano vinyl cage polysilsesquioxane is 360 °C, the flash point is 210 °C.
本实施例还提供了一种交联聚乙烯复合材料的制备方法，包括以下步骤：This embodiment also provides a preparation method of cross-linked polyethylene composite material, comprising the following steps:
(1)将氮化硼置于干燥箱中在110℃下烘干12h，制备醇水溶液(乙醇和水的体积比为95ml：5ml)，将硅烷偶联剂γ-氨丙基三乙氧基硅烷加入到醇水溶液中溶解，硅烷偶联剂质量为氮化硼质量的1％，搅拌20分钟后将烘干的氮化硼加入到溶液中。用超声波将混合液分散1h后，继续在80℃水浴中搅拌3h。将经超声分散的溶液置于干燥箱中在110℃下烘干24h，烘干后仔细研磨筛选后即得到表面处理的氮化硼颗粒；(1) Put the boron nitride in a drying oven and dry it at 110°C for 12 hours to prepare an aqueous alcohol solution (the volume ratio of ethanol to water is 95ml:5ml), and the silane coupling agent γ-aminopropyltriethoxy The silane is added into the aqueous alcohol solution to dissolve, the mass of the silane coupling agent is 1% of the mass of the boron nitride, and the dried boron nitride is added into the solution after stirring for 20 minutes. After the mixture was dispersed for 1 h by ultrasonic waves, it was stirred in a water bath at 80° C. for 3 h. Place the ultrasonically dispersed solution in a drying oven and dry at 110°C for 24 hours. After drying, carefully grind and screen to obtain surface-treated boron nitride particles;
(2)将低密度聚乙烯、过氧化二异丙苯、三烯丙基三聚氰酸酯、抗氧剂1010和纳米乙烯基笼型聚倍半硅氧烷及氮化硼置于干燥箱中在110℃下烘干12h，然后在密炼机中充分混合30min得到混合物，密炼机的温度为110℃，密炼机的转 速为100r/min；(2) Place low-density polyethylene, dicumyl peroxide, triallyl cyanurate, antioxidant 1010, and nano-vinyl cage polysilsesquioxane and boron nitride in a drying oven Dry at 110°C for 12 hours, then fully mix in an internal mixer for 30 minutes to obtain the mixture, the temperature of the internal mixer is 110°C, and the rotational speed of the internal mixer is 100r/min;
(3)称取步骤(2)所得混合物50g，置于平板硫化机中，120℃预热15min，使混合物充分熔融；之后，平板硫化机加压至30MPa，同时温度升高至185℃，压制45min，然后关闭平板硫化机电源，维持压力不变，使试样自然冷却至室温，然后将试样置于80℃的真空干燥箱内，真空干燥48h，即得所述交联聚乙烯复合材料，所得交联聚乙烯复合材料的边长80mm×80mm，厚度2.1mm。(3) Weigh 50g of the mixture obtained in step (2), place it in a flat vulcanizer, preheat it at 120°C for 15 minutes, and fully melt the mixture; after that, pressurize the flat vulcanizer to 30MPa, and raise the temperature to 185°C at the same time, press 45min, then turn off the power supply of the flat vulcanizer, keep the pressure constant, let the sample cool down to room temperature naturally, then place the sample in a vacuum drying oven at 80°C, and dry it in vacuum for 48h to obtain the cross-linked polyethylene composite material , the obtained cross-linked polyethylene composite material has a side length of 80mm×80mm and a thickness of 2.1mm.
实施例5Example 5
本实施例提供了一种交联聚乙烯复合材料，包括以下质量份的组分：100份低密度聚乙烯、1.8份过氧化二异丙苯、0.4份三烯丙基三聚氰酸酯、0.2份抗氧剂1010、1份纳米乙烯基笼型聚倍半硅氧烷和25份氮化硼；所述氮化硼由粒径为微米级的氮化硼和粒径为纳米级的氮化硼组成，所述粒径为微米级的氮化硼和粒径为纳米级的氮化硼的质量比为3:1。This embodiment provides a cross-linked polyethylene composite material, comprising the following components in parts by mass: 100 parts of low-density polyethylene, 1.8 parts of dicumyl peroxide, 0.4 parts of triallyl cyanurate, 0.2 parts of antioxidant 1010, 1 part of nanometer vinyl cage polysilsesquioxane and 25 parts of boron nitride; Boron nitride composition, the mass ratio of boron nitride with a particle size of micron and boron nitride with a particle size of nanometer is 3:1.
