CN107793696A - A kind of preparation method of the ageing-resistant cable insulation material of super-pressure - Google Patents
A kind of preparation method of the ageing-resistant cable insulation material of super-pressure Download PDFInfo
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- 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
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- 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
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- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/18—Protection against damage caused by wear, mechanical force or pressure; Sheaths; Armouring
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Abstract
The present invention relates to a kind of preparation method of the ageing-resistant cable insulation material of super-pressure, the cable insulation material includes modified nano-ZnO/10 20 parts of low density polyethylene (LDPE)/modified attapulgite, 80 100 parts of phenolic resin, 10 20 parts of carbonitride, 20 30 parts of polystyrene, 30 40 parts of epoxy resin, 58 parts of antioxidant, 5 10 parts of plasticizer, 10 15 parts of glass fibre, improve the heat resistance and intensity of insulating materials, reduce the ageing time of insulating materials, it can keep super-pressure, it is non-degradable for a long time under high temperature action.
Description
Technical field
The present invention relates to a kind of preparation method of cable insulation material, the cable insulation material includes low density polyethylene
Nano inorganic-organic composite material of alkene/modified attapulgite, the heat resistance and intensity of insulating materials can be improved, reduce insulation
The ageing time of material, it can keep non-degradable for a long time under high temperature action.
Background technology
Cable is mainly made up of following 4 part:1. conducting wire center, it is made of high conductivity material (copper or aluminium).2. insulate
Layer, the insulating materials as cable should have a high insulaion resistance, high breakdown field strength, low dielectric loss and low
Dielectric constant.The insulating materials commonly used in cable has oil-paper, polyvinyl chloride, polyethylene, crosslinked polyethylene, rubber etc..It is 3. close
Closure set, protect protection insulated wire heart from the damage of machinery, moisture, moisture, chemical substance, light etc..Insulation for moisture-sensitive, one
As use lead or aluminium extrusion sealing sheath.4. coating is protected, to protect sealing sheath from mechanical damage.It is general to use plating
Zinc steel band, steel wire or copper strips, copper wire etc. surround outside sheath (title armored cable) as armor, and armor plays electric field shielding simultaneously
With the effect for preventing external electromagnetic wave interference.
At present, it is high polymer material that the insulating barrier of cable is most commonly used.On electrotechnics, specific insulation is more than
109The material that Ω cm material is formed is referred to as insulating materials, that is, for making device electrically to prevent electric current
The material passed through.Crosslinked polyethylene has excellent dielectric properties and mechanical performance, and oneself is widely used in high pressure and super-pressure
In plastic insulating power cable.With the development of super-pressure, extra-high voltage direct-current power transmission and transformation system, the insulation ag(e)ing in running
Problem is increasingly severe, and oneself turns into the major obstacle that insulated cable develops to super-pressure.When the applied electric field of insulating polymer is strong
When degree reaches 1/10th of breakdown field strength, poplar bundles can be caused in the Electric Power Equipment Insulation to work long hours, reduce electricity
Cable service life.The high voltage power cable insulating materials being made up of low density polyethylene (LDPE), by various in During Process of Long-term Operation
The gradual aging of influence of aging action, causes the decline of the dielectric properties and mechanical performance of material.According to the classification of aging action
Voltage ageing, heat ageing, mechanical aging and Electrochemical Ageing can be divided into.Wherein heat ageing is the main of PE cable insulation infringement
Inducement, different thermal aging times and condition can cause the difference of polyethylene inner molecular structure, and then influence its space charge spy
Property.
Research shows, under DC electric field effect, space charge is easily formed in polymer insulation, and space charge can make
Electric Field Distribution is distorted, and aggravates polymer insulation aging, and the aging of material result in the decline of material electric property.Polymer
Space-charge is mainly by the same polarity space charge and insulator that enter sunken carrier or transportable current-carrying of electrode injection
Organic or inorganic impurity ionized under electric field action caused by heteropolarity electricity.In order to suppress the formation of space charge, it is necessary to poly-
It is ethylene modified so as to change trap energy therein and distribution, change distribution of space charge, lower distortion probability, improve polymer
Dielectric properties, polymer insulation aging is reduced, and do not influence the processing characteristics of polymer simultaneously.
