CN109096572A - A kind of olefin polymerization nanometer composite insulating material and preparation method thereof of high dc breakdown intensity - Google Patents
A kind of olefin polymerization nanometer composite insulating material and preparation method thereof of high dc breakdown intensity Download PDFInfo
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Abstract
The invention discloses a kind of olefin polymerization nanometer composite insulating materials and preparation method thereof of high dc breakdown intensity.The polyolefin dielectric insulation composite material includes 96~99.75% polyolefin dielectric base body and 0.25~4% modified Nano particle filler；The modified Nano particle filler is the nanoparticle of voltage stabilizer functionalization.The present invention is reacted by click chemistry is grafted voltage stabilizer as filler in nanoparticle surface, and the dc breakdown intensity of composite material can be improved.Wherein, voltage stabilizer can not only capture high energy electron, consume its energy to reduce the electrical break down of electronics and polymer collisions initiation, and can be improved the compatibility between nanoparticle and polyolefin.And nanoparticle can then play the role of inhibiting voltage stabilizer migration and space charge accumulation and injection.Obtained composite material has the characteristics that high dc breakdown intensity and high thermal stability, is suitable for high-voltage direct-current cable insulation field.
Description
Technical field
The invention belongs to high voltage electrical insulating materials preparation fields, are related to electric insulation polyolefin dielectric, specifically relate to
And a kind of olefin polymerization nanometer composite insulating material and preparation method thereof of high dc breakdown intensity.
Background technique
The dielectric dielectric constant of polyolefin is low, dielectric loss is low, resistivity is high, dc breakdown intensity is high, thermodynamics
The excellent and excellent chemicals-resistant characteristic of energy, is widely used in high voltage electrical insulation applications.Under high DC electric field, high energy
Amount electronics and polymer molecular chain, which collide, causes serious voltage ageing phenomenon.In addition, a large amount of joules that DC current generates
Heat can significantly reduce the breakdown strength of polymer.Therefore, it is necessary to improve the dielectric dc breakdown intensity of polyolefin and thermostabilization
Property, and then improve the service life of electrical insulating material.Voltage stabilizer in nanoparticle surface grafting captures high energy electron
And its energy is consumed, reduce high energy electron and polymer collisions bring voltage ageing.Meanwhile voltage stabilizer connects as organic matter
Branch enhances nanofiller and the dielectric compatibility of polyolefin and interface binding power on inorganic nano-particle surface.It is inorganic to receive
Rice corpuscles can form a large amount of charge trap, limitation space charge movement in particle surface with special skin effect with it
Ability changes distribution of space charge, to improve the breakdown strength of nanocomposite.In addition, by voltage stabilizer small molecule
It is grafted on nanoparticle surface and effectively inhibits migratory behaviour of the small molecule in polyolefin dielectric.By voltage stabilizer and
Nanoparticle combines, and can learn from other's strong points to offset one's weaknesses, and prepares the nanometer insulated compound material of high dc breakdown intensity and high thermal stability
Material.
Summary of the invention
In view of the shortcomings of the prior art, it is an object of the invention to efficiently promoted the dc breakdown intensity of electrical insulating material with
Suitable for high-voltage direct-current working environment, the olefin polymerization nanometer composite insulating material and its system of a kind of high dc breakdown intensity are provided
Preparation Method.By the grafting and activating voltage stabilizer on the nanoparticle that silane coupling agent is modified, voltage stabilizer function is formed
The nanoparticle of change.The voltage stabilizer being grafted on nanoparticle has the ability for capturing high energy electron and consuming its energy, from
And electronics and the electrical breakdown of polymer collisions bring are reduced, it is furthermore possible to improve compatible between inorganic nano-particle and polyolefin
Property and interface binding power.Nanoparticle has the function of inhibiting voltage stabilizer migration and inhibits space charge injection and accumulation.
Therefore, the nanoparticle of voltage stabilizer functionalization can promote polyolefin dielectric dc breakdown intensity and thermal stability, from
And composite material is made to have excellent electrical insulation properties.
The purpose of the present invention is what is be achieved through the following technical solutions:
The present invention provides a kind of olefin polymerization nanometer composite insulating material of high dc breakdown intensity, the polyolefin electricity is situated between
Matter insulating composite material is in terms of mass fraction 100%, including 96~99.75% polyolefin dielectric base body and 0.25~4%
Modified Nano particle filler；
The modified Nano particle filler is the nanoparticle of voltage stabilizer functionalization；The voltage stabilizer is selected from
Diphenylthanedione, to methoxyl group diphenylthanedione, to hydroxy diphenyl second diketone, to amide groups diphenylthanedione, right
Aminodiphenyl base second diketone, 9- thioxanthones, 2- hydroxyl -9- thioxanthones, 2- hydroxyl -4- methoxyl group -9- thioxanthones, 2- hydroxyl -4-
Amide groups -9- thioxanthones, 2- amino-4-methoxyl -9- thioxanthones it is one or more.
Preferably, the nanoparticle is nano silica, nano magnesia, nano zine oxide, nanometer titanium dioxide
One or more of titanium, nano aluminium oxide, nano barium phthalate, nm-class boron nitride and graphene.