其中氮化硼为六方氮化硼，所述粒径为微米级的氮化硼的平均中位粒径为10μm；所述粒径为纳米级的氮化硼的平均中位粒径为50nm，纯度为99.1％；低密度聚乙烯的密度为0.9210g/cm 3，熔体流动速率为1.5g/10min，凝胶含量为86％；纳米乙烯基笼型聚倍半硅氧烷的熔点为360℃，闪点为210℃。 Wherein boron nitride is hexagonal boron nitride, and the average median particle diameter of micron-scale boron nitride is 10 μm; the average median particle diameter of nanometer-scale boron nitride is 50 nm. The purity is 99.1%; the density of low-density polyethylene is 0.9210g/cm 3 , the melt flow rate is 1.5g/10min, and the gel content is 86%; the melting point of nano vinyl cage polysilsesquioxane is 360 °C, the flash point is 210 °C.
本实施例还提供了一种交联聚乙烯复合材料的制备方法，包括以下步骤：This embodiment also provides a preparation method of cross-linked polyethylene composite material, comprising the following steps:
(1)将氮化硼置于干燥箱中在110℃下烘干12h，制备醇水溶液(乙醇和水的体积比为95ml：5ml)，将硅烷偶联剂γ-氨丙基三乙氧基硅烷加入到醇水溶液中溶解，硅烷偶联剂质量为氮化硼质量的1％，搅拌20分钟后将烘干的氮化硼加入到溶液中。用超声波将混合液分散1h后，继续在80℃水浴中搅拌3h。将经超声分散的溶液置于干燥箱中在110℃下烘干24h，烘干后仔细研磨筛选后即得到表面处理的氮化硼颗粒，制备过程示意图如图1所示；(1) Put the boron nitride in a drying oven and dry it at 110°C for 12 hours to prepare an aqueous alcohol solution (the volume ratio of ethanol to water is 95ml:5ml), and the silane coupling agent γ-aminopropyltriethoxy The silane is added into the aqueous alcohol solution to dissolve, the mass of the silane coupling agent is 1% of the mass of the boron nitride, and the dried boron nitride is added into the solution after stirring for 20 minutes. After the mixture was dispersed for 1 h by ultrasonic waves, it was stirred in a water bath at 80° C. for 3 h. Place the ultrasonically dispersed solution in a drying oven and dry at 110°C for 24 hours. After drying, carefully grind and screen to obtain surface-treated boron nitride particles. The schematic diagram of the preparation process is shown in Figure 1;
(2)将低密度聚乙烯、过氧化二异丙苯、三烯丙基三聚氰酸酯、抗氧剂1010和纳米乙烯基笼型聚倍半硅氧烷及氮化硼置于干燥箱中在110℃下烘干12h，然后在密炼机中充分混合30min得到混合物，密炼机的温度为110℃，密炼机的转 速为100r/min；(2) Place low-density polyethylene, dicumyl peroxide, triallyl cyanurate, antioxidant 1010, and nano-vinyl cage polysilsesquioxane and boron nitride in a drying oven Dry at 110°C for 12 hours, then fully mix in an internal mixer for 30 minutes to obtain the mixture, the temperature of the internal mixer is 110°C, and the rotational speed of the internal mixer is 100r/min;
(3)称取步骤(2)所得混合物50g，置于平板硫化机中，120℃预热15min，使混合物充分熔融；之后，平板硫化机加压至30MPa，同时温度升高至185℃，压制45min，然后关闭平板硫化机电源，维持压力不变，使试样自然冷却至室温，然后将试样置于80℃的真空干燥箱内，真空干燥48h，即得所述交联聚乙烯复合材料，所得交联聚乙烯复合材料的边长为80mm×80mm，厚度2mm。(3) Weigh 50g of the mixture obtained in step (2), place it in a flat vulcanizer, preheat it at 120°C for 15 minutes, and fully melt the mixture; after that, pressurize the flat vulcanizer to 30MPa, and raise the temperature to 185°C at the same time, press 45min, then turn off the power supply of the flat vulcanizer, keep the pressure constant, let the sample cool down to room temperature naturally, then place the sample in a vacuum drying oven at 80°C, and dry it in vacuum for 48h to obtain the cross-linked polyethylene composite material , the obtained cross-linked polyethylene composite material has a side length of 80mm×80mm and a thickness of 2mm.