Concave convex rod is also known as palygorskite(Palygorskite)Or Palygorskite, it is a kind of magnesium containing Shuifu County for having chain layer structure
Aluminosilicate clays mineral.Its structure belongs to 2:1 type clay mineral.Each 2:In 1 unit structure layer, tetrahedron chip angle top every
Certain distance direction overturns, forming layer chain.Concave-convex clay rod refers to attapulgite(attapulgite)For key component
A kind of clay mineral.Attapulgite is that a kind of crystalloid is hydrated alumina magnesia silicate, has unique layer chain structure feature,
Crystal lattice in its structure be present, contain variable amount of Na in crystal+、Ca2+、Fe3+、Al3+, crystal is in needle-like, threadiness or
Fiber collection shape.There is attapulgite the good colloidal natures such as unique scattered, high temperature resistant, salt resistance alkali and higher absorption to take off
Color ability, and there is certain plasticity and cohesive force, its preferable chemical molecular formula is:Mg5Si8O20(OH)2(OH2)4·
4H2O.With the intermediate structure between chain structure and layer structure.Due to the unique crystal structure of attapulgite, it is allowed to
With many special materializations and processing performance.Main physical and chemical performance and processing performance have:Cation interchangeability, water imbibition,
Adsorption bleaching, big specific surface area(9.6~36m2/g)And colloid index and expansion capacity.The current attapulgite mineral products money in China
Source reserves are entirely capable of meeting industrial demand, and have obvious performance compared with the Resource Properties of other various countries of the world
Advantage.Attapulgite has preferable draw ratio and abundant inner duct, is both that preferable reinforcing material has fire retardation again,
Lose constitution water at high temperature and produce vapor, can with blocking oxygen, and can produce better heat stability with MgO, Al2O3
Based on oxide-isolation layer.
Poletene/lamina material has certain advantage, and mainly lighter than Conventional filler compound, density is relatively low, tool
There are higher heat resistance, high intensity, high-modulus, high gas-obstructing character and the relatively low coefficient of expansion, electricity can be widely used in
Son, household electrical appliances, power industry.
The content of the invention
Dielectric Properties at present on polyethylene/attapulgite material are less, although attapulgite has cheap, performance
The features such as good, but its surface has certain hydrophily, it is not easy to merged with polymer surfaces, therefore, present invention research is logical
Cross attapulgite modified, using its space layer chain structure, stable space layer chain is then formed with polyethylene and combine, reduces bumps
The surface free energy of rod, the dissipation rate of charge migration speed and space charge is improved, electricity is refused so as to suppress media interior
Severe distortion, suppress space charge accumulation, reduce space charge amount, improve distribution of space charge, improve charge transport, can be with
Significantly reduce the aging phenomenon of insulating materials.And because attapulgite material has good heat resistance in itself, by changing
Property after can obstruct the heat in the external world and think heat transfer inside polyvinyl alcohol material, prevent the thermal diffusion of high temperature degradation, Ke Yiti
The resistance to elevated temperatures of high insulating materials.
First, in order to improve the surface acidity of concave convex rod, increase polar group, be modified using weak acid, increase concave convex rod
Specific surface area, gap structure distribution is improved, optimization layer chain space structure, increases lamella and chain length, is advantageous to and polyethylene knot
Close, so as to avoid only internal intercalation, Dispersion on surface can also be formed and polymerize, be advantageous to combining closely for the two;The present invention
The organic monoacid of use includes acetic acid, citric acid, malic acid, concentration 0.1-2mol/l, the acid functional that above-mentioned organic acid includes
Group is more, that is, avoids destruction of the strong acid to the layer chain of concave convex rod, gentle stable, but also can form certain space effect
Should, beneficial to CO-, NH- isopolarity small molecule groups occupy active room, are configured to the surface of concave convex rod and interior layer link tight
Close combination, it, with dispersion space electric charge, can be advantageous to prevent the aggregation of space charge with low density polyethylene (LDPE) after mixing, so as to have
Beneficial to anti-aging.
Polyimides is one of optimal high-molecular organic material of combination property, and high temperature resistant makes for a long time up to more than 400 DEG C
With temperature range -200~300 DEG C, no sharp melting point, high insulating property, 103 Dielectric constant 4.0 under Hz, dielectric loss is only
0.004~0.007, category F to H class F insulating material Fs.And with the characteristic such as low friction, wear-resistant, it is commonly used for protection materials.
Polyimides is to contain imide ring on main chain(-CO-NH-CO-)A kind of polymer, while there is CO-, NH-
Polar micromolecules group, concave convex rod is carried out to polyimide modified, the increase polar micromolecules degree of polymerization, further increase lamella sky
Between, and due to small polarity CO-, NH- presence adds the degree of polymerization of interior volume and surface polyethylene, and process is overcritical
After extraction, the expansion of piece sheaf space, density of material is reduced with polymer combination latter aspect, forms more light material, separately
On the one hand the surface free energy of concave convex rod is reduced, the dissipation rate of electric charge is improved, prevents space charge to gather, reduces insulation
The aging of material.Polyimides has good resistance to elevated temperatures in itself, and on the one hand concave convex rod is modified, and on the one hand may be used also
With play it is resistant to elevated temperatures a little, improve insulating materials system resistance to elevated temperatures, further optimize insulating materials.
The impact of low density polyethylene (LDPE)/modified attapulgite nano composite material is measured using izodtest method
Intensity, this method principle are that the sample that will be perpendicular to cantilever beam support is destroyed with pendulum one-shot, measurement sample fracture when institute
The ratio between the impact energy of absorption, the cross-sectional area that impact energy is hit with sample is impact strength.Result of the test shows, low
The impact strength of density polyethylene/modified attapulgite nano-composite insulating material is 29.8kJ/m2;And common low density polyethylene (LDPE)
Impact strength be only 20kJ/m2。
Using CONCEPT80 broadband dielectric spectrum measurement systems, it can be seen that modified nano zinc oxide-low density polyethylene
The real part of the complex dielectric permittivity of alkene/modified attapulgite active component is all higher than common low-density polyethylene material with imaginary part, can
With 105-106Reach in the range of Hz in the range of 2.9-3.1, significantly larger than the 2.0-2.1 scopes of common polythene, due to compound
The complex dielectric permittivity increase of material, hole and the increase of electron injection difficulty, cause the space charge of aggregation to reduce, old so as to reduce
Change.
Electrostrictive polymer ageing process and electric charge enter to fall into and detrapping process is relevant, enter and fall into the releasing along with energy with detrapping
Put and shift.Ultraviolet radioactive caused by electronics and hole-recombination is cause depolymerization main in electrostrictive polymer ageing process
Factor.Degraded according to light, voltage ageing similitude and polymer light theoretical, a small amount of inorganic nano oxygen is introduced toward polyethylene base-material is interior
Compound particle, as nano magnesia, nano zine oxide are respectively provided with good light scattering ability and larger specific surface area, favorably
In the Charge Transport Proper ty for improving polyethylene, aging is reduced, improves service life.
Titanate coupling agent TMC-201, i.e. isopropyl three(Dioctylphyrophosphoric acid acyloxy)Titanate esters, nanometer can be improved
The rheological performance of zinc oxide, improves mechanical strength, and nano zine oxide improves with after mixed with polymers, adding trap quantity
Electric charge flowing, adds average breakdown strength, is advantageous to improve the service life of insulating materials.
It is described the present invention relates to a kind of cable insulation material preparation method for including low density polyethylene (LDPE)/modified attapulgite
Cable insulation material include modified nano-ZnO/low density polyethylene (LDPE)/modified attapulgite 10-20 parts, phenolic resin 80-100 parts,
Carbonitride 10-20 parts, polystyrene 20-30 parts, epoxy resin 30-40 parts, antioxidant 5-8 parts, plasticizer 5-10 parts, glass fibers
Tie up 10-15 parts, wherein modified attapulgite refer to concave convex rod by after low-kappa number by polyimide grafted modification.
The plasticizer is acetyl tributyl citrate.The particle diameter of the nano zine oxide is 30-100nm, preferably
30-70nm.The antioxidant master can effectively prevent the autoxidation of polymer, mainly using antioxidant 1024, antioxidant
565th, antioxidant 1010 etc., and it is not limited to antioxidant material commonly used in the art.
Wherein, the mass ratio of low density polyethylene (LDPE)/modified attapulgite is 20-40:2-10, preferably 10-20:2-10, it is modified
It is 0.5-1.5% that nano-ZnO, which accounts for low density polyethylene (LDPE)/modified attapulgite nano composite material mass percent,.
The insulating materials is to be prepared in accordance with the following steps:
(1)Prepare modified attapulgite:Concave convex rod original ore soil is added in 150mL distilled water, mistake after 10~30min of ultrasonic disperse
The large particulate matter except beaker bottom is filtered off, is centrifuged, is dried, is ground, roasting;Baked attapulgite is placed in into concentration is
React 1~2h in 0.1-2mol/L acetum after ultrasonic disperse at 80 DEG C~90 DEG C, finally filter, wash in
Property, drying.The attapulgite of acidifying is added in toluene 15~20min of ultrasonic disperse under nitrogen protection, then by temperature
It is added to after rising to 110~120 DEG C in the aqueous solution of polyimides, reacts 5 at 80~100 DEG C after ultrasonic 20-30min is scattered
~6h, then filter, washed with distilled water and absolute ethyl alcohol, being dried in vacuo 10~12h at 60~80 DEG C, obtaining modified attapulgite
Soil.
(2)Prepare low density polyethylene (LDPE)/modified attapulgite nano composite material:Using high shear type double screw extruder,
Modified attapulgite is dropped under agitation to be well mixed with low density polyethylene (LDPE), with twin-screw extrusion mixed material, is granulated,
Shaping.
(3)Prepare surface-treated nano-ZnO:Nano ZnO powder is placed in baking oven and dries 2h, takes dried receive
Rice ZnO powders are dissolved in cyclopentanol, and add a small amount of deionized water, ultrasonic disperse, while by isopropyl three(Dioctyl Jiao's phosphorus
Sour acyloxy)Titanate esters are dissolved in cyclohexane solution, are stirring evenly and then adding into nano-ZnO/cyclopentanol mixed solution.Mixing
Solution ultrasonic disperse 2h, 2h then is stirred at a temperature of 100 DEG C, then disperse 2h with ultrasonic wave, be subsequently placed in 120 DEG C of temperature
12h is dried in vacuo in vacuum drying oven, mills to obtain through the surface-treated ZnO Nanoparticles of titanate coupling agent, nano-ZnO
The particle diameter of particle is 30-100nm, preferably 30-70nm;Isopropyl three(Dioctylphyrophosphoric acid acyloxy)The addition of titanate esters accounts for
The 2-10% of modified nano-ZnO quality.
(4)Low density polyethylene (LDPE)/modified attapulgite nano composite material is taken to be dissolved in toluene solution, then by modified Nano
ZnO particles are added in above-mentioned solution, and temperature is kept for 80-120 DEG C, stir 2h, ultrasonic disperse 2h.Then by the mixed liquor of preparation
Desolventizing in baking oven is placed in, so as to which the nanometer nothing for including modified nano-ZnO particle/low density polyethylene (LDPE)/modified attapulgite be made
Machine-organic composite material;
(5)By phenolic resin 80-100 parts, carbonitride 10-20 parts, polystyrene 20-30 parts, epoxy resin 30-40 parts, antioxygen
Agent 5-8 parts, plasticizer 5-10 parts, glass fibre 10-15 parts and step(4)Obtained composite 10-20 parts mixing, pours into height
Fast mixer, at room temperature first using 800-1000 revs/min speed stir 30 minutes, then 60 DEG C with 3000-4000 turn/
The speed stirring 30min of minute, the batch mixing to stir is discharged, then melts, injection molding, obtains the cable insulation material
Material.The melting temperature is 200-280 DEG C, and the injection molding temperature is 120-150 DEG C, preferably 130-150 DEG C.
Composite cable insulating materials can be substantially reduced in the application in high pressure and super-pressure plastic insulating power cable
Aging, improve the high temperature resistant and intensity of cable insulation material.
Embodiment
With reference to embodiment, the present invention is further detailed explanation.
Embodiment 1
(1)Prepare modified attapulgite:Concave convex rod original ore soil is added in 150mL distilled water, filtered off after ultrasonic disperse 10min
Except the large particulate matter of beaker bottom, centrifuge, dry, grind, roasting;Baked attapulgite is placed in into concentration is
React 1h in 0.5mol/L acetum after ultrasonic disperse at 80 DEG C, finally filter, wash until neutral, drying.By acid
The attapulgite of change is added in toluene ultrasonic disperse 20min under nitrogen protection, is added to after temperature then is risen into 120 DEG C
In the aqueous solution of polyimides, 6h is reacted at 100 DEG C after ultrasonic 20min is scattered, then filtering, with distilled water and absolute ethyl alcohol
Wash, be dried in vacuo 12h at 80 DEG C, obtain attapulgite modified.
(2)Prepare low density polyethylene (LDPE)/modified attapulgite nano composite material:Using high shear type double screw extruder,
Modified attapulgite is well mixed with low density polyethylene (LDPE) under agitation, with twin-screw extrusion mixed material, is granulated,
Shaping.
(3)Nano ZnO powder is placed in baking oven and dries 2h, takes dried nano ZnO powder to be dissolved in cyclopentanol,
And a small amount of deionized water is added, ultrasonic disperse, while by isopropyl three(Dioctylphyrophosphoric acid acyloxy)Titanate esters are dissolved in hexamethylene
In alkane solution, it is stirring evenly and then adding into nano-ZnO/cyclopentanol mixed solution.Mixed solution ultrasonic disperse 2h, then 100 DEG C
At a temperature of stir 2h, ultrasonic wave disperses 2h, is subsequently placed in the vacuum drying oven of 120 DEG C of temperature and is dried in vacuo 12h, mills
To through the surface-treated ZnO Nanoparticles of titanate coupling agent, the particle diameter 30nm of modified nano-ZnO particle;Isopropyl three(Two
Octyl group pyrophosphoric acid acyloxy)The addition of titanate esters accounts for the 2% of modified nano-ZnO quality.
(4)Low density polyethylene (LDPE)/modified attapulgite nano composite material is taken to be dissolved in toluene solution, then by modified Nano
ZnO particles are added in above-mentioned solution, and temperature is kept for 120 DEG C, stir 2h, ultrasonic disperse 2h.Then the mixed liquor of preparation is put
The desolventizing in baking oven, so as to which the inorganic-organic for including modified nano-ZnO particle/low density polyethylene (LDPE)/modified attapulgite be made
Composite;
(5)By 80 parts of phenolic resin, 10 parts of carbonitride, 20 parts of polystyrene, 30 parts of epoxy resin, 5 parts of antioxidant, plasticizer 5
Part, 10 parts of glass fibre and step(4)The 10 parts of mixing of obtained composite, pour into homogenizer, first use 800 at room temperature
Rev/min speed stir 30 minutes, 30min is then stirred with 3000 revs/min of speed at 60 DEG C, it is mixed by what is stirred
Material discharge, then after 200 DEG C of meltings, 120 DEG C of injection moldings, obtain the cable insulation material.
Embodiment 2
(1)Prepare modified attapulgite:Concave convex rod original ore soil is added in 150mL distilled water, filtered off after ultrasonic disperse 30min
Except the large particulate matter of beaker bottom, centrifuge, dry, grind, roasting;Baked attapulgite is placed in into concentration is
React 1~2h in 0.5mol/L acetum after ultrasonic disperse at 90 DEG C, finally filter, wash until neutral, drying.Will
The attapulgite of acidifying is added in toluene ultrasonic disperse 15min under nitrogen protection, is added after temperature then is risen into 120 DEG C
Into the aqueous solution of polyimides, 5h is reacted at 100 DEG C after ultrasonic 20-30min is scattered, then filtering, with distilled water and nothing
Water-ethanol washs, is dried in vacuo 10h at 80 DEG C, obtains attapulgite modified.
(2)Prepare low density polyethylene (LDPE)/modified attapulgite nano composite material:Using high shear type double screw extruder,
Modified attapulgite is well mixed with low density polyethylene (LDPE) under agitation, with twin-screw extrusion mixed material, is granulated,
Shaping.
(3)Prepare surface-treated nano-ZnO:Nano ZnO powder is placed in baking oven and dries 2h, takes dried receive
Rice ZnO powders are dissolved in cyclopentanol, and add a small amount of deionized water, ultrasonic disperse, while by isopropyl three(Dioctyl Jiao's phosphorus
Sour acyloxy)Titanate esters are dissolved in cyclohexane solution, are stirring evenly and then adding into nano-ZnO/cyclopentanol mixed solution.Mixing
Solution ultrasonic disperse 2h, 2h then is stirred at a temperature of 100 DEG C, then disperse 2h with ultrasonic wave, be subsequently placed in 120 DEG C of temperature
12h is dried in vacuo in vacuum drying oven, mills to obtain through the surface-treated ZnO Nanoparticles of titanate coupling agent, modified Nano
The particle diameter of ZnO particles is 50nm;Isopropyl three(Dioctylphyrophosphoric acid acyloxy)The addition of titanate esters accounts for modified nano-ZnO matter
The 5% of amount.
(4)Low density polyethylene (LDPE)/modified attapulgite nano composite material is taken to be dissolved in toluene solution, then by modified Nano
ZnO particles are added in above-mentioned solution, and temperature is kept for 120 DEG C, stir 2h, ultrasonic disperse 2h.Then the mixed liquor of preparation is put
The desolventizing in baking oven, so that the obtained nano inorganic comprising modified nano-ZnO particle/low density polyethylene (LDPE)/modified attapulgite-
Organic composite material;
(5)By 100 parts of phenolic resin, 10 parts of carbonitride, 20 parts of polystyrene, 30 parts of epoxy resin, 6 parts of antioxidant, plasticizer 6
Part, 10 parts of glass fibre and step(4)The 10 parts of mixing of obtained composite, pour into homogenizer, first use at room temperature
1000 revs/min of speed stirs 30 minutes, then stirs 30min with 4000 revs/min of speed at 60 DEG C, will stir
Batch mixing discharge, 220 DEG C melting, then 150 DEG C of injection moldings, obtain the cable insulation material.
Embodiment 3
(1)Prepare modified attapulgite:Concave convex rod original ore soil is added in 150mL distilled water, filtered off after ultrasonic disperse 30min
Except the large particulate matter of beaker bottom, centrifuge, dry, grind, roasting;It is 1mol/L that baked attapulgite is placed in into concentration
Acetum in 1h is reacted at 80 DEG C after ultrasonic disperse, finally filter, wash until neutral, drying.By the bumps of acidifying
Rod soil is added in toluene ultrasonic disperse 20min under nitrogen protection, and polyimides is added to after temperature then is risen into 120 DEG C
The aqueous solution in, 6h is reacted at 100 DEG C after ultrasonic 30min is scattered, then filtering, washed with distilled water and absolute ethyl alcohol,
80 DEG C of vacuum drying 12h, are obtained attapulgite modified.
(2)Using high shear type double screw extruder, under agitation by modified attapulgite and low density polyethylene
Alkene is well mixed, and with twin-screw extrusion mixed material, is granulated, shaping.
(3)Prepare surface-treated nano-ZnO:Nano ZnO powder is placed in baking oven and dries 2h, takes dried receive
Rice ZnO powders are dissolved in cyclopentanol, and add a small amount of deionized water, ultrasonic disperse, while by isopropyl three(Dioctyl Jiao's phosphorus
Sour acyloxy)Titanate esters are dissolved in cyclohexane solution, are stirring evenly and then adding into nano-ZnO/cyclopentanol mixed solution.Mixing
Solution ultrasonic disperse 2h, 2h then is stirred at a temperature of 100 DEG C, then disperse 2h with ultrasonic wave, be subsequently placed in the vacuum of 120 DEG C of temperature
12h is dried in vacuo in baking oven, mills to obtain through the surface-treated ZnO Nanoparticles of titanate coupling agent, modification is prepared
The particle diameter of ZnO Nanoparticles is 70nm;Isopropyl three(Dioctylphyrophosphoric acid acyloxy)The addition of titanate esters accounts for modified Nano
The 6% of ZnO mass.
(4)Low density polyethylene (LDPE)/modified attapulgite nano composite material is taken to be dissolved in toluene solution, then by modified Nano
ZnO particles are added in above-mentioned solution, and temperature is kept for 80-120 DEG C, stir 2h, ultrasonic disperse 2h.Then by the mixed liquor of preparation
Be placed in desolventizing in baking oven, so as to be made comprising modified nano-ZnO particle/low density polyethylene (LDPE)/modified attapulgite nano inorganic-
Organic composite material;
(5)By 100 parts of phenolic resin, 20 parts of carbonitride, 30 parts of polystyrene, 40 parts of epoxy resin, 8 parts of antioxidant, plasticizer
10 parts, 15 parts of glass fibre and step(4)The 20 parts of mixing of obtained composite, pour into homogenizer, first use at room temperature
1000 revs/min of speed stirs 30 minutes, then stirs 30min with 3000 revs/min of speed at 60 DEG C, will stir
Batch mixing discharge, then 250 DEG C melting, 120 injection moldings, obtain the cable insulation material.
Comparative example 1
Only with common attapulgite, without modifying process, other experiment parameters are the same as embodiment 1.
Comparative example 2
Modified nano zinc oxide is added without, other experiment parameters are the same as embodiment 1.
Comparative example 3
Add without modified common nano zine oxide, other experiment parameters are the same as embodiment 1.
Specific detection
Detect the tensile strength (σ t/MPa) of above-mentioned anti-aging cable insulation material, elongation at break (δ/ %), density, hardness,
Then above-mentioned anti-aging cable insulation material was subjected to hot air aging all over the world by 200 DEG C × 30 days, 250 DEG C × 30, then
Detect stretching strength retentivity (E1/ %) and elongation at break conservation rate (E2/ %), concrete outcome is shown in Table 1.
The each Testing index of the Electric insulation material of table 1
Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
Density, g/cm3 | 1.021 | 1.071 | 1.12 | 1.25 | 1.28 | 1.347 |
Hardness, ShoreA | 90 | 92 | 88 | 80 | 75 | 78 |
Tensile strength, MPa | 50 | 51 | 49 | 40 | 37 | 42 |
Elongation at break % | 550 | 570 | 580 | 400 | 380 | 420 |
200 DEG C × 30 days, E1/ % | 98.5 | 98.2 | 98.1 | 79.5 | 80.1 | 82.1 |
200 DEG C × 30 days, E2/ % | 93.7 | 94.2 | 95.1 | 88.7 | 82.3 | 84.5 |
250 DEG C × 30 days, E1/ % | 97.5 | 98.0 | 97.7 | 77.1 | 74.0 | 75.3 |
250 DEG C × 30 days, E2/ % | 91.4 | 90.8 | 96.4 | 65.9 | 69.8 | 70.7 |
There are the above results to can be seen that after modified attapulgite cross-link low-density polyethylene, add a small amount of modified inorganic nanometer
Zinc oxide forms active component, then further advantageously reduces the density of insulating materials with other components mixed-forming, improves
The heat resistance and intensity of insulating materials, the ageing time of insulating materials is reduced, can kept under high temperature action for a long time(200℃
× 30 days, 250 DEG C × 30 days)It is non-degradable.
The foregoing is only a specific embodiment of the invention, but protection scope of the present invention is not limited thereto, any
Those skilled in the art disclosed herein technical scope in, can without the change that creative work is expected or
Replace, should all be included within the scope of the present invention.Therefore, protection scope of the present invention should be limited with claims
Fixed protection domain is defined.
Claims (6)
1. a kind of preparation method of the ageing-resistant cable insulation material of super-pressure, it is characterised in that the cable insulation is using following
Step obtains:
(1)Prepare attapulgite modified:Concave convex rod by low-kappa number is added in the aqueous solution of polyimides and reacts 5-
6h, obtain attapulgite modified;
(2)Using high shear type double screw extruder, modified attapulgite is mixed with low density polyethylene (LDPE) under agitation
Close uniformly, with twin-screw extrusion mixed material, be granulated, shaping;
(3)Modified nano zinc oxide:Nano ZnO powder is placed in baking oven and dries 2h, takes dried nano ZnO powder to be dissolved in
In cyclopentanol, and a small amount of deionized water is added, ultrasonic disperse, while by isopropyl three(Dioctylphyrophosphoric acid acyloxy)Metatitanic acid
Ester is dissolved in cyclohexane solution, is stirring evenly and then adding into nano-ZnO/cyclopentanol mixed solution, mixed solution ultrasonic disperse
2h, 2h then is stirred at a temperature of 100 DEG C, then disperse 2h with ultrasonic wave, be subsequently placed in vacuum in the vacuum drying oven of 120 DEG C of temperature and do
Dry 12h, mill to obtain through the surface-treated ZnO Nanoparticles of titanate coupling agent, wherein isopropyl three(Dioctyl Jiao's phosphorus
Sour acyloxy)The addition of titanate esters accounts for the 2-10% of modified nano-ZnO quality;
(4)Low density polyethylene (LDPE)/attapulgite modified nano composite material is taken to be dissolved in toluene solution, then by nano modification
ZnO particles are added in above-mentioned solution, and nano modification ZnO/ low density polyethylene (LDPE)s/attapulgite modified nano inorganic-, which are made, to be had
Machine composite;
(5)By phenolic resin 80-100 parts, carbonitride 10-20 parts, polystyrene 20-30 parts, epoxy resin 30-40 parts, antioxygen
Agent 5-8 parts, plasticizer 5-10 parts, glass fibre 10-15 parts and step(4)Obtained composite about 10-20 parts mix, and pour into
Homogenizer, first stirred 30 minutes using 1000 revs/min of speed at room temperature, then at 60 DEG C with 3000 revs/min
Speed stirring 30min, by the batch mixing to stir discharge, melting, injection molding, obtain the cable insulation material.
2. preparation method as claimed in claim 1, it is characterised in that the particle diameter of the ZnO Nanoparticles is 30-100nm;Institute
The addition for stating coupling agent accounts for the 2-10% of nano-ZnO quality.
3. preparation method as claimed in claim 1 or 2, it is characterised in that plasticizer is acetyl tributyl citrate.
4. preparation method as claimed in claim 1 or 2, it is characterised in that the step(1)Detailed process be:By bumps
Rod original ore soil is added in 150mL distilled water, and the bulky grain thing except beaker bottom is filtered off after ultrasonic disperse about 10~30min
Matter, centrifuge, dry, grind, roasting;Baked attapulgite is placed in ultrasound in the acetum that concentration is 0.1-2mol/L
1~2h is reacted after scattered at 80 DEG C~90 DEG C, finally filters, wash until neutral, drying;The attapulgite of acidifying is added
15~20min of ultrasonic disperse under nitrogen protection into toluene, then temperature is risen to after 110~120 DEG C and is added to polyamