WO2017133310A1 - 具有抑制电树枝生长能力的聚合物纳米介孔复合材料及其制备方法 - Google Patents

具有抑制电树枝生长能力的聚合物纳米介孔复合材料及其制备方法 Download PDF

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WO2017133310A1
WO2017133310A1 PCT/CN2016/108082 CN2016108082W WO2017133310A1 WO 2017133310 A1 WO2017133310 A1 WO 2017133310A1 CN 2016108082 W CN2016108082 W CN 2016108082W WO 2017133310 A1 WO2017133310 A1 WO 2017133310A1
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nanoparticles
mesoporous
polymer
composite material
electric tree
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French (fr)
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何金良
杨洋
胡军
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Tsinghua University
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    • 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—Polyethylene
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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

Definitions

  • the present invention relates to the field of materials, and in particular, to a polymer nano-mesoporous composite material having the ability to inhibit electric tree branch growth and a preparation method thereof.
  • High-voltage insulation materials are easy to insulate and even break down due to long-term work under strong electric fields.
  • Common insulating materials usually use polymer materials and their composites. Insulation aging or breakdown damage of commonly used polymeric insulating materials is usually due to the formation of electrical branches within the insulating material.
  • An electric branch is a microdischarge defect having a dendritic fractal structure that rapidly penetrates the insulating layer under strong electric field and high temperature and eventually causes breakdown and insulation failure. Therefore, suppressing the formation and development of electric tree branches, improving the durability of engineering insulation materials, and prolonging the working life of high-voltage equipment are important issues that need to be solved for high-voltage insulation materials.
  • the present invention is based on the discovery and recognition of the following facts and problems by the inventors:
  • insulating polymers based on nanoparticle doping often have unsatisfactory electrical breakdown resistance.
  • the inventors have conducted in-depth research and a large number of experiments and found that this is due to the small size of the nanoparticles, so that it has a large surface energy, and when the doping concentration is high, it is easy to form micron-sized agglomerates in the substrate, so that the micron-sized agglomerates are actually obtained.
  • the particle-doped polymer which causes the polymer breakdown strength and the like, is not ideal; and when the nanoparticle doping concentration is low, it is difficult to effectively block the growth extension path of the electric branch in the material.
  • the present invention provides a polymer nano-mesoporous composite material having the ability to inhibit electric tree branch growth.
  • the composite material comprises: a body, the body is absolutely a rim polymer; and nanoparticles, the nanoparticles being dispersed in the body, and the nanoparticles having a mesoporous structure.
  • the mesoporous structure in the nanoparticles can be utilized to increase the phase interface region between the nanoparticles and the body, thereby improving the compatibility of the two phases and solving the agglomeration problem of the nanoparticles.
  • the mesoporous structure and the filled functional material can effectively absorb the gas molecules in the aging product of the electric tree, alleviate the electrical stress and mechanical stress in the electric tree region, and slow down the growth of the electric tree.
  • the nanoparticles comprise at least one of silica, silicates, aluminosilicates, phosphates and metal oxides.
  • the above materials are chemically stable and low in cost, and the process for preparing mesoporous nanoparticles is mature.
  • the nanoparticle further includes: a filler material filled in the mesoporous structure, the filler material containing polyethyleneimine, N-methyldiethanolamine (MDEA), and At least one of triethylene thiophosphate (TEPA).
  • MDEA N-methyldiethanolamine
  • TEPA triethylene thiophosphate
  • the content of the nanoparticles is from 0.1 to 0.5% by weight, based on the total mass of the polymer. Since the above-mentioned nanoparticles contain a mesoporous structure and have a larger phase interface region, it is possible to suppress electric tree growth by a lower doping concentration.
  • the body comprises low density polyethylene, crosslinked polyethylene, epoxy, and polypropylene.
  • the invention provides a method of making the composite material previously described.
  • the method comprises: (1) mixing the nanoparticles and the body to obtain a mixture; and (2) subjecting the mixture to a melt blending treatment to obtain the polymer.
  • the composite material according to the embodiment of the present invention can be easily obtained, and the higher melting temperature in the melt blending preparation process can be used to remove impurities which may be adsorbed in the mesopores of the nanoparticles, thereby improving the anti-electricity of the composite material. Tree growth performance.
  • step (1) before the step (1), further comprising: filling the mesoporous structure of the nanoparticles with a filling material.
  • the filler material composed of the above organic amines can be utilized to enhance the ability of the nanoparticles to adsorb acid gas molecules in the electric tree aging product, thereby enhancing the ability of the polymer to resist insulation aging.
  • filling the filling material in the mesoporous structure of the nanoparticles is accomplished by: (a) adding the nanoparticles to a filling material solution for immersion treatment; b) subjecting the impregnated nanoparticles to a low temperature evaporation treatment to fill the filling material in the mesoporous structure of the nanoparticles.
  • the filler material can be easily filled into the mesoporous structure of the nanoparticles.
  • the filling material solution comprises the filling material and a solvent, the solvent comprising There is at least one of methanol, ethanol, chloroform, dimethylformamide, and acetone.
  • the above solvent has a small molecular weight and is volatile, and can be easily removed during the low-temperature evaporation treatment.
  • the immersion time is from 30 to 60 minutes.
  • the temperature of the low temperature evaporation treatment is 50 to 75 degrees Celsius.
  • Figure 1 shows a schematic structural view of a polymer according to an embodiment of the present invention
  • FIG. 2 shows a schematic structural view of a nanoparticle according to an embodiment of the present invention
  • FIG. 3 is a schematic view showing the structure of a nanoparticle according to another embodiment of the present invention.
  • FIG. 4 shows a flow chart of a method of preparing a polymer in accordance with one embodiment of the present invention
  • Figure 5 shows a flow chart of a method of preparing a polymer in accordance with another embodiment of the present invention
  • Figure 6 shows a sample structure diagram of an electric tree aging performance test in accordance with one embodiment of the present invention.
  • the invention provides a polymeric nano-mesoporous composite having the ability to inhibit electrical tree growth.
  • the composite material includes a body 100 and nanoparticles 10.
  • the body 100 is an insulating polymer
  • the nanoparticles 10 are dispersed in the body 100
  • the nanoparticles 10 have a mesoporous structure 20.
  • the mesopores in the nanoparticles can be utilized to increase the phase interface region between the nanoparticles and the body, thereby improving the agglomeration problem of the nanoparticles.
  • the mesoporous structure (mesoporous channel) can effectively adsorb the gas molecules in the aging products of the electric tree, and alleviate the electrical stress and mechanical stress in the electric tree region.
  • the composite material can slow down the growth of electric trees and prolong the service life.