实施例6Example 6
本实施例提供了一种交联聚乙烯复合材料，包括以下质量份的组分：100份低密度聚乙烯、1.8份过氧化二异丙苯、0.4份三烯丙基三聚氰酸酯、0.2份抗氧剂1010、5份纳米乙烯基笼型聚倍半硅氧烷和45份氮化硼；所述氮化硼由粒径为微米级的氮化硼和粒径为纳米级的氮化硼组成，所述粒径为微米级的氮化硼和粒径为纳米级的氮化硼的质量比为3:1。This embodiment provides a cross-linked polyethylene composite material, comprising the following components in parts by mass: 100 parts of low-density polyethylene, 1.8 parts of dicumyl peroxide, 0.4 parts of triallyl cyanurate, 0.2 parts of antioxidant 1010, 5 parts of nanometer vinyl cage polysilsesquioxane and 45 parts of boron nitride; Boron nitride composition, the mass ratio of boron nitride with a particle size of micron and boron nitride with a particle size of nanometer is 3:1.
其中氮化硼为六方氮化硼，所述粒径为微米级的氮化硼的平均中位粒径为10μm；所述粒径为纳米级的氮化硼的平均中位粒径为50nm，纯度为99.1％；低密度聚乙烯的密度为0.9210g/cm 3，熔体流动速率为1.5g/10min，凝胶含量为86％；纳米乙烯基笼型聚倍半硅氧烷的熔点为360℃，闪点为210℃。 Wherein boron nitride is hexagonal boron nitride, and the average median particle diameter of micron-scale boron nitride is 10 μm; the average median particle diameter of nanometer-scale boron nitride is 50 nm. The purity is 99.1%; the density of low-density polyethylene is 0.9210g/cm 3 , the melt flow rate is 1.5g/10min, and the gel content is 86%; the melting point of nano vinyl cage polysilsesquioxane is 360 °C, the flash point is 210 °C.
本实施例还提供了一种交联聚乙烯复合材料的制备方法，包括以下步骤：This embodiment also provides a preparation method of cross-linked polyethylene composite material, comprising the following steps:
(1)将氮化硼置于干燥箱中在110℃下烘干12h，制备醇水溶液(乙醇和水的体积比为95ml：5ml)，将硅烷偶联剂γ-氨丙基三乙氧基硅烷加入到醇水溶液中溶解，硅烷偶联剂质量为氮化硼质量的1％，搅拌20分钟后将烘干的氮化硼加入到溶液中。用超声波将混合液分散1h后，继续在80℃水浴中搅拌3h。将经超声分散的溶液置于干燥箱中在110℃下烘干24h，烘干后仔细研磨筛选后即得到表面处理的氮化硼颗粒，制备过程示意图如图1所示；(1) Put the boron nitride in a drying oven and dry it at 110°C for 12 hours to prepare an aqueous alcohol solution (the volume ratio of ethanol to water is 95ml:5ml), and the silane coupling agent γ-aminopropyltriethoxy The silane is added into the aqueous alcohol solution to dissolve, the mass of the silane coupling agent is 1% of the mass of the boron nitride, and the dried boron nitride is added into the solution after stirring for 20 minutes. After the mixture was dispersed for 1 h by ultrasonic waves, it was stirred in a water bath at 80° C. for 3 h. Place the ultrasonically dispersed solution in a drying oven and dry at 110°C for 24 hours. After drying, carefully grind and screen to obtain surface-treated boron nitride particles. The schematic diagram of the preparation process is shown in Figure 1;
(2)将低密度聚乙烯、过氧化二异丙苯、三烯丙基三聚氰酸酯、抗氧剂1010和纳米乙烯基笼型聚倍半硅氧烷及氮化硼置于干燥箱中在110℃下烘干12h，然后在密炼机中充分混合30min得到混合物，密炼机的温度为110℃，密炼机的转 速为100r/min；(2) Place low-density polyethylene, dicumyl peroxide, triallyl cyanurate, antioxidant 1010, and nano-vinyl cage polysilsesquioxane and boron nitride in a drying oven Dry at 110°C for 12 hours, then fully mix in an internal mixer for 30 minutes to obtain the mixture, the temperature of the internal mixer is 110°C, and the rotational speed of the internal mixer is 100r/min;
(3)称取步骤(2)所得混合物50g，置于平板硫化机中，120℃预热15min，使混合物充分熔融；之后，平板硫化机加压至30MPa，同时温度升高至185℃，压制45min，然后关闭平板硫化机电源，维持压力不变，使试样自然冷却至室温，然后将试样置于80℃的真空干燥箱内，真空干燥48h，即得所述交联聚乙烯复合材料，所得交联聚乙烯复合材料的边长为80mm×80mm，厚度2mm。(3) Weigh 50g of the mixture obtained in step (2), place it in a flat vulcanizer, preheat it at 120°C for 15 minutes, and fully melt the mixture; after that, pressurize the flat vulcanizer to 30MPa, and raise the temperature to 185°C at the same time, press 45min, then turn off the power supply of the flat vulcanizer, keep the pressure constant, let the sample cool down to room temperature naturally, then place the sample in a vacuum drying oven at 80°C, and dry it in vacuum for 48h to obtain the cross-linked polyethylene composite material , the obtained cross-linked polyethylene composite material has a side length of 80mm×80mm and a thickness of 2mm.