Preferably, the nanoparticle of the voltage stabilizer functionalization preparation the following steps are included:
A. the activation of voltage stabilizer: dispersing voltage stabilizer in acid solution and carry out hydroxylating, then incites somebody to action
The hydroxylating voltage stabilizer arrived is reacted with methacrylic chloride, and products therefrom is again with acetic anhydride, the voltage activated
Stabilizer；
B. silane coupling agent coats nanoparticle: nanoparticle being reacted with silane coupling agent, obtains silane coupling agent packet
The nanoparticle covered；
C. the nanoparticle of voltage stabilizer functionalization: the nanoparticle of silane coupling agent cladding, the voltage of activation is steady
Determine agent and initiator for reaction to get.
Preferably, in step A, the acid solution includes the acetic acid and hydrobromic acid that volume ratio is 1:1~5, and the voltage is steady
The solid-to-liquid ratio for determining agent and acid solution is 1:10~50, hydroxylating 10~48 hours；The hydroxylating voltage stabilizer and first
The mass ratio of base acryloyl chloride is 1:1, is reacted 2~5 hours under ice bath；The mass ratio of products therefrom and acetic anhydride be 1:1,60~
It is reacted 10~48 hours at 100 DEG C.The solid-to-liquid ratio of above-mentioned reaction is excessively high, then reactant is difficult to effectively disperse in a solvent, causes
Reaction carries out incomplete；If solid-to-liquid ratio is too low, reactant is reduced in solvent kind concentration, and reaction rate substantially reduces.
Preferably, in step A, after the hydroxylating voltage stabilizer is dissolved in methylene chloride, then it is anti-with methacrylic chloride
It answers；After the product is dissolved in pyridine, then with acetic anhydride；
The solid-to-liquid ratio of the hydroxylating voltage stabilizer and methylene chloride is 1:5-20；The solid-to-liquid ratio of the product and pyridine
For 1:5-25.The solid-to-liquid ratio is excessively high, then reactant is difficult to effectively disperse in a solvent, causes reaction to carry out incomplete；If
Solid-to-liquid ratio is too low, then reactant is reduced in solvent kind concentration, and reaction rate substantially reduces.
Preferably, in step B, the silane coupling agent is gamma-mercaptopropyltriethoxysilane, the quality with nanoparticle
Than for 1:0.5~2；The reaction is specifically reacted 12~60 hours at 80~100 DEG C.If silane coupling agent dosage is excessive,
It will cause it and auto polymerization occur in a solvent, the effect of cladding nanoparticle is not achieved；If silane coupling agent dosage is very few,
Cause covered effect bad, the demand of reaction in next step is not achieved in nanoparticle surface number of functional groups.
Preferably, in step C, the dosage of the voltage stabilizer of the activation be nanoparticle quality in step B 5~
20%；If voltage stabilizer dosage is excessive, it will lead to voltage stabilizer and be adsorbed on nanoparticle surface, so that voltage stabilizer
It is difficult to react by click chemistry by the end of nanoparticle surface；If voltage stabilizer dosage is very few, it will lead to be grafted to and receive
Content on rice corpuscles is less, does not have the effect for efficiently improving polyolefin dielectric insulation composite material.
The mass ratio of the activation voltage stabilizer and initiator is 1:0.25~4；Initiator amount is excessive, it is difficult to go
It removes, dosage is very few cannot to cause click chemical reaction completely, and the grafting rate of voltage stabilizer reduces.
The reaction is specifically reacted 12~60 hours using 60~70 DEG C under nitrogen atmosphere.
Preferably, in step B, the nanoparticle is dispersed in toluene, is then reacted with silane coupling agent；The nanometer
The solid-to-liquid ratio of particle and solvent is 1:20-50；If solvent usage is very few, causes silane coupling agent concentration to increase, make it molten
The probability that auto polymerization occurs in agent greatly improves, and it is bad to eventually lead to covered effect.
The solvent is toluene, ethyl alcohol, ethyl alcohol water mixed solvent or water.
In step C, the reaction carries out in n,N-Dimethylformamide；The nanoparticle of the silane coupling agent cladding
Solid-to-liquid ratio with N,N-dimethylformamide is 1:5-25.The solid-to-liquid ratio is excessively high, and reactant cannot be completely dispersed, and reduces voltage
Stabilizer grafting rate, solid-to-liquid ratio is too low, then reduces reaction rate.
It is further preferred that the nanoparticle that silane coupling agent coats is dispersed in n,N-Dimethylformamide, and in a water bath
It is 0.5-4 hours ultrasonic.
It is highly preferred that the initiator is azodiisobutyronitrile.
Preferably, the polyolefin dielectric base body be high density polyethylene (HDPE), low density polyethylene (LDPE), isotactic polypropylene,
One of syndiotactic polypropylene, random polypropylene, ethylene-octene copolymer, ethylene-propylene copolymer are a variety of.
The present invention also provides a kind of preparation method of the polyolefin dielectric insulation composite material of high dc breakdown intensity,
Described method includes following steps:
S1, by part polyolefin dielectric base body and modified Nano particle filler melt blending, obtain masterbatch；
S2, by masterbatch and remaining polyolefin dielectric base body in melt blending, obtain the polyene of high dc breakdown intensity
Hydrocarbon dielectric insulation composite material granular；
S3, the polyolefin dielectric insulation composite material granular hot pressing of high dc breakdown intensity is formed a film, through high annealing
Afterwards to get the polyolefin dielectric insulation composite material of the high dc breakdown intensity.
Preferably, in step S1, the polyolefin dielectric base body and modified Nano particle filler are in minipool rheology
Melt blending in instrument, condition are 140~200 DEG C, 40~60rmp, 5~15min.