  • the inventors have conducted in-depth research and a large number of experiments and found that in the micro-discharge defect region where the electric tree branches are formed, the electrical stress and mechanical stress of the region are greater than the intact regions in the polymer due to the presence of the electrical tree aging product. Therefore, the above-mentioned micro-discharge defect region is extremely easy to grow and eventually causes breakdown of the insulating polymer. And the above electric tree is old Chemical products, mostly acid gas molecules. Since the above gas molecules in the composite material cannot discharge the body of the composite material, electrical stress and mechanical stress in the region are large.
  • the conventional polymer having the function of suppressing electric tree growth forms a "barrier" on the path of micro-discharge defect growth of the electric tree by doping the polymer with inorganic particles having high dielectric strength, thereby blocking or delaying the electricity.
  • the growth of the tree The inventors have conducted in-depth research and a large number of experiments and found that in the conventional polymer having the function of suppressing electric tree growth doped with microparticles, the dielectric loss and the breakdown strength of the composite after doping are often degraded. The problem, which is mainly due to the introduction of larger-sized microparticles, affects the overall performance of the material.
  • the doping concentration of the nanoparticles is difficult to control.
  • the surface energy is large, and the high doping concentration causes the nanoparticles to agglomerate to form micron-sized agglomerates, thereby affecting the overall performance of the composite; and when the doping concentration is low, At this time, it is impossible to form enough "barriers" around the micro defects to block the growth of the electric tree.
  • the above-mentioned polymer doped with microparticles or nanoparticles does not solve the problem that the gas molecules in the electric tree aging product cannot be discharged from the polymer body.
  • the present invention replaces conventional nanoparticles with nanoscale inorganic particles having a mesoporous size (50-2 nm) pore structure. Since the nanoparticles 10 having the mesoporous structure 20 have an extremely large specific surface area, the composite material according to the present invention can introduce more phase interface regions than conventional nanocomposites, by enhancing the ability of the nanoparticles to adsorb electric tree aging products, Realize the growth of the suppression tree. Thus, the composite material according to an embodiment of the present invention can achieve suppression of electric tree growth by a lower doping concentration and solve the problem of agglomeration of nanoparticles during doping.
  • nanoparticles 10 having a smaller size and a lower concentration do not adversely affect the performance of the body 100.
  • the nanoparticle 10 is interpenetrated with the body 100 by the loose frame structure having the mesoporous structure 20, and the strong insulation strength of the nanoparticle 10 can effectively block the formation and development of the electric branch defect. .
  • the nanoparticles 10 may contain at least one of silica, silicate, aluminosilicate, phosphate, and metal oxide.
  • a mesoporous structure 20 exists in the nanoparticle 10 formed of the above-described nanoscale (particle diameter of 100 nm to 200 nm or less).
  • mesoporous silicon, zeolite, or the like can be used as the nano-particles 10. The preparation process of such materials is relatively mature and low in cost, and currently there are mainly hydrothermal synthesis methods, hydrothermal conversion methods and ions. Exchange method, etc.
  • the nanoparticles can be formed by using the above-mentioned preparation process, which is mature, chemically stable, and low in cost. Further, the nanoparticles 10 formed of the above inorganic material have strong dielectric strength, and thus can function to prevent electrical breakdown and suppress electric tree growth.
  • the nanoparticle 10 having the mesoporous structure 20 has a porous structure, so that the polymer molecular chain of the body 100 can be inserted into the mesoporous structure and form an interpenetrating network, thereby enabling Achieve better inorganic-organic two-phase compatibility and further improve various aspects of the composite can. Therefore, for the composite material according to the embodiment of the present invention, better dispersibility can be obtained without special chemical modification of the nanoparticles 10.
  • the content of the nanoparticles 10 is 0.1 to 0.5% by weight based on the total mass of the polymer.
  • the nanoparticle 10 according to the embodiment of the present invention contains the mesoporous structure 20, it is possible to introduce more phase interface regions than the conventional nanocomposite material, and to enhance the ability of the nanoparticle to adsorb the electric tree aging product. Suppress the growth of electric trees. Thereby, suppression of electric tree growth can be achieved by a lower doping concentration.
  • the specific material constituting the polymer body 100 is not particularly limited, and the body 100 may be an insulating material commonly used in the art.
  • the body 100 may be an insulating polymer material, and specifically, according to an embodiment of the present invention, the body 100 may be low density polyethylene (LDPE), crosslinked polyethylene (XLPE), epoxy resin, and polypropylene (PP).
  • LDPE low density polyethylene
  • XLPE crosslinked polyethylene
  • PP polypropylene
  • a person skilled in the art can select an appropriate insulating polymer to form the body 100 according to an embodiment of the present invention according to actual needs.
  • the nanoparticles 10 may further comprise a filler material 30, in accordance with an embodiment of the present invention, with reference to FIG.
  • the inventors have conducted in-depth research and a large number of experiments to find that nanomaterials with mesoporous structure, such as mesoporous molecular sieves, have limited adsorption capacity under high temperature conditions, and gas molecules adsorbed at normal temperature will also desorb after temperature rise, so Under high temperature operating conditions, such as a large-capacity transmission cable, the electric tree aging product gas molecules adsorbed by the nanoparticles 10 are easily desorbed back into the body 100.
  • an organic amine is used as a chemical filler to form a filler material 30 in the mesoporous structure 20, which can be used to stabilize the acid gas aging acid gas product (mainly carbon dioxide) in a certain temperature range. Adsorption.
  • the filler material 30 may be formed of at least one selected from the group consisting of polyethyleneimine, N-methyldiethanolamine (MDEA), and triethylene thiophosphoric acid amine (TEPA), and the filler material 30 is filled in the mesoporous structure 20 in.
  • a filler material 30 having a specific functional group, for example, an amino group By adding a filler material 30 having a specific functional group, for example, an amino group, to the mesostructure 20 of the nanoparticle 10, stable adsorption of the polymer electric tree aging product can be achieved.
  • the filler material 30 formed by the above organic amine-based material can enhance the ability of the nanoparticle 10 to adsorb the acid electric tree aging gas product, thereby improving the ability of the composite material to inhibit electric tree branch growth. It should be noted that in order to ensure the overall performance of the composite material having the filler material 30 and the electrical breakdown resistance, the material forming the filler material 30 needs to have a relatively low molecular weight and good thermal stability.
  • PEI polyethyleneimine
  • TGA thermogravimetric analysis
  • the composite material according to an embodiment of the present invention has the following features and advantages:
  • the mesoporous structure can be used to increase the phase interface between the nanoparticles and the body, and the agglomeration problem in the doping process of the nanoparticles is improved.
  • the mesoporous structure can effectively adsorb the gas molecules in the aging products of the electric tree, thereby alleviating the electrical stress and mechanical stress in the electric tree region and slowing the growth of the electric tree.
  • the content of the nano particles is low, and the effective anti-breakdown and retardation of the electric tree growth can be achieved by low concentration doping, thereby improving the performance of the polymer under the working condition of strong electric field.