实施例7Example 7
本实施例提供了一种交联聚乙烯复合材料，包括以下质量份的组分：100份低密度聚乙烯、1.8份过氧化二异丙苯、0.4份三烯丙基三聚氰酸酯、0.2份抗氧剂1010。This embodiment provides a cross-linked polyethylene composite material, comprising the following components in parts by mass: 100 parts of low-density polyethylene, 1.8 parts of dicumyl peroxide, 0.4 parts of triallyl cyanurate, 0.2 parts Antioxidant 1010.
其中低密度聚乙烯的密度为0.9210g/cm 3，熔体流动速率为1.5g/10min，凝胶含量为86％。 The low density polyethylene has a density of 0.9210g/cm 3 , a melt flow rate of 1.5g/10min and a gel content of 86%.
本实施例还提供了一种交联聚乙烯复合材料的制备方法，包括以下步骤：This embodiment also provides a preparation method of cross-linked polyethylene composite material, comprising the following steps:
(1)将低密度聚乙烯、过氧化二异丙苯、三烯丙基三聚氰酸酯、抗氧剂1010置于干燥箱中在110℃下烘干12h，然后在密炼机中充分混合30min得到混合物，密炼机的温度为110℃，密炼机的转速为100r/min；(1) Place low-density polyethylene, dicumyl peroxide, triallyl cyanurate, and antioxidant 1010 in a drying oven at 110°C for 12 hours, and then fully Mix 30min to obtain mixture, the temperature of internal mixer is 110 ℃, and the rotating speed of internal mixer is 100r/min;
(2)称取步骤(1)所得混合物50g，置于平板硫化机中，120℃预热15min，使混合物充分熔融；之后，平板硫化机加压至30MPa，同时温度升高至185℃，压制45min，然后关闭平板硫化机电源，维持压力不变，使试样自然冷却至室温，然后将试样置于80℃的真空干燥箱内，真空干燥48h，即得所述交联聚乙烯复合材料，所得交联聚乙烯复合材料的边长为80mm×80mm，厚度2mm。(2) Weigh 50g of the mixture obtained in step (1), place it in a flat vulcanizer, preheat it at 120°C for 15 minutes, and fully melt the mixture; after that, pressurize the flat vulcanizer to 30MPa, and raise the temperature to 185°C at the same time, press 45min, then turn off the power supply of the flat vulcanizer, keep the pressure constant, let the sample cool down to room temperature naturally, then place the sample in a vacuum drying oven at 80°C, and dry it in vacuum for 48h to obtain the cross-linked polyethylene composite material , the obtained cross-linked polyethylene composite material has a side length of 80mm×80mm and a thickness of 2mm.
实施例8Example 8
测试实施例1～7所得交联聚乙烯复合材料的交流击穿场强。The AC breakdown field strength of the cross-linked polyethylene composite material obtained in Examples 1-7 was tested.
测试方法：将实施例1～7所得交联聚乙烯复合材料，在1kV/s的升压速度下，测试复合材料的击穿电压。Test method: test the breakdown voltage of the cross-linked polyethylene composite material obtained in Examples 1 to 7 at a boosting speed of 1 kV/s.