Preferably, in step S2, the masterbatch and polyolefin the dielectric base body melt blending in minipool rheometer,
Condition is 140~200 DEG C, 40~60rmp, 5~15min.
Preferably, in step S3, the polyolefin dielectric insulation composite material granular of the high dc breakdown intensity exists
The processing conditions that hot pressing forms a film in vulcanizing press is 150~210 DEG C of temperature, 10~15MPa of pressure, preheats 2~20min, heat
2~20min is pressed, 2~20min is cold-pressed；The condition of the high annealing is 80~120 DEG C of 8~12h of vacuum annealing.
Preferably, in step A, the quality of the part polyolefin dielectric base body is polyolefin dielectric base body gross mass
4.76%-80.40%.
The present invention does filler using nanoparticle, makees matrix with the exsertile polyolefin dielectric medium of electric insulating quality, passes through
Click chemistry is grafted upper voltage stabilizer in nanoparticle surface, to realize that low sizing additive amount can be obviously improved polyolefin
The purpose of dielectric dc breakdown intensity and thermal stability prepares the polyene with high dc breakdown intensity and high thermal stability
Hydrocarbon insulating composite material.
Compared with prior art, the present invention have it is following the utility model has the advantages that
1, it selects the nanoparticle of voltage stabilizer functionalization as filler, is selection voltage stabilization compared with the existing technology
Agent will lead to that the stability in insulating materials is poor as additive, and the high problem of mobility, the present invention is for the first time by voltage stabilizer
Small molecule reduces its mobility in polyolefin by the end of the surface of inorganic nano-particle；
2, the nanoparticle of voltage stabilizer functionalization added by the present invention, due to inorganic nano-particle surface modification
Organic matter, so improve its compatibility and interface binding power between polymeric matrix, band can more capture electronics
Trap；
3, the nanoparticle of voltage stabilizer functionalization added by the present invention, in conjunction with voltage stabilizer and nanoparticle
Advantage in terms of improving polyolefin dielectric dc breakdown intensity realizes low sizing additive amount i.e. dc breakdown can be improved and is strong
The effect of degree.
4, the present inventor selects suitable polyolefin as matrix, the electricity of different content by continuous research
It presses the nanoparticle of stabilizer functionalization as filler, has obtained expected inventive result.Prepared high dc breakdown intensity
Polyolefin dielectric insulation composite material there is dc breakdown intensity height and the strong performance of thermal stability, be suitable for high voltage electricity
Gas insulation applications etc..
Detailed description of the invention
Upon reading the detailed description of non-limiting embodiments with reference to the following drawings, other feature of the invention,
Objects and advantages will become more apparent upon:
Fig. 1 is the preparation process schematic diagram of the nanoparticle of voltage stabilizer functionalization of the present invention；
Fig. 2 is the dc breakdown intensity Weibull distribution map of polyolefin insulation composite material prepared by embodiment 1；
Fig. 3 is the thermogravimetric curve figure of polyolefin insulation composite material prepared by embodiment 2；
Fig. 4 is the transmission electron microscope photo of polyolefin insulation composite material frozen section prepared by embodiment 3.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, several changes and improvements can also be made.These belong to the present invention
Protection scope.
Following embodiment is using minipool rheometer (minilab II, German HAAKE company) to filler and polyolefin-based
Body carries out melt blending；Hot pressing is carried out to composite polyolefine material using vulcanizing press (Shanghai rubber machinery plant, QLB-D type)
Molding.
The dc breakdown intensity of olefin polymerization nanometer insulating composite material prepared by following embodiment uses DC high voltage
Generator (AHDZ-10/100 type, upper sea blue wave Co., Ltd) test.
The dispersibility of filler uses Transmission Electron in olefin polymerization nanometer insulating composite material prepared by following embodiment
Microscope (TEM) (JEOL JEM-2100 type, Jeol Ltd.) is observed.
The thermal stability of sample prepared by following embodiment uses thermogravimetric analyzer (TG 209F3 type, German Netzsch
Company) it is measured.
Embodiment 1
The present embodiment is related to a kind of olefin polymerization nanometer composite insulating material of high dc breakdown intensity, the composite material by
The low density polyethylene (LDPE) of 98% mass fraction is made as the nanoparticle of the voltage stabilizer functionalization of matrix and 2% mass fraction
For filler composition.Wherein the preparation process of the nanoparticle of voltage stabilizer functionalization is as shown in Figure 1, pass through following steps system
It is standby:
A, the activation of voltage stabilizer: selection is scattered in hydrobromic acid and acetum (hydrogen to methoxyl group diphenylthanedione
Bromic acid acetic acid volume ratio is reaction in 5:1), solid-to-liquid ratio 1:20, back flow reaction 48h.Then hydroxylating voltage stabilization will be obtained
Agent is dissolved in methylene chloride, and solid-to-liquid ratio 1:10 is 1 to 1 with methacrylic chloride feed ratio, and ice bath reaction 4 is small under nitrogen protection
When.Products therefrom is dissolved in pyridine, and solid-to-liquid ratio 1:20 is reacted 40 hours with 1 to 1,80 DEG C of acetic anhydride feed ratio, activated
Voltage stabilizer.
B, silane coupling agent coats nanoparticle: nano magnesia being dispersed in toluene, solid-to-liquid ratio 1:40, with silane idol
Join the anti-mass ratio 1:2 of agent, reaction 12 hours is carried out at 100 DEG C, obtains the nano magnesia of silane coupling agent cladding.