  • the composite material according to the embodiment of the invention can ensure that the performance of the polymer itself is not affected under the premise of having better anti-breakdown and retarding the growth ability of the electric tree.
  • the invention provides a method of preparing a polymeric nano-mesoporous composite having the ability to inhibit electrical tree growth as previously described. According to an embodiment of the present invention, referring to FIG. 4, the method includes:
  • the nanoparticles and the body are mixed.
  • the nanoparticle has a mesoporous structure.
  • the mesoporous structure in the nanoparticle can be used to increase the phase interface region between the nanoparticle and the body, improve the agglomeration problem in the doping process of the nanoparticle, and can effectively adsorb the gas in the aging product of the electric tree by using the mesoporous structure. Molecules, thereby alleviating the electrical stress and mechanical stress in the electric tree area, thereby slowing the growth of electric trees.
  • the specific composition and structure of the nanoparticles have been described in detail above and will not be described herein.
  • the method further includes:
  • a filler material is filled in the mesoporous structure of the nanoparticles.
  • the filler material composed of the above organic amines can be utilized to enhance the ability of the nanoparticles to adsorb acid gas molecules in the electric tree aging product, thereby enhancing the ability of the composite material to resist insulation aging.
  • the specific types and functions of the filling materials have been described in detail above and will not be described herein.
  • the filling material can be set by the following steps:
  • the nanoparticles are added to the filling material solution for the immersion treatment.
  • a solution containing a filler is prepared, and the nanoparticles are immersed in the solution to perform a stirring immersion treatment.
  • the specific composition of the solvent of the solution containing the filler material is not particularly limited as long as it has good compatibility with the filler material, and the solvent molecule itself is volatile, which is convenient for use in subsequent processing. The operation such as drying can be removed.
  • the solvent may be methanol, ethanol, At least one of chloroform, dimethylformamide, and acetone.
  • the content of the filling material in the above filling material solution, may be 10 to 50% by weight.
  • the filling material concentration in the immersion liquid may be 10 to 20% by weight, impregnated.
  • the time can be 30 to 60 minutes.
  • the content of the filler in the preparation of the obtained nanoparticles, may be 10 to 50% by weight based on the total mass of the nanoparticles.
  • the above solvent has good compatibility with the filler material, and the solvent molecule is small and volatile, and the solvent is removed in the subsequent step to obtain the nanoparticle according to the embodiment of the present invention.
  • the impregnated nanoparticles are treated by low-temperature evaporation, and the solvent in the filling material solution is removed to obtain nanoparticles.
  • the filler material solution containing the nanoparticles is filtered to obtain nanoparticles impregnated with the filler material, and then the residual solvent is removed by evaporation.
  • the drying temperature may be 50 to 75 degrees Celsius.
  • a composite material according to an embodiment of the present invention is obtained by a melt blending technique.
  • the higher melting temperature in the melt blending preparation process can be utilized to remove impurities which may be adsorbed in the mesopores of the nanoparticles, thereby improving the anti-electric tree growth performance of the composite material.
  • the nanoparticle and the mixture of bulk compositions can be melt blended to form a composite material according to the present invention.
  • the specific material for forming the body according to the embodiment of the present invention has been described in detail above and will not be described herein.
  • the content of the nanoparticles may be from 0.1 to 0.5% by weight in the polymer body and the mixture of nanoparticles.
  • the nanoparticle according to the embodiment of the present invention contains a mesoporous structure, it is possible to introduce more phase interface regions than the conventional nanocomposite material, and to enhance the electric power by enhancing the ability of the nanoparticle to adsorb the electric tree aging product. The growth of the tree. Thereby, suppression of electric tree growth can be achieved by a lower doping concentration.
  • the mesoporous structure can be used to increase the phase interface between the nanoparticles and the body, and the agglomeration problem in the doping process of the nanoparticles is improved.
  • the mesoporous structure can effectively adsorb the gas molecules in the aging products of the electric tree, thereby alleviating the electrical stress and mechanical stress in the electric tree region and slowing the growth of the electric tree.
  • the polymer according to the embodiment of the invention has low nano-particle content, can achieve effective anti-breakdown and retard electric tree growth by low concentration doping, thereby improving the performance of the composite material under strong electric field working conditions.
  • the composite material according to the embodiment of the invention can ensure that the performance of the polymer itself is not affected under the premise of having better anti-breakdown and retarding the growth ability of the electric tree.
  • the method has the advantages of simple processing steps and low production cost, and is favorable for the large-scale preparation of the polymer prepared by the method. Promotion.
  • Polypropylene (PP) is used as the polymer body, and MCM-41 mesoporous silica having a particle diameter of 100-200 nm is a nanoparticle.
  • the mesoporous silica was mixed with PP, and the content of the intervening silica of the mixture was 0.5% by weight.
  • Set the melt blending temperature to 200 degrees Celsius.
  • the above mixture was placed in an internal mixer, and the rotor rotation speed was set to 60 rpm, and the mixing time was 10 minutes.
  • a PP/MCM-41 composite material was obtained.
  • MCM-41 mesoporous silica having a particle diameter of 100 to 200 nm was used as the nanoparticles.
  • a 50 wt% PEI solution was prepared using methanol and polyethyleneimine, and MCM-41 mesoporous silica having a particle diameter of 100 to 200 nm was immersed in the PEI solution, and immersed and stirred at room temperature for 30 minutes. After filtration, the methanol solvent was removed by drying at 50 degrees Celsius to obtain PEI-filled nanoparticles.
  • the PEI-filled nanoparticles were mixed with PP, and the content of the inter-site silica was 0.5 wt%.
  • the above mixture was placed in an internal mixer, and the rotor rotation speed was set to 60 rpm, and the mixing time was 10 minutes.
  • a PP/MCM-41-PEI composite material was obtained.
  • the preparation method was the same as in Example 1, except that solid silica having a particle diameter similar to that of mesoporous nanoparticles (200 to 300 nm) was used as a nanoparticle for doping.
  • the content of solid silica in the mixture was also 0.5% by weight.
  • the inventors examined the porosity of the mesoporous silica nanoparticles used in Example 1 and Example 2.
  • the pore volume of the MCM-41 mesoporous material used by the nitrogen adsorption-desorption method is about 0.3 ml/g.
  • the density of silica is about 2.2 g/cm 3
  • the density ratio of the mesoporous silica nanoparticles and the solid silica nanoparticles was calculated to be 1:1.66.
  • the volumetric doping percentage of the doped mesoporous silica nanoparticles in Examples 1 and 2 is similar when the volume fraction of solid silica nanoparticles in the polymer is 0.83%.
  • Comparative Example 2 was the same as that of Example 1, except that solid silica having a particle diameter similar to that of mesoporous nanoparticles (200 to 300 nm) was used as a nanoparticle for doping.