测试结果如图2所示。The test results are shown in Figure 2.
图2为实施例1至实施例7所得交联聚乙烯复合材料交流击穿场强威布尔分布图。从图2中可以看出，在同等概率的情况下，实施例1-4所得复合材料的击穿场强均在49kV/mm以上，相较于实施例7纯交联聚乙烯材料的击穿场强，提高了1.69倍，实施例5和6因改变的添加剂含量不在本发明范围内，导致击穿场强相比于实施例1-4有所下降，说明本发明技术方案能够有效提高交联聚乙烯的击穿场强。Fig. 2 is a Weibull distribution diagram of the AC breakdown field strength of the cross-linked polyethylene composite material obtained in Examples 1 to 7. It can be seen from Figure 2 that under the same probability, the breakdown field strengths of the composite materials obtained in Examples 1-4 are all above 49kV/mm, compared with the breakdown field strength of the pure cross-linked polyethylene material in Example 7 The field strength has been increased by 1.69 times. The changed additive content of Examples 5 and 6 is not within the scope of the present invention, resulting in a decrease in the breakdown field strength compared to Examples 1-4, which shows that the technical solution of the present invention can effectively improve the crossover field strength. The breakdown field strength of linked polyethylene.
实施例9Example 9
本实施例进一步研究了氮化硼中粒径为微米级的氮化硼和粒径为纳米级的氮化硼的质量比对本发明交联聚乙烯复合材料的高压交流电缆载流量和绝缘击穿场强的影响。测试方法如实施例8所述，本实施例设置了试验组a～g组，每组的配方仅改变粒径为微米级的氮化硼和粒径为纳米级的氮化硼的质量比，如表1所示，本实施例的交联聚乙烯复合材料所述的其他成分、制备方法与实施例1相同。测试结果如图3所示。This embodiment further studies the mass ratio of boron nitride with micron-scale particle size and nano-scale boron nitride particle size in boron nitride to the high-voltage AC cable ampacity and insulation breakdown of the cross-linked polyethylene composite material of the present invention The influence of field strength. The test method is as described in Example 8. In this example, test groups a to g are set, and the formula of each group only changes the mass ratio of boron nitride with a particle size of micron scale and boron nitride with a particle size of nanoscale. As shown in Table 1, the other components and preparation method of the cross-linked polyethylene composite material in this example are the same as those in Example 1. The test results are shown in Figure 3.
表1Table 1
Figure PCTCN2021125265-appb-000001
Figure PCTCN2021125265-appb-000001
图2为实施例1至实施例7所得交联聚乙烯复合材料交流击穿场强威布尔分布图。从图3可知，7个试验组中，c～f组的复合材料击穿场强最高，均在50kV/mm以上，而a、b组和g组因改变的质量比不在本发明范围内，导致击穿场强相比c～f组有所下降，说明本发明技术方案能够有效提高交联聚乙烯的击穿场强。Fig. 2 is a Weibull distribution diagram of the AC breakdown field strength of the cross-linked polyethylene composite material obtained in Examples 1 to 7. It can be seen from Fig. 3 that among the 7 test groups, the breakdown field strength of composite materials in groups c to f is the highest, all above 50kV/mm, while groups a, b and g are not within the scope of the present invention due to changes in the mass ratio. As a result, the breakdown field strength decreased compared with groups c to f, indicating that the technical solution of the present invention can effectively improve the breakdown field strength of cross-linked polyethylene.
最后所应当说明的是，以上实施例用以说明本发明的技术方案而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者同等替换，而不 脱离本发明技术方案的实质和范围。Finally, it should be noted that the above embodiments are used to illustrate the technical solutions of the present invention rather than limit the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that they can The technical solution of the present invention shall be modified or equivalently replaced without departing from the spirit and scope of the technical solution of the present invention.

Claims (10)

  1. 一种交联聚乙烯复合材料，其特征在于，包括以下质量份的组分：100份低密度聚乙烯、1.8-2份交联剂、0.3-0.5份助交联剂、2-4份纳米乙烯基笼型聚倍半硅氧烷和30-40份氮化硼；A cross-linked polyethylene composite material, characterized in that it includes the following components by mass: 100 parts of low-density polyethylene, 1.8-2 parts of cross-linking agent, 0.3-0.5 parts of auxiliary cross-linking agent, 2-4 parts of nano Vinyl cage polysilsesquioxane and 30-40 parts boron nitride;
    所述氮化硼由粒径为微米级的氮化硼和粒径为纳米级的氮化硼组成，所述粒径为微米级的氮化硼和粒径为纳米级的氮化硼的质量比为2～6:1。The boron nitride is composed of boron nitride with a particle size of micron and boron nitride with a particle size of nanometer, and the particle size is the mass of boron nitride with a particle size of micron and boron nitride with a particle size of nanometer The ratio is 2 to 6:1.
  2. 如权利要求1所述交联聚乙烯复合材料，其特征在于，所述粒径为微米级的氮化硼和粒径为纳米级的氮化硼的质量比为3～6:1。The cross-linked polyethylene composite material according to claim 1, characterized in that the mass ratio of the boron nitride with a particle size of micron to the boron nitride with a particle size of nanometer is 3-6:1.
  3. 如权利要求1或2所述的交联聚乙烯复合材料，其特征在于，所述粒径为微米级的氮化硼的平均中位粒径为5～15μm；所述粒径为纳米级的氮化硼的平均中位粒径为40～60nm。The cross-linked polyethylene composite material according to claim 1 or 2, characterized in that, the average median particle size of boron nitride with a micron-scale particle size is 5-15 μm; the particle size is nano-scale The average median particle diameter of boron nitride is 40-60 nm.
  4. 如权利要求1所述的交联聚乙烯复合材料，其特征在于，所述低密度聚乙烯的密度<0.9230g/cm 3，凝胶含量≥82％。 The cross-linked polyethylene composite material according to claim 1, characterized in that the density of the low-density polyethylene is <0.9230g/cm 3 and the gel content is ≥82%.
  5. 如权利要求1所述的交联聚乙烯复合材料，其特征在于，所述交联剂为过氧化二异丙苯或过氧化乙烷。The cross-linked polyethylene composite material according to claim 1, wherein the cross-linking agent is dicumyl peroxide or ethylene peroxide.
  6. 如权利要求1所述的交联聚乙烯复合材料，其特征在于，所述助交联剂为三烯丙基三聚氰酸酯、三烯丙基异三聚氰酸酯、三羟甲基丙烷三甲基丙烯酸酯中的一种。The cross-linked polyethylene composite material according to claim 1, wherein the auxiliary cross-linking agent is triallyl cyanurate, triallyl isocyanurate, trimethylol One of propane trimethacrylate.
  7. 如权利要求1所述的交联聚乙烯复合材料，其特征在于，所述纳米乙烯基笼型聚倍半硅氧烷的熔点>350℃，闪点>200℃。The cross-linked polyethylene composite material according to claim 1, characterized in that, the nano vinyl cage polysilsesquioxane has a melting point of >350°C and a flash point of >200°C.
  8. 如权利要求1所述的交联聚乙烯复合材料，其特征在于，所述交联聚乙烯复合材料还包括0.2-0.3质量份抗氧剂。The cross-linked polyethylene composite material according to claim 1, characterized in that, the cross-linked polyethylene composite material further comprises 0.2-0.3 mass parts antioxidant.
  9. 如权利要求1～8任一项所述交联聚乙烯复合材料的制备方法，其特征在于，包括以下步骤：The preparation method of the cross-linked polyethylene composite material according to any one of claims 1 to 8, characterized in that it comprises the following steps:
    (1)将硅烷偶联剂加入到醇水溶液中，搅拌均匀后，加入干燥后的氮化硼，得到混合液，用超声波分散混合液，然后在水浴中搅拌，最后烘干研磨筛选得到表面处理后的氮化硼；(1) Add the silane coupling agent to the alcohol aqueous solution, stir evenly, add the dried boron nitride to obtain the mixed solution, disperse the mixed solution with ultrasonic waves, then stir in the water bath, and finally dry, grind and screen to obtain the surface treatment After boron nitride;
    (2)将干燥后的低密度聚乙烯、抗氧剂、交联剂、助交联剂、纳米乙烯基笼型聚倍半硅氧烷和步骤(1)所得表面处理后的氮化硼加入密炼机中，充分混合，得到混合物；(2) Add dried low-density polyethylene, antioxidant, crosslinking agent, co-crosslinking agent, nano vinyl cage polysilsesquioxane and surface-treated boron nitride obtained in step (1) In an internal mixer, mix thoroughly to obtain a mixture;
    (3)将步骤(2)所得混合物用硫化机预热使混合物充分熔融后，将硫化机加压至30～50MPa、升温至165～185℃，压制充分熔融的混合物30～60min，然后维持压力不变冷却至室温，之后进行干燥得到所述交联聚乙烯复合材料。(3) Preheat the mixture obtained in step (2) with a vulcanizer to fully melt the mixture, pressurize the vulcanizer to 30-50MPa, raise the temperature to 165-185°C, press the fully melted mixture for 30-60min, and then maintain the pressure Cool to room temperature without changing, and then dry to obtain the cross-linked polyethylene composite material.