C, the nanoparticle of voltage stabilizer functionalization: the nanoparticle of silane coupling agent cladding, the voltage of activation is steady
Determine agent and initiator azodiisobutyronitrile mass ratio 100:20:5 is dispersed in n,N-Dimethylformamide, nanoparticle and solvent
Solid-to-liquid ratio 1:20 is reacted for 24 hours at 60 DEG C, under nitrogen protection to get the nano magnesia of voltage stabilizer functionalization.
The present embodiment further relates to a kind of preparation method of the olefin polymerization nanometer composite insulating material of high dc breakdown intensity, institute
The method of stating includes the following steps:
Step 1, by the nano magnesia of low-density polyethylene body described in 3.8g and 0.2g voltage stabilizer functionalization,
Melt blending in minipool rheometer, processing conditions are 150 DEG C, and 50rmp, 10min obtain masterbatch；
Step 2, it by masterbatch described in 1.6g and 2.4g low-density polyethylene body, is melted altogether in minipool rheometer
Mixed, processing conditions is 150 DEG C, and 50rmp, 10min obtain pellet；
Step 3, pellet is hot-forming in vulcanizing press, processing conditions is 160 DEG C of temperature, pressure 12MPa, preheating
2min, hot pressing 3min, be cold-pressed 20min, 80 DEG C of vacuum annealing 10h to get the high dc breakdown intensity polyolefin dielectric
Insulating composite material.
Embodiment 2
The present embodiment is related to a kind of olefin polymerization nanometer composite insulating material of high dc breakdown intensity, the composite material by
Nanoparticle conduct of the isotactic polypropylene of 99% mass fraction as the voltage stabilizer functionalization of matrix and 1% mass fraction
Filler composition.Wherein the preparation process of the nanoparticle of voltage stabilizer functionalization by following steps as shown in Figure 1, prepared:
A, the activation of voltage stabilizer: selection 2- hydroxyl -4- methoxyl group -9- thioxanthones is scattered in hydrobromic acid and acetum
Reaction in (hydrobromic acid acetic acid volume ratio is 2.5:1), solid-to-liquid ratio 1:30, back flow reaction 36h.Then hydroxylating voltage will be obtained
Stabilizer is dissolved in methylene chloride, and solid-to-liquid ratio 1:15 is 1 to 1 with methacrylic chloride feed ratio, and ice bath reacts under nitrogen protection
2 hours.Products therefrom is dissolved in pyridine, and solid-to-liquid ratio 1:15 is reacted 30 hours with 1 to 1,80 DEG C of acetic anhydride feed ratio, lived
The voltage stabilizer of change.
B, silane coupling agent coats nanoparticle: nano silica being dispersed in toluene, nanoparticle and solvent are solid
Liquor ratio 1:30, with the anti-mass ratio 1:0.5 of silane coupling agent, 100 DEG C carry out reaction 40 hours, obtain receiving for silane coupling agent cladding
Rice silica.
C, the nanoparticle of voltage stabilizer functionalization: the nanoparticle of silane coupling agent cladding, the voltage of activation is steady
Determine agent and initiator azodiisobutyronitrile mass ratio 100:16:8 is dispersed in n,N-Dimethylformamide, solid-to-liquid ratio 1:15,
65 DEG C, 12h is reacted under nitrogen protection to get the nano magnesia of voltage stabilizer functionalization.
The present embodiment further relates to a kind of preparation method of the olefin polymerization nanometer composite insulating material of high dc breakdown intensity, institute
The method of stating includes the following steps:
Step 1, by the nano magnesia of isotactic polypropylene matrix described in 3.8g and 0.2g voltage stabilizer functionalization, micro-
Amount mixing rheometer in melt blending, processing conditions be DEG C, 50rmp, 8min obtain masterbatch；
Step 2, by masterbatch described in 0.8g and 3.2g isotactic polypropylene matrix, the melt blending in minipool rheometer,
Processing conditions be DEG C, 50rmp, 8min obtain pellet；
Step 3, pellet is hot-forming in vulcanizing press, processing conditions is 200 DEG C of temperature, pressure 15MPa, preheating
15min, hot pressing 15min, are cold-pressed 10min, and 100 DEG C of vacuum annealing 12h are situated between to get the polyolefin electricity of the high dc breakdown intensity
Matter insulating composite material.
Embodiment 3
The present embodiment is related to a kind of olefin polymerization nanometer composite insulating material of high dc breakdown intensity, the composite material by
Nanoparticle of the ethylene-propylene copolymer of 99.75% mass fraction as the voltage stabilizer functionalization of matrix and 0.25% mass fraction
Son is formed as filler.Wherein the preparation process of the nanoparticle of voltage stabilizer functionalization is as shown in Figure 1, pass through following steps
Preparation:
A, the activation of voltage stabilizer: selection 2- amino-4-methoxyl -9- thioxanthones is scattered in hydrobromic acid and acetum
Reaction in (hydrobromic acid acetic acid volume ratio is 2:1), solid-to-liquid ratio 1:25, back flow reaction is for 24 hours.Then it is steady that hydroxylating voltage will be obtained
Determine agent and be dissolved in methylene chloride, solid-to-liquid ratio 1:15 is 1 to 1 with methacrylic chloride feed ratio, ice bath reaction 2 under nitrogen protection
Hour.Products therefrom is dissolved in pyridine, and solid-to-liquid ratio 1:25 is reacted 10 hours with 1 to 1,95 DEG C of acetic anhydride feed ratio, activated
Voltage stabilizer.
B, silane coupling agent coats nanoparticle: nano aluminium oxide being dispersed in toluene, nanoparticle and solvent solid-liquid
Than 1:50, mass ratio 1:1 with silane coupling agent carries out reaction 60 hours at 95 DEG C, obtains the nanometer of silane coupling agent cladding
Aluminium oxide.
C, the nanoparticle of voltage stabilizer functionalization: by the aluminium oxide of silane coupling agent cladding, the voltage stabilization of activation
Agent and initiator azodiisobutyronitrile mass ratio 100:30:15 are dispersed in n,N-Dimethylformamide, solid-to-liquid ratio 1:25,60
DEG C, 18h is reacted under nitrogen protection to get the nano magnesia of voltage stabilizer functionalization.
The present embodiment further relates to a kind of preparation method of the olefin polymerization nanometer composite insulating material of high dc breakdown intensity, institute
The method of stating includes the following steps:
Step 1, using ethylene-propylene copolymer described in 3.8g as the nano magnesia of matrix and 0.2g voltage stabilizer functionalization,
The melt blending in minipool rheometer, processing conditions are 170 DEG C, and 40rmp, 12min obtain masterbatch；
Step 2, it using masterbatch described in 0.2g and 3.8g ethylene-propylene copolymer as matrix, is melted altogether in minipool rheometer
Mixed, processing conditions is 170 DEG C, and 40rmp, 12min obtain pellet；
Step 3, pellet is hot-forming in vulcanizing press, processing conditions is 175 DEG C of temperature, pressure 10MPa, preheating
10min, hot pressing 10min, be cold-pressed 8min, 90 DEG C of vacuum annealing 12h to get the high dc breakdown intensity polyolefin dielectric
Insulating composite material.
Comparative example 1
This comparative example is related to a kind of olefin polymerization nanometer composite insulating material of high dc breakdown intensity, the composite material by
The polyethylene of 98% mass fraction is formed as the voltage stabilizer of matrix and 2% mass fraction as filler.Wherein voltage is steady
The preparation of the nanoparticle of agent functionalization is determined with embodiment 1.
This comparative example further relates to a kind of preparation method of the olefin polymerization nanometer composite insulating material of high dc breakdown intensity, institute
Stating preparation method can be summarized as following steps:
Step 1, by the nano magnesia of low-density polyethylene body described in 3.8g and 0.2g voltage stabilizer functionalization,
Melt blending in minipool rheometer, processing conditions are 140 DEG C, and 40rmp, 5min obtain masterbatch；
Step 2, it by masterbatch described in 1.6g and 2.4g low-density polyethylene body, is melted altogether in minipool rheometer
Mixed, processing conditions is 140 DEG C, and 40rmp, 5min obtain pellet；
Step 3, pellet is hot-forming in vulcanizing press, processing conditions is 150 DEG C of temperature, pressure 10MPa, preheating
2min, hot pressing 2min, are cold-pressed 2min, and 80 DEG C of vacuum annealing 8h are exhausted to get the polyolefin dielectric of the high dc breakdown intensity
Edge composite material.
Comparative example 2
This comparative example is related to a kind of olefin polymerization nanometer composite insulating material of high dc breakdown intensity, the composite material
Component and content are substantially the same manner as Example 2, the difference is that only: this comparative example is using without voltage stabilizer function
The nanoparticle of change.
This comparative example further relates to a kind of preparation method of the olefin polymerization nanometer composite insulating material of high dc breakdown intensity, institute
Preparation method is stated with embodiment 2.
Comparative example 3
This comparative example is related to a kind of olefin polymerization nanometer composite insulating material of high dc breakdown intensity, the composite material
Component and content are substantially the same manner as Example 2, the difference is that only: this comparative example is received using what silane coupling agent coated
The preparation of rice corpuscles, the nanoparticle of the silane coupling agent cladding is prepared using the method for the step B in embodiment 3.
This comparative example further relates to a kind of preparation method of the olefin polymerization nanometer composite insulating material of high dc breakdown intensity, institute
Preparation method is stated with embodiment 3.
Implementation result: the dc breakdown intensity of polyolefin insulation composite material prepared by comparative example 1 is 300.5kV/mm,
Polyolefin insulation composite material dc breakdown intensity prepared by embodiment 1 is 347.2kV/mm, by voltage stabilizer and institute
The polymer compatibility used is poor, and prepared polymer surfaces have the antioxidant migrated out, seriously affects the straight of polymer
Flow the raising of breakdown strength.The dc breakdown intensity of polyolefin insulation composite material prepared by comparative example 2 is 354.6kV/mm,
Polyolefin insulation composite material dc breakdown intensity prepared by embodiment 2 is 487.6kV/mm, this explanation only uses nanoparticle
Son is poor as the structural homogeneity of filler polyolefin insulation composite material, and is limited to the raising degree of dc breakdown intensity
, and the nanoparticle of voltage stabilizer functionalization is obvious to the improvement effect of composite material dc breakdown intensity, is only to add
Several times of nanoparticle are more than；In comparative example 3, the nanoparticle of silane coupling agent modification and the compatibility of polyolefin have centainly
The raising of degree, but still not as good as the nanoparticle of voltage stabilizer functionalization and polyolefin and compatibility, moreover,
The dc breakdown intensity of polyolefin insulation composite material prepared by comparative example 3 is 265.1kV/mm, and prepared by embodiment 3
Polyolefin insulation composite material dc breakdown intensity is 356.8kV/mm, this illustrates the voltage stabilizer being grafted in nanoparticle point
Son has vital effect to the raising of dc breakdown intensity.
Fig. 2 is the dc breakdown intensity Weibull distribution map of polyolefin insulation composite material prepared by embodiment 1, by
Figure it is found that high dc breakdown strength low-density polyethylene insulation composite material dc breakdown intensity be 347.2kV/mm, it is low close
The dc breakdown intensity 257.2kV/mm of polyethylene is spent, dc breakdown intensity improves about 35.0%.
Fig. 3 is the thermogravimetric curve figure of polyolefin insulation composite material prepared by embodiment 2, as seen from the figure, high direct current
The temperature of initial decomposition of breakdown strength isotactic polypropylene insulating composite material is about 373 DEG C, the initial decomposition temperature of isotactic polypropylene
About 299 DEG C of degree, temperature of initial decomposition improves about 24.7%.
Fig. 4 is the transmission electron microscope photo of polyolefin insulation composite material frozen section prepared by embodiment 3, by
For figure it is found that voltage stabilizer functional nanoparticle size in polyolefin substrate is distributed within the scope of 50~100nm, distribution is equal
Even, voltage stabilizer functional nanoparticle and polyolefin substrate have good compatibility.
Embodiment 4
The present embodiment is related to a kind of olefin polymerization nanometer composite insulating material of high dc breakdown intensity, the composite material by
The low density polyethylene (LDPE) of 96% mass fraction is made as the nanoparticle of the voltage stabilizer functionalization of matrix and 4% mass fraction
For filler composition.Wherein the preparation process of the nanoparticle of voltage stabilizer functionalization is as shown in Figure 1, pass through following steps system
It is standby:
A, the activation of voltage stabilizer: selection is scattered in hydrobromic acid and acetum (hydrogen bromine to hydroxy diphenyl second diketone
Vinegar acid volume ratio is reaction in 5:1), solid-to-liquid ratio 1:10, back flow reaction 10h.Then hydroxylating voltage stabilizer will be obtained
It is dissolved in methylene chloride, solid-to-liquid ratio 1:5 is 1 to 1 with methacrylic chloride feed ratio, and ice bath reacts 5 hours under nitrogen protection.
Products therefrom is dissolved in pyridine, and solid-to-liquid ratio 1:5 reacts 10 hours, the electricity activated with 1 to 1,100 DEG C of acetic anhydride feed ratio
Press stabilizer.
B, silane coupling agent coats nanoparticle: boron nitride nanosheet being dispersed in toluene, solid-to-liquid ratio 1:20, with silane
Coupling agent anti-mass ratio 1:2 carries out reaction 12 hours at 100 DEG C, obtains the boron nitride nanosheet of silane coupling agent cladding.
C, the nanoparticle of voltage stabilizer functionalization: the nanoparticle of silane coupling agent cladding, the voltage of activation is steady
Determine agent and initiator azodiisobutyronitrile mass ratio 100:10:10 is dispersed in n,N-Dimethylformamide, nanoparticle and molten
Agent solid-to-liquid ratio 1:20 is reacted for 24 hours at 60 DEG C, under nitrogen protection to get the boron nitride nanosheet of voltage stabilizer functionalization.
The present embodiment further relates to a kind of preparation method of the olefin polymerization nanometer composite insulating material of high dc breakdown intensity, institute
The method of stating includes the following steps:
Step 1, the boron nitride of the pungent dilute polymer matrices of ethylene-described in 4.75g and 0.25g voltage stabilizer functionalization is received
Rice piece, the melt blending in minipool rheometer, processing conditions are 140 DEG C, and 40rmp, 5min obtain masterbatch；
Step 2, it by masterbatch described in 3.25g and the pungent dilute polymer matrices of 0.75g ethylene-, is melted in minipool rheometer
Melt blending, processing conditions is 140 DEG C, and 40rmp, 5min obtain pellet；
Step 3, pellet is hot-forming in vulcanizing press, processing conditions is 150 DEG C of temperature, pressure 10MPa, preheating
2min, hot pressing 3min, are cold-pressed 2min, and 80 DEG C of vacuum annealing 8h are exhausted to get the polyolefin dielectric of the high dc breakdown intensity
Edge composite material.
Polyolefin insulation composite material dc breakdown intensity prepared by the present embodiment is 331.2kV/mm, initial decomposition temperature
About 441.5 DEG C of degree, voltage stabilizer functional nanoparticle size in the pungent dilute polymer matrices of ethylene-is distributed in 50~
It within the scope of 100nm, is evenly distributed, voltage stabilizer functional nanoparticle has good phase with the pungent dilute polymer matrices of ethylene-
Capacitive.
Embodiment 5
The present embodiment is related to a kind of olefin polymerization nanometer composite insulating material of high dc breakdown intensity, the composite material by
Nanoparticle of the syndiotactic polypropylene of 99.5% mass fraction as the voltage stabilizer functionalization of matrix and 0.5% mass fraction
It is formed as filler.Wherein the preparation process of the nanoparticle of voltage stabilizer functionalization is as shown in Figure 1, pass through following steps system
It is standby:
A, the activation of voltage stabilizer: selection is scattered in hydrobromic acid and acetum (hydrogen to amide groups diphenylthanedione
Bromic acid acetic acid volume ratio is reaction in 5:1), solid-to-liquid ratio 1:50, back flow reaction 36h.Then hydroxylating voltage stabilization will be obtained
Agent is dissolved in methylene chloride, and solid-to-liquid ratio 1:20 is 1 to 1 with methacrylic chloride feed ratio, and ice bath reaction 2 is small under nitrogen protection
When.Products therefrom is dissolved in pyridine, and solid-to-liquid ratio 1:25 is reacted 48 hours with 1 to 1,100 DEG C of acetic anhydride feed ratio, activated
Voltage stabilizer.
B, silane coupling agent coats nanoparticle: nano-titanium dioxide being dispersed in toluene, nanoparticle and solvent are solid
Liquor ratio 1:30, with the anti-mass ratio 1:0.5 of silane coupling agent, 100 DEG C carry out reaction 40 hours, obtain receiving for silane coupling agent cladding
Rice silica.
C, the nanoparticle of voltage stabilizer functionalization: the nanoparticle of silane coupling agent cladding, the voltage of activation is steady
Determine agent and initiator azodiisobutyronitrile mass ratio 100:16:8 is dispersed in n,N-Dimethylformamide, solid-to-liquid ratio 1:15,
65 DEG C, 12h is reacted under nitrogen protection to get the nano-titanium dioxide of voltage stabilizer functionalization
The present embodiment further relates to a kind of preparation method of the olefin polymerization nanometer composite insulating material of high dc breakdown intensity, institute
The method of stating includes the following steps:
Step 1, by the nano-titanium dioxide of syndiotactic polypropylene matrix described in 3.8g and 0.2g voltage stabilizer functionalization,
Melt blending in minipool rheometer, processing conditions are 200 DEG C, and 60rmp, 15min obtain masterbatch；
Step 2, by masterbatch described in 0.4g and 3.6g syndiotactic polypropylene matrix, the melt blending in minipool rheometer,
Processing conditions is 200 DEG C, and 60rmp, 15min obtain pellet；
Step 3, pellet is hot-forming in vulcanizing press, processing conditions is 210 DEG C of temperature, pressure 15MPa, preheating
20min, hot pressing 20min, are cold-pressed 20min, and 120 DEG C of vacuum annealing 12h are situated between to get the polyolefin electricity of the high dc breakdown intensity
Matter insulating composite material.
Polyolefin insulation composite material dc breakdown intensity prepared by the present embodiment is 460.4kV/mm, initial decomposition temperature
About 384 DEG C of degree, voltage stabilizer functional nanoparticle size in the pungent dilute polymer matrices of ethylene-is distributed in 50~
It within the scope of 100nm, is evenly distributed, voltage stabilizer functional nanoparticle has good phase with the pungent dilute polymer matrices of ethylene-
Capacitive.
In conclusion the present invention is grafted voltage stabilization agent molecule by click chemistry on nanoparticle, it is steady to form voltage
Determine the nanoparticle of agent functionalization.The collective effect of nanoparticle and voltage stabilizer can be efficient and polyene is greatly improved
The dc breakdown intensity of hydrocarbon dielectric insulation composite material makes composite material have excellent high voltage electrical property.Moreover,
Organic matter layer can be improved compatibility and interface binding power between inorganic nano-particle and polymer；Nanoparticle can reduce
Voltage stabilizer small molecule improves its stability in mobility.Therefore, the nanoparticle and polyolefin of voltage stabilizer functionalization
Dielectric is compound, can obtain the nanocomposite for having excellent electric insulation performance, is applied to high-voltage cable electric wire material
In material.
Practical application approach of the present invention has very much, above are only the preferred embodiments of the invention.It should be noted that above-mentioned reality
It applies example to be only used for illustrating the present invention, but not limitation institute's protection scope of the present invention.The those of ordinary skill being related to for this technology
For, under the premise of not departing from mechanism of the present invention, several variations can also be carried out, these variations should also be regarded as guarantor of the invention
Within the scope of shield.
Claims (10)
1. a kind of olefin polymerization nanometer composite insulating material of high dc breakdown intensity, which is characterized in that the polyolefin dielectric
Insulating composite material is in terms of mass fraction 100%, including 96~99.75% polyolefin dielectric base body and 0.25~4%
Modified Nano particle filler；
The modified Nano particle filler is the nanoparticle of voltage stabilizer functionalization；The voltage stabilizer is selected from hexichol
Base second diketone, to methoxyl group diphenylthanedione, to hydroxy diphenyl second diketone, to amide groups diphenylthanedione, to amino
Diphenylthanedione, 9- thioxanthones, 2- hydroxyl -9- thioxanthones, 2- hydroxyl -4- methoxyl group -9- thioxanthones, 2- hydroxyl -4- amide
Base -9- thioxanthones, 2- amino-4-methoxyl -9- thioxanthones it is one or more.
2. the olefin polymerization nanometer composite insulating material of high dc breakdown intensity according to claim 1, which is characterized in that institute
The nanoparticle stated is nano silica, nano magnesia, nano zine oxide, nano-titanium dioxide, nano aluminium oxide, nanometer
One or more of barium titanate, nm-class boron nitride and graphene.
3. the olefin polymerization nanometer composite insulating material of high dc breakdown intensity according to claim 1 or 2, feature exist
In, the nanoparticle of the voltage stabilizer functionalization preparation the following steps are included:
A. the activation of voltage stabilizer: dispersing voltage stabilizer in acid solution and carry out hydroxylating, then will obtain
Hydroxylating voltage stabilizer is reacted with methacrylic chloride, and products therefrom is again with acetic anhydride, the voltage stabilization activated
Agent；
B. silane coupling agent coats nanoparticle: nanoparticle being reacted with silane coupling agent, obtains silane coupling agent cladding
Nanoparticle；
C. the nanoparticle of voltage stabilizer functionalization: by the nanoparticle of silane coupling agent cladding, the voltage stabilizer of activation
With initiator for reaction to get.
4. the polyolefin dielectric insulation composite material of high dc breakdown intensity according to claim 3, which is characterized in that
In step A, the acid solution includes the acetic acid and hydrobromic acid that volume ratio is 1:1~5, and the voltage stabilizer and acid solution are consolidated
Liquor ratio be 1:10~50, hydroxylating 10~48 hours；The quality of the hydroxylating voltage stabilizer and methacrylic chloride
Frequently it is 1:1, is reacted 2~5 hours under ice bath；The mass ratio of products therefrom and acetic anhydride is 1:1, reacts 10 at 60~100 DEG C
~48 hours.
5. the polyolefin dielectric insulation composite material of high dc breakdown intensity according to claim 3, which is characterized in that
In step A, after the hydroxylating voltage stabilizer is dissolved in methylene chloride, then react with methacrylic chloride；The product is dissolved in
After pyridine, then with acetic anhydride；
The solid-to-liquid ratio of the hydroxylating voltage stabilizer and methylene chloride is 1:5-20；The solid-to-liquid ratio of the product and pyridine is 1:
5-25。
6. the polyolefin dielectric insulation composite material of high dc breakdown intensity according to claim 3, which is characterized in that
In step B, the silane coupling agent is gamma-mercaptopropyltriethoxysilane, and the mass ratio with nanoparticle is 1:0.5~2；Institute
Reaction is stated specifically to react 12~60 hours at 80~100 DEG C.
7. the polyolefin dielectric insulation composite material of high dc breakdown intensity according to claim 3, which is characterized in that
In step C, the dosage of the voltage stabilizer of the activation is 5~20% of nanoparticle quality in step B；The activation voltage
The mass ratio of stabilizer and initiator is 1:0.25~4；The reaction is specifically using 60~70 DEG C under nitrogen atmosphere reactions 12
~60 hours.
8. the polyolefin dielectric insulation composite material of high dc breakdown intensity according to claim 3, which is characterized in that
In step B, the nanoparticle dispersion in a solvent, is then reacted with silane coupling agent；The nanoparticle and solvent are consolidated
Liquor ratio is 1:20-50；
In step C, the reaction carries out in n,N-Dimethylformamide；The nanoparticle and N of the silane coupling agent cladding,
The solid-to-liquid ratio of dinethylformamide is 1:5-25.
9. the polyolefin dielectric insulation composite material of high dc breakdown intensity according to claim 1, which is characterized in that
The polyolefin dielectric base body is high density polyethylene (HDPE), low density polyethylene (LDPE), isotactic polypropylene, syndiotactic polypropylene, random
One of polypropylene, ethylene-octene copolymer, ethylene-propylene copolymer are a variety of.
10. a kind of preparation side of the polyolefin dielectric insulation composite material of high dc breakdown intensity as described in claim 1
Method, which is characterized in that described method includes following steps:
S1, by part polyolefin dielectric base body and modified Nano particle filler melt blending, obtain masterbatch；
S2, by masterbatch and remaining polyolefin dielectric base body in melt blending, obtain the polyolefin electricity of high dc breakdown intensity
Dielectric insulation composite material granular；
S3, the polyolefin dielectric insulation composite material granular hot pressing of high dc breakdown intensity is formed a film, after high annealing, i.e.,
Obtain the polyolefin dielectric insulation composite material of the high dc breakdown intensity.
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| CN110229402A (en) * | 2019-05-28 | 2019-09-13 | 东南大学 | A kind of Cross-linked Polyethylene Composites and preparation method thereof of high dc breakdown field strength |
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| CN111286082A (en) * | 2020-02-17 | 2020-06-16 | 安徽华文塑胶科技有限公司 | High-voltage cable stabilizer and preparation method thereof |
| CN112280145A (en) * | 2020-10-22 | 2021-01-29 | 中电材料科技(嘉兴)有限公司 | High-voltage-resistance insulating material and preparation method thereof |
| CN112745638A (en) * | 2021-01-19 | 2021-05-04 | 中国科学院合肥物质科学研究院 | High-voltage-resistant m-ABA-SiO2Alicyclic epoxy resin nano composite insulating material and preparation method thereof |
| CN112745638B (en) * | 2021-01-19 | 2022-04-26 | 中国科学院合肥物质科学研究院 | High-voltage-resistant m-ABA-SiO2Alicyclic epoxy resin nano composite insulating material and preparation method thereof |
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| CN114347522A (en) * | 2022-01-27 | 2022-04-15 | 西安交通大学 | Sandwich polypropylene composite dielectric with high energy storage density and preparation method thereof |
| CN114395193A (en) * | 2022-03-04 | 2022-04-26 | 安徽飞达电气科技有限公司 | Polypropylene film and preparation method thereof |
| CN116376142A (en) * | 2023-04-12 | 2023-07-04 | 河北德容塑料包装制品股份有限公司 | Micro-foaming PE material, preparation method and packaging cover |
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