  • the volume percentage of solid silica in the mixture was 0.83%.
  • the random copolymer polypropylene PP-R/4220 (provided by Yanshan Petrochemical Co., Ltd.) was used as a control, and the polymer aging properties of the polymers prepared in Comparative Example 1, Comparative Example 2, Example 1 and Example 2 were tested. .
  • Samples for electric tree aging were prepared by hot press molding of a flat vulcanizer and a steel die. Before hot pressing, the stainless steel needle electrode is inserted into a piece of conductive rubber and pre-buried in the steel mold together with the sample material. The conductive rubber facilitates the contact of the external electrode, and the obtained sample shows the structure as shown in FIG. Among them, the sample obtained by lamination is a rectangular parallelepiped shape, 15 mm long, 3 mm wide, and 20 mm high. The conductive paste is located on the top of the rectangular parallelepiped sample, and the bottom of the needle electrode connected to the conductive paste is 7 mm away from the bottom of the rectangular parallelepiped sample.
  • the sample was held between two plate electrodes, the electrode was in contact with the conductive rubber, and the other electrode was grounded.
  • the voltage applied during the test was 30 kV at a power frequency of 50 Hz.
  • the electric tree aging experiment needs to be carried out under high temperature conditions.
  • the eucalyptus experiment is an important indicator to measure the aging resistance of insulating materials, and the eucalyptus process needs to be continuously observed by optical microscopy to obtain it, which is difficult to implement under high temperature conditions. Therefore, in this embodiment, two kinds of electric tree aging tests are used to study the electric tree aging characteristics under electric tree framing and high temperature conditions, respectively.
  • Example 1 and Example 2 are nanocomposites doped with mesoporous silica materials (PP/MCM-41-PEI and PP/MCM-41), compared with pure PP substrates and comparative examples.
  • the composite material of the solid silica nanoparticles (PP/SiO 2 ) of 1 and Comparative Example 2 both exhibited a stronger ability to inhibit electric tree growth, and the aging time of the electric tree size of Example 1 and Example 2 was extended by 2 ⁇ 5 times.
  • the high temperature electric tree experiment further verified that mesoporous nanoparticles loaded with organic amines can further inhibit electric tree aging at high temperatures. Under the same aging time, PP/MCM-41-PEI composites showed lower degradation than PP/MCM-41 composites.
  • the former has the same electrical branch size as about half of the latter.
  • the dielectric strength of the composite is characterized primarily by electrical breakdown tests on the film samples.
  • the PP and various composite materials are hot pressed into a film having a thickness of 60 to 80 ⁇ m by using a flat vulcanizer and a steel die, and then the film sample is held between the ball-sphere electrodes having a diameter of 1 cm and immersed in the silicone oil.
  • the electrode voltage is uniformly increased, and the breakdown voltage value is automatically recorded by the experimental system at the time of sample breakdown.
  • the power frequency AC breakdown and DC breakdown experiments are performed, and the boosting rates are 1kV rms/sec and 1kV/sec, respectively.
  • the experimental methods and devices refer to the International Electrotechnical Commission respectively. Member standards IEC 60243-1:1998 and IEC 60243-2:2001.
  • E is the breakdown field strength of the data points
  • ⁇ is the probability characteristic value of 63.2%
  • ⁇ is the shape parameter of the Weibull distribution, which is used to characterize the discreteness of the experimental data.
  • a breakdown field strength corresponding to a breakthrough probability point of 63.2% can be obtained.
  • the breakdown field strength can represent the breakdown strength of the sample.
  • the results of DC breakdown experiments show that the composite material doped with organic amine-doped mesoporous nanoparticles (Example 2) has a breakdown strength of nearly 550 kV/mm, which is about 18% higher than the DC breakdown strength of pure substrate PP. .

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Abstract

提出了具有抑制电树枝生长能力的聚合物纳米介孔复合材料。根据本发明的实施例，该复合材料包括：本体，所述本体为绝缘聚合物；以及纳米颗粒，所述纳米颗粒分散于所述本体中，且所述纳米颗粒具有介孔结构。

Description

具有抑制电树枝生长能力的聚合物纳米介孔复合材料及其制备方法
优先权信息
本申请请求2016年02月05日向中国国家知识产权局提交的、专利申请号为201610081293.X的专利申请的优先权和权益，并且通过参照将其全文并入此处。
技术领域
本发明涉及材料领域，具体地，本发明涉及具有抑制电树枝生长能力的聚合物纳米介孔复合材料及其制备方法。
背景技术
高压绝缘材料因长期工作在强电场下，易绝缘老化甚至被击穿破坏。常见的绝缘材料通常采用高分子材料及其复合物。常用的高分子绝缘材料的绝缘老化或其击穿破坏通常是由于在绝缘材料内部形成了电树枝。电树枝是一种具有树枝状分形结构的微放电缺陷，这种放电通道在强电场和高温下会迅速贯穿绝缘层并最终导致击穿和绝缘失效。因此，抑制电树枝的形成和发展，提高工程绝缘材料的耐久度，延长高压设备的工作寿命，是高压绝缘材料需要解决的重要问题。
目前抑制电树枝生长的方法，通常是通过在聚合物基材中掺杂一定浓度的绝缘颗粒而实现的。最初的掺杂物多为绝缘强度较高的微米级氧化物颗粒，如氧化铝，氧化镁，氧化硅等。所得到的聚合物基复合材料虽然能够在某些性能上得到提升，但微米级掺杂往往带来其他性能的降低，如介电损耗增大和击穿强度降低等。随着纳米技术的发展，纳米颗粒也被掺杂于聚合物中用于抑制电树枝的形成。
然而，目前抑制绝缘聚合物中电树枝生长的技术仍有待改进。
发明内容
本发明是基于发明人对以下事实和问题的发现和认识做出的：
目前基于纳米颗粒掺杂的绝缘聚合物，常常存在防电击穿性能不理想的情况。发明人经过深入研究以及大量实验发现，这是由于纳米颗粒尺寸较小，因此具有较大的表面能，掺杂浓度高时容易在基材中形成微米级团块，因此实际获得的是具有微米颗粒掺杂的聚合物，从而造成聚合物击穿强度等性能不理想；而当纳米颗粒掺杂浓度低时，又难以在材料中对电树枝的生长延伸路径进行有效的阻挡。
有鉴于此，在本发明的第一方面，本发明提出了一种具有抑制电树枝生长能力的聚合物纳米介孔复合材料。根据本发明的实施例，该复合材料包括：本体，所述本体为绝 缘聚合物；以及纳米颗粒，所述纳米颗粒分散于所述本体中，且所述纳米颗粒具有介孔结构。由此，可利用纳米颗粒中的介孔结构，增加纳米颗粒与本体之间的相界面区域，进而改善两相相容性并解决纳米颗粒的团聚问题。并且可以利用介孔结构及填充的功能材料有效吸附电树老化产物中的气体分子，缓解电树区域的电气应力以及机械应力，减缓电树生长。
根据本发明的实施例，所述纳米颗粒含有二氧化硅、硅酸盐、硅铝酸盐、磷酸盐以及金属氧化物的至少之一。上述物质化学性质稳定且成本低廉，制备介孔纳米颗粒的工艺成熟。
根据本发明的实施例，所述纳米颗粒进一步包括：填充材料，所述填充材料填充在所述介孔结构中，所述填充材料含有聚乙烯亚胺、N-甲基二乙醇胺(MDEA)以及三乙烯硫代磷酸胺(TEPA)的至少之一。利用上述有机胺类物质构成填充材料，可以加强纳米颗粒吸附电树老化产物中的酸性气体分子的能力，从而可以增强该聚合物抗绝缘老化的能力。
根据本发明的实施例，基于所述聚合物的总质量，所述纳米颗粒的含量为0.1～0.5wt％。由于上述纳米颗粒中含有介孔结构，具有更大的相界面区域，因此，可以通过较低的掺杂浓度，实现抑制电树生长。
根据本发明的实施例，所述本体包括低密度聚乙烯、交联聚乙烯、环氧树脂以及聚丙烯。
在本发明的另一方面，本发明提出了一种制备前面所述的复合材料的方法。根据本发明的实施例，该方法包括：(1)将纳米颗粒以及本体混合，以便获得混合物；以及(2)对所述混合物进行熔融共混处理，以便获得所述聚合物。由此，可以简便地获得根据本发明实施例的复合材料，并利用熔融共混制备过程中较高的熔融温度，除去纳米颗粒的介孔中有可能吸附的杂质，提高该复合材料的防电树生长性能。
根据本发明的实施例，在步骤(1)之前，进一步包括：在所述纳米颗粒的所述介孔结构中填充填充材料。由此，可以利用上述有机胺类物质构成的填充材料，加强纳米颗粒吸附电树老化产物中的酸性气体分子的能力，从而可以增强该聚合物抗绝缘老化的能力。
根据本发明的实施例，在所述纳米颗粒的所述介孔结构中填充所述填充材料是通过下列步骤完成的：(a)将所述纳米颗粒加入到填充材料溶液中进行浸渍处理；(b)经过所述浸渍处理的纳米颗粒进行低温蒸发处理，以便在所述纳米颗粒的所述介孔结构中填充所述填充材料。由此，可以简便地将填充材料填充到纳米颗粒的介孔结构中。
根据本发明的实施例，所述填充材料溶液包含所述填充材料以及溶剂，所述溶剂含 有甲醇、乙醇、氯仿、二甲基甲酰胺以及丙酮的至少之一。上述溶剂分子量小、易挥发，可以简便地在低温蒸发处理过程中被除去。
根据本发明的实施例，所述浸渍的时间为30～60分钟。
根据本发明的实施例，低温蒸发处理的温度为50～75摄氏度。
附图说明
图1显示了根据本发明一个实施例的聚合物的结构示意图；
图2显示了根据本发明一个实施例的纳米颗粒的结构示意图；
图3显示了根据本发明另一个实施例的纳米颗粒的结构示意图；
图4显示了根据本发明一个实施例的制备聚合物的方法的流程图；
图5显示了根据本发明另一个实施例的制备聚合物的方法的流程图；以及
图6显示了根据本发明一个实施例的电树老化性能测试的样品结构图。
附图标记：
100：本体
10：纳米颗粒
20：介孔结构
30：填充材料。
具体实施方式
下面详细描述本发明的实施例，所述实施例的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的，仅用于解释本发明，而不能理解为对本发明的限制。
在本发明的第一方面，本发明提出了一种具有抑制电树枝生长能力的聚合物纳米介孔复合材料。根据本发明的实施例，参考图1以及图2，该复合材料包括：本体100以及纳米颗粒10。具体地，根据本发明的实施例，本体100为绝缘聚合物，纳米颗粒10分散在本体100中，且纳米颗粒10具有介孔结构20。由此，可利用纳米颗粒中的介孔增加纳米颗粒与本体之间的相界面区域，改善纳米颗粒的团聚问题。介孔结构(介孔通道)可以有效吸附电树老化产物中的气体分子，缓解电树区域的电气应力以及机械应力。该复合材料可以减缓电树生长，延长使用寿命。
发明人经过深入研究以及大量实验发现，在上述形成电树枝的微放电缺陷区域，由于电树老化产物的存在，使得该区域的电气应力以及机械应力均大于聚合物中的完好区域。因此上述微放电缺陷区域极易生长，并最终导致绝缘聚合物的击穿。而上述电树老 化产物，多为酸性气体分子。由于复合材料中的上述气体分子无法排出复合材料的本体，从而造成该区域的电气应力以及机械应力较大。传统的具有抑制电树生长功能的聚合物，通过在聚合物中掺杂具有高绝缘强度的无机物颗粒，在形成电树的微放电缺陷生长的路径上形成“障碍”，实现阻挡或者延缓电树的生长。发明人经过深入研究以及大量实验发现，采用微米颗粒进行掺杂的传统的具有抑制电树生长功能的聚合物中，常常出现掺杂后复合材料整体的介电损耗以及击穿强度等性能下降的问题，而这一问题主要是由于引入了尺寸较大的微米颗粒，从而影响了材料整体的性能。而如果降低掺杂颗粒的尺寸，采用纳米颗粒进行掺杂来实现抗电树生长，则会出现纳米颗粒掺杂浓度难以调控的问题。如前所述，由于纳米颗粒尺寸较小，表面能较大，掺杂浓度高时会导致纳米颗粒团聚形成微米级团块，从而对复合材料整体的性能造成影响；而当掺杂浓度较低时，则无法在微缺陷周围形成足够多的“障碍”阻挡电树的生长。并且，上述利用微米颗粒或者纳米颗粒进行掺杂的聚合物，并不能解决电树老化产物中的气体分子不能排出聚合物本体所带来的问题。
基于发明人的上述发现，本发明采用具有介孔尺度(50-2nm)孔道结构的纳米级无机物颗粒代替传统的纳米颗粒。由于具有介孔结构20的纳米颗粒10具有极大的比表面积，因此根据本发明的复合材料能够引入比传统纳米复合材料更多的相界面区域，通过增强纳米颗粒吸附电树老化产物的能力，实现抑制电树的生长。因而，根据本发明实施例的复合材料可以通过更低的掺杂浓度实现抑制电树生长，并解决了纳米颗粒在掺杂过程中团聚的问题。并且，具有较小尺寸以及较低浓度的纳米颗粒10也不会对本体100的性能造成负面影响。具体地，根据本发明的实施例，纳米颗粒10依靠具有介孔结构20的疏松框架结构与本体100相互贯穿，利用纳米颗粒10较强的绝缘强度，能够有效地阻挡电树枝缺陷的形成和发展。
具体地，根据本发明的实施例，纳米颗粒10可以含有二氧化硅、硅酸盐、硅铝酸盐、磷酸盐以及金属氧化物的至少之一。参考图2，在上述纳米级(粒径为100nm～200nm或更小)的无机物形成的纳米颗粒10中，存在介孔结构20。例如，根据本发明的具体实施例，可以采用介孔硅、沸石等作为纳米颗粒10，此类材料的制备工艺较为成熟且成本较低，目前主要有水热合成法，水热转化法和离子交换法等。由此，可以利用上述制备工艺成熟、化学性质稳定且成本低廉的物质形成纳米颗粒。并且，上述无机材料形成的纳米颗粒10具有较强的绝缘强度，因此可以起到良好的防止电击穿以及抑制电树生长的作用。在制备根据本发明的复合材料的过程中，具有介孔结构20的纳米颗粒10由于具有多孔结构，可以使得本体100的聚合物分子链伸入介孔结构中，并形成互穿网络，从而能够实现较好的无机-有机两相相容性，并进一步提高该复合材料的各方面性 能。因此，对于根据本发明实施例的复合材料，不需要对纳米颗粒10进行特别的化学修饰就可以得到较好的分散性。
根据本发明的实施例，基于聚合物的总质量，纳米颗粒10的含量为0.1～0.5wt％。如前所述，由于根据本发明实施例的纳米颗粒10中含有介孔结构20，因此可以引入比传统纳米复合材料更多的相界面区域，通过增强纳米颗粒吸附电树老化产物的能力，实现抑制电树的生长。由此，可以通过较低的掺杂浓度，实现抑制电树生长。
需要说明的是，在本发明中，构成聚合物本体100的具体材料不受特别限制，本体100可以为本领域常用的绝缘材料。例如，可以为绝缘的高分子材料，具体地，根据本发明的实施例，本体100可以为低密度聚乙烯(LDPE)、交联聚乙烯(XLPE)、环氧树脂以及聚丙烯(PP)等。本领域技术人员可以根据实际需求，选择适当的绝缘聚合物形成根据本发明实施例的本体100。
为了进一步提高该复合材料的绝缘性能，特别是高温运行条件下的绝缘性能，根据本发明的实施例，参考图3，纳米颗粒10还可以进一步包括填充材料30。发明人经过深入研究以及大量实验发现，具有介孔结构的纳米材料，例如介孔分子筛等，在高温条件下吸附能力有限，常温下吸附的气体分子在温度升高后也会脱附，因此针对高温运行条件，如大容量输电电缆等，纳米颗粒10吸附的电树老化产物气体分子容易脱附回到本体100中。发明人经过大量实验发现，采用有机胺作为化学填充剂，在介孔结构20中形成填充材料30，可以利用其在一定温度范围内对电树老化的酸性气体产物(主要是二氧化碳)进行稳定的吸附。具体地，填充材料30可以由选自聚乙烯亚胺、N-甲基二乙醇胺(MDEA)以及三乙烯硫代磷酸胺(TEPA)的至少之一形成，且填充材料30填充在介孔结构20中。通过向纳米颗粒10的介孔结构20中添加有特定官能基团，例如，氨基，的填充材料30，可以实现对聚合物电树老化产物的稳定吸附。上述有机胺类材料形成的填充材料30，能够加强纳米颗粒10吸附酸性电树老化气体产物的能力，从而可以提高复合材料抑制电树枝生长的能力。需要说明的是，为了保证具有填充材料30的复合材料的整体性能以及抗电击穿能力，形成填充材料30的材料需要具有相对较低的分子量和较好的热稳定性。由于目前常采用熔融共混技术制备含有掺杂颗粒的聚合物，因此较小的分子量以及较好的热稳定性有利于保证熔融共混技术的制备过程不会对含有填充材料30的聚合物造成负面影响。例如，根据本发明的具体实施例，通过二氧化碳氛围下的热重分析(TGA)，聚乙烯亚胺(PEI)在挤塑电缆的工作温度(60～150℃)范围内表现出明显的二氧化碳吸收峰，而在挤塑电缆的加工成型温度(180～200℃)下二氧化碳会再次脱附。因此用PEI作为填充材料30可以在电缆运行温度下实现电树微缺陷降解产物(二氧化碳)的稳定吸附，同时该填充材料30可以保证在正常的挤塑加 工过程后保持活性。
综上所述，根据本发明实施例的复合材料具有以下特征以及优点：
1、通过具有介孔结构的纳米颗粒掺杂，可以利用介孔结构增加纳米颗粒与本体之间的相界面区域，改善纳米颗粒掺杂过程中的团聚问题。
2、利用介孔结构能够有效吸附电树老化产物中的气体分子，从而缓解电树区域的电气应力以及机械应力，减缓电树生长。
3、根据本发明实施例的复合材料中，纳米颗粒含量低，可以通过低浓度掺杂实现有效的抗击穿、延缓电树生长，从而可以提高该聚合物在强电场工作条件下的性能。
4、根据本发明实施例的复合材料，在具有较好的抗击穿、延缓电树生长能力的前提下，能够保证聚合物自身的性能不受影响。
在本发明的另一方面，本发明提出了一种制备前面所述的具有抑制电树枝生长能力的聚合物纳米介孔复合材料的方法。根据本发明的实施例，参考图4，该方法包括：
S100混合
根据本发明的实施例，在该步骤中，将纳米颗粒以及本体混合。其中，该纳米颗粒具有介孔结构。由此，可利用纳米颗粒中的介孔结构增加纳米颗粒与本体之间的相界面区域，改善纳米颗粒掺杂过程中的团聚问题，并且可以利用介孔结构有效吸附电树老化产物中的气体分子，从而缓解电树区域的电气应力以及机械应力，从而减缓电树生长。关于纳米颗粒的具体组成以及结构，前面已经进行了详细的描述，在此不再赘述。
为了进一步提高利用该方法制备的聚合物防止电击穿、延缓电树生长的能力，根据本发明的实施例，参考图5，在步骤(1)之前还可以进一步包括：
S10填充填充材料
根据本发明的实施例，在该步骤中，在纳米颗粒的介孔结构中填充填充材料。由此，可以利用上述有机胺类物质构成的填充材料，加强纳米颗粒吸附电树老化产物中的酸性气体分子的能力，从而可以增强该复合材料抗绝缘老化的能力。关于填充材料的具体种类以及作用，前面已经进行了详细的描述，在此不再赘述。
具体地，根据本发明的实施例，填充材料可以通过下列步骤设置：
(a)浸渍处理
根据本发明的实施例，在该步骤中，将纳米颗粒加入到填充材料溶液中进行浸渍处理。具体地，配制含有填充材料的溶液，将纳米颗粒浸入该溶液中，进行搅拌浸渍处理。其中，本领域技术人员能够理解，含有填充材料的溶液的溶剂的具体组成不受特别限制，只要与填充材料具有较好的相容性，且溶剂分子本身易挥发，便于在后续处理中利用简单的干燥等操作除去即可。例如，根据本发明的具体实施例，溶剂可以采用甲醇、乙醇、 氯仿、二甲基甲酰胺以及丙酮的至少之一。根据本发明的实施例，在上述填充材料溶液中，填充材料的含量可以为10～50wt％，例如，根据本发明的具体实施例，浸渍液中填充材料浓度可以为10～20wt％，浸渍的时间可以为30～60分钟。制备获得的纳米颗粒中，基于纳米颗粒的总质量，填充材料的含量可以为10～50wt％。上述溶剂与填充材料具有较好的相容性，且溶剂分子较小，易挥发，便于后续步骤中除去溶剂获得根据本发明实施例的纳米颗粒。
(b)低温蒸发处理
根据本发明的实施例，在该步骤中，采用低温蒸发处理经过浸渍处理的纳米颗粒，除去所述填充材料溶液中的溶剂，以便获得纳米颗粒。具体地，过滤含有纳米颗粒的填充材料溶液，获得浸渍有填充材料的纳米颗粒，然后通过蒸发，除去残留的溶剂。例如，根据本发明的实施例，干燥温度可以为50～75摄氏度。由此，可以简便地将填充材料填充到纳米颗粒的介孔结构中。
S200熔融共混
根据本发明的实施例，在该步骤中，利用熔融共混技术，获得根据本发明实施例的复合材料。由此，可以利用熔融共混制备过程中较高的熔融温度，除去纳米颗粒的介孔中有可能吸附的杂质，从而可以提高该复合材料的防电树生长性能。具体地，可以将纳米颗粒以及本体组成的混合物，通过熔融共混，形成根据本发明的复合材料。关于形成根据本发明实施例的本体的具体材料，前面已经进行了详细的描述，在此不再赘述。在聚合物本体以及纳米颗粒的混合物中，纳米颗粒的含量可以为0.1～0.5wt％。如前所述，由于根据本发明实施例的纳米颗粒中含有介孔结构，因此可以引入比传统纳米复合材料更多的相界面区域，通过增强纳米颗粒吸附电树老化产物的能力，实现抑制电树的生长。由此，可以通过较低的掺杂浓度，实现抑制电树生长。
综上所述，根据本发明实施例的方法具有以下特征以及优点：
1、通过具有介孔结构的纳米颗粒掺杂，可以利用介孔结构增加纳米颗粒与本体之间的相界面区域，改善纳米颗粒掺杂过程中的团聚问题。
2、利用介孔结构能够有效吸附电树老化产物中的气体分子，从而缓解电树区域的电气应力以及机械应力，减缓电树生长。
3、根据本发明实施例的聚合物中，纳米颗粒含量低，可以通过低浓度掺杂实现有效的抗击穿、延缓电树生长，从而可以提高该复合材料在强电场工作条件下的性能。
4、根据本发明实施例的复合材料，在具有较好的抗击穿、延缓电树生长能力的前提下，能够保证聚合物自身的性能不受影响。
5、该方法加工步骤简便、生产成本低廉，有利于利用该方法制备的聚合物的大范 围推广。
下面通过具体实施例对本发明进行说明，需要说明的是，下面的具体实施例仅仅是用于说明的目的，而不以任何方式限制本发明的范围，另外，如无特殊说明，则未具体记载条件或者步骤的方法均为常规方法，所采用的试剂和材料均可从商业途径获得。
实施例1制备含有纳米颗粒的复合材料
采用聚丙烯(PP)作为聚合物本体，粒径为100-200纳米的MCM-41介孔二氧化硅为纳米颗粒。将介孔二氧化硅与PP混合，混合物中介孔二氧化硅的含量为0.5wt％。设置熔融共混温度为200摄氏度。将上述混合物置于密炼机中，设置转子转速60转/分钟，密炼时间10分钟。由此，获得PP/MCM-41复合材料。
实施例2制备含有填充材料以及纳米颗粒的复合材料
采用粒径为100-200纳米的MCM-41介孔二氧化硅为纳米颗粒。
采用甲醇以及聚乙烯亚胺配置50wt％的PEI溶液，将粒径为100-200纳米的MCM-41介孔二氧化硅浸入PEI溶液中，在室温下浸渍搅拌30分钟。过滤后在50摄氏度下干燥除去甲醇溶剂，获得具有PEI填充的纳米颗粒。
将具有PEI填充的纳米颗粒与PP混合，混合物中介孔二氧化硅的含量为0.5wt％。设置熔融共混温度为200摄氏度。将上述混合物置于密炼机中，设置转子转速60转/分钟，密炼时间10分钟。由此，获得PP/MCM-41-PEI复合材料。
对比例1制备含有实心二氧化硅纳米颗粒的复合材料
制备方法同实施例1，所不同的是，采用与介孔纳米颗粒粒径相近(200～300nm)的实心二氧化硅作为纳米颗粒进行掺杂。混合物中实心二氧化硅的含量也为0.5wt％。
对比例2制备含有实心二氧化硅纳米颗粒的复合材料
为了考察体积掺杂百分比对于聚合物电树老化性能的影响，发明人对实施例1以及实施例2中使用的介孔二氧化硅纳米颗粒的孔隙率进行了检测。由氮气吸脱附法测定的所用MCM-41介孔材料的孔容约为0.3ml/g，考虑到二氧化硅的密度约为2.2g/cm3，介孔二氧化硅纳米颗粒的密度为2.2/(1+0.3×2.2)＝1.33g/cm3。由此，计算得出介孔二氧化硅纳米颗粒以及实心二氧化硅纳米颗粒的密度比为1:1.66。因此，当聚合物中实心二氧化硅纳米颗粒的体积百分比0.83％时，与实施例1以及实施例2中掺杂介孔二氧化硅纳米颗粒的体积掺杂百分比相似。
因此，对比例2的制备方法同实施例1，所不同的是，采用与介孔纳米颗粒粒径相近(200～300nm)的实心二氧化硅作为纳米颗粒进行掺杂。混合物中实心二氧化硅的体积百分比为0.83％。
电树老化性能测试：
采用无规共聚聚丙烯PP-R/4220(燕山石油化工有限公司提供)作为对照，对对比例1、对比例2、实施例1以及实施例2中制备的聚合物延缓电树老化性能进行测试。用于电树老化的样品通过平板硫化机和钢模热压成型制得。热压前，将不锈钢针电极插入一块导电橡胶，并与样品材料一同预埋在钢模中，导电橡胶便于外接电极的接触，所得样品示结构如图6所示。其中，压膜获得的样品为长方体型，长15mm，宽3mm，高20mm。导电胶位于长方体样品顶部，与导电胶连接的针电极的底部距离长方体样品的底部距离为7mm。
在本实施例的电树试验中，上述样品加持在两块平板电极之间，电极与导电橡胶接触，另一电极接地。试验中所施加的电压为工频50Hz交流30kV。为了验证所述材料在实际电力电缆运行高温条件(60～90℃)下抑制电树老化的能力，电树老化实验需要在高温条件下进行。此外，起树实验是衡量绝缘材料耐电树老化性能的重要指标，而起树过程需要通过光学显微镜持续观测才能得到，难以在高温条件下实施。因此，本实施例采用两种电树老化试验分别研究电树起树和高温条件下的电树老化特性。
电树实验I：在室温下持续观测样品电树老化的各个阶段(包括起树阶段，电树生长，以及电树枝化)，分别得到不同样品在电树起始、电树生长至250微米(单一电树通道生长)，以及电树生长至375微米(电树通道出现明显枝化)时所需要的时间。
电树实验II：在80℃高温条件下，将不同样品加压老化1，2，5，10，20分钟后，记录最长电树枝的尺寸，代表样品的老化程度。
实验结果表明，实施例1以及实施例2，即掺杂了介孔二氧化硅材料的纳米复合物(PP/MCM-41-PEI和PP/MCM-41)，比纯PP基材以及对比例1和对比例2的实心二氧化硅纳米颗粒的复合材料(PP/SiO2)均表现出更强的抑制电树生长的能力，实施例1以及实施例2电树尺寸的老化时间延长了2～5倍。高温电树实验进一步验证，负载有机胺的介孔纳米颗粒能够进一步抑制高温下的电树枝老化。相同的老化时间下，PP/MCM-41-PEI复合材料比PP/MCM-41复合材料表现出了更低的劣化程度，前者电树枝尺寸仅为后者的一半左右。
电气击穿性能测试：
复合材料的介电强度，主要通过对薄膜样品的电气击穿实验来表征。首先采用平板硫化机和钢模将所述PP及各种复合材料热压成厚度为60～80微米的薄膜，然后将薄膜样品加持在直径为1厘米的球-球电极之间并浸泡在硅油中，均匀升高电极电压，在样品击穿瞬间由实验系统自动记录击穿电压值。本实施例进行了工频交流击穿和直流击穿实验，升压速率分别为1kV有效值/秒和1kV/秒，实验方法和装置分别参照国际电工委 员会标准IEC 60243-1:1998和IEC 60243-2:2001。
每个样品进行30次击穿实验，计算得到击穿场强后，筛选与平均值偏差小于一个标准差的数据(约20个数据点)作为有效实验数据。根据国际电工委员会推荐的电气绝缘击穿数据处理指南IEC-62539:2007，采用二参数Weibull分布对数据进行拟合作图，公式如下:
Figure PCTCN2016108082-appb-000001
其中E为数据点的击穿场强，α为63.2％概率特征值，β为Weibull分布的形状参数，用于表征实验数据的离散性。由此可得到63.2％击穿概率点对应的击穿场强，根据国际电工委员会电气绝缘击穿数据处理指南IEC-62539:2007，该击穿场强可以代表样品的击穿强度。
工频交流击穿实验结果表明，实施例1以及实施例2的交流击穿强度(α值)均在200～213kV/mm，差异不明显。可以认为纳米掺杂对交流击穿强度影响不大，本发明所述材料不会降低材料的交流击穿强度。
直流击穿实验结果表明，掺杂负载有机胺的介孔纳米颗粒的复合材料(实施例2)击穿强度达到了将近550kV/mm，比纯基材PP的直流击穿强度提高了约18％。而掺杂相同质量(对比例1)和体积百分比的同粒径实心二氧化硅纳米颗粒的复合材料(对比例2)，其击穿强度为470～490kV/mm，比纯基材PP提高了不到5％。因此，本发明所述的纳米介孔复合材料在直流击穿强度方面远高于传统的纳米复合材料。
在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。
尽管上面已经示出和描述了本发明的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本发明的限制，本领域的普通技术人员在本发明的范围内可以对上述实施例进行变化、修改、替换和变型。

Claims (12)

  1. 一种具有抑制电树枝生长能力的聚合物纳米介孔复合材料，其特征在于，包括：
    本体，所述本体为绝缘聚合物；以及
    纳米颗粒，所述纳米颗粒分散于所述本体中，且所述纳米颗粒具有介孔结构。
  2. 根据权利要求1所述的聚合物纳米介孔复合材料，其特征在于，所述纳米颗粒含有二氧化硅、硅酸盐、硅铝酸盐、磷酸盐以及金属氧化物的至少之一。
  3. 根据权利要求1所述的聚合物纳米介孔复合材料，其特征在于，所述纳米颗粒进一步包括：填充材料，所述填充材料填充在所述介孔结构中。
  4. 根据权利要求3所述的聚合物纳米介孔复合材料，其特征在于，所述填充材料含有聚乙烯亚胺、N-甲基二乙醇胺以及三乙烯硫代磷酸胺的至少之一。
  5. 根据权利要求1所述的聚合物纳米介孔复合材料，其特征在于，基于所述聚合物的总质量，所述纳米颗粒的含量为0.1～0.5wt％。
  6. 根据权利要求1所述的聚合物纳米介孔复合材料，其特征在于，所述本体包括低密度聚乙烯、交联聚乙烯、环氧树脂以及聚丙烯。
  7. 一种制备权利要求1-6任一项所述的聚合物纳米介孔复合材料的方法，其特征在于，包括：
    (1)将纳米颗粒以及本体混合，以便获得混合物；以及
    (2)对所述混合物进行熔融共混处理，以便获得所述聚合物。
  8. 根据权利要求7所述的方法，其特征在于，在步骤(1)之前，进一步包括：在所述纳米颗粒的所述介孔结构中填充填充材料。
  9. 根据权利要求8所述的方法，其特征在于，在所述纳米颗粒的所述介孔结构中填充所述填充材料是通过下列步骤完成的：
    (a)将所述纳米颗粒加入到填充材料溶液中进行浸渍处理；
    (b)对经过所述浸渍处理的纳米颗粒进行低温蒸发处理，以便在所述纳米颗粒的所述介孔结构中填充所述填充材料。
  10. 根据权利要求9所述的方法，其特征在于，所述填充材料溶液包含所述填充材料以及溶剂，所述溶剂含有甲醇、乙醇、氯仿、二甲基甲酰胺以及丙酮的至少之一。
  11. 根据权利要求9所述的方法，其特征在于，所述浸渍的时间为30～60分钟。
  12. 根据权利要求9所述的方法，其特征在于，低温蒸发处理的温度为50～75摄氏度。
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