  10. 一种高压交流电缆料，包括权利要求1-8所述的交联聚乙烯复合材料。A high-voltage AC cable material, comprising the cross-linked polyethylene composite material according to claims 1-8.
PCT/CN2021/125265 2021-05-19 2021-10-21 Cross-linked polyethylene composite material, and preparation method therefor and application thereof WO2022242026A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202110548743.2A CN113402799A (en) 2021-05-19 2021-05-19 Crosslinked polyethylene composite material and preparation method and application thereof
CN202110548743.2 2021-05-19

Publications (1)

Publication Number Publication Date
WO2022242026A1 true WO2022242026A1 (en) 2022-11-24

Family

ID=77679136

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/125265 WO2022242026A1 (en) 2021-05-19 2021-10-21 Cross-linked polyethylene composite material, and preparation method therefor and application thereof

Country Status (2)

Country Link
CN (1) CN113402799A (en)
WO (1) WO2022242026A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113402799A (en) * 2021-05-19 2021-09-17 南方电网科学研究院有限责任公司 Crosslinked polyethylene composite material and preparation method and application thereof
CN115028775A (en) * 2022-06-23 2022-09-09 哈尔滨理工大学 Graft modified crosslinked polyethylene insulating layer and preparation method and application thereof
CN115785550A (en) * 2022-11-15 2023-03-14 仲恺农业工程学院 Crosslinked polyethylene high-voltage cable insulation layer material and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104761831A (en) * 2015-04-10 2015-07-08 安徽华能电缆集团有限公司 Micro-nano filler based ethylene propylene rubber nuclear cable insulation material and preparation method
CN106380848A (en) * 2016-08-29 2017-02-08 北京石油化工学院 Low-dielectric-constant high-thermal-conductivity silicone rubber composite material and preparation method thereof
CN106633303A (en) * 2016-12-21 2017-05-10 西安交通大学 Nano composite crosslinked polyethylene insulating material with high direct current breakdown field strength and preparation method of nano composite crosslinked polyethylene insulating material
CN109111742A (en) * 2018-07-10 2019-01-01 淄博职业学院 A kind of computer CPU heat-conducting silicone grease and preparation method thereof
CN110452443A (en) * 2019-08-27 2019-11-15 国网四川省电力公司电力科学研究院 A kind of Cross-linked Polyethylene Composites and preparation method, application
CN113402799A (en) * 2021-05-19 2021-09-17 南方电网科学研究院有限责任公司 Crosslinked polyethylene composite material and preparation method and application thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101389701A (en) * 2006-02-27 2009-03-18 联合碳化化学及塑料技术有限责任公司 Polyolefin-based high dielectric strength (hds) nanocomposites
WO2014000820A1 (en) * 2012-06-29 2014-01-03 Abb Research Ltd Insulating composition for electrical power applications
CN104277182B (en) * 2014-05-12 2016-09-14 浙江大学 A kind of preparation method of cross-link low-density polyethylene
CN110041597A (en) * 2019-04-08 2019-07-23 天津大学 The method of distribution of traps based on micro-nano granules regulation cables of nuclear power polythene material
CN111961276A (en) * 2020-08-18 2020-11-20 大连工业大学 Polyethylene composite material containing long-chain alkyl modified silsesquioxane and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104761831A (en) * 2015-04-10 2015-07-08 安徽华能电缆集团有限公司 Micro-nano filler based ethylene propylene rubber nuclear cable insulation material and preparation method
CN106380848A (en) * 2016-08-29 2017-02-08 北京石油化工学院 Low-dielectric-constant high-thermal-conductivity silicone rubber composite material and preparation method thereof
CN106633303A (en) * 2016-12-21 2017-05-10 西安交通大学 Nano composite crosslinked polyethylene insulating material with high direct current breakdown field strength and preparation method of nano composite crosslinked polyethylene insulating material
CN109111742A (en) * 2018-07-10 2019-01-01 淄博职业学院 A kind of computer CPU heat-conducting silicone grease and preparation method thereof
CN110452443A (en) * 2019-08-27 2019-11-15 国网四川省电力公司电力科学研究院 A kind of Cross-linked Polyethylene Composites and preparation method, application
CN113402799A (en) * 2021-05-19 2021-09-17 南方电网科学研究院有限责任公司 Crosslinked polyethylene composite material and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
NAZIR MUHAMMAD TARIQ; PHUNG BAO TOAN; ZHANG YUANYUAN; LI SHENGTAO: "Dielectric and thermal properties of micro/nano boron nitride co-filled EPDM composites for high-voltage insulation", MICRO & NANO LETTERS, THE INSTITUTION OF ENGINEERING AND TECHNOLOGY, MICHAEL FARADAY HOUSE, SIX HILLS WAY, STEVENAGE, HERTS. SG1 2AY, UK, vol. 14, no. 2, 1 January 1900 (1900-01-01), Michael Faraday House, Six Hills Way, Stevenage, Herts. SG1 2AY, UK , pages 150 - 153, XP006087568, DOI: 10.1049/mnl.2018.5168 *

Also Published As

Publication number Publication date
CN113402799A (en) 2021-09-17

Similar Documents

Publication Publication Date Title
WO2022242026A1 (en) Cross-linked polyethylene composite material, and preparation method therefor and application thereof
Zhao et al. A critical review of the preparation strategies of thermally conductive and electrically insulating polymeric materials and their applications in heat dissipation of electronic devices
CN107337902B (en) Glass fiber and carbon nanotube co-modified epoxy composite material and preparation method thereof
CN110452443A (en) A kind of Cross-linked Polyethylene Composites and preparation method, application
Chi et al. SiC/SiO 2 filler reinforced EP composite with excellent nonlinear conductivity and high breakdown strength
CN109942932A (en) A kind of heatproof high-voltage cable insulating material and preparation method thereof
CN109206731A (en) A kind of power cable shielding material of containing graphene and preparation method thereof
CN114854087B (en) Polyimide composite material with double heat-conducting networks and preparation method thereof
CN113150438A (en) Graphene-doped semiconductive shielding material for thermoplastic cable and preparation method thereof
CN112662134A (en) Preparation method of epoxy resin composite material filled with MOF nanosheets
CN106009693A (en) Silicone rubber with excellent tracking resistance and high heat conductivity
CN113292859A (en) Nano-modified rapid-forming high-molecular insulating material and preparation method thereof
CN106633303A (en) Nano composite crosslinked polyethylene insulating material with high direct current breakdown field strength and preparation method of nano composite crosslinked polyethylene insulating material
Zha et al. Effect of multi-dimensional zinc oxide on electrical properties of polypropylene nanocomposites for HVDC cables
CN108530726A (en) A kind of insulating materials and preparation method thereof of low temperature sensibility
Wang et al. Dielectric film with high energy density based on polypropylene/maleic anhydride-grafted polypropylene/boron nitride nanosheet ternary system
CN114292466A (en) Modified polypropylene insulating material for medium and low voltage power cable and preparation method thereof
CN103665525A (en) High voltage direct current cable insulation material
He et al. Progress in eco-friendly high voltage cable insulation materials
CN109206748B (en) Polypropylene-based composite insulating material and preparation method thereof
CN108003437A (en) A kind of high voltage direct current cable is modified CABLE MATERIALS and preparation method thereof with graphene
CN114539783B (en) High-heat-conductivity high-insulation gasket and preparation method thereof
CN110452444B (en) Crosslinked polyethylene composite material with super-hydrophobic characteristic, preparation method and application
CN106867077A (en) A kind of crosslinked polyethylene insulation material and preparation method thereof
CN102304258A (en) Functional composite material used for spacecraft and preparation method thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21940472

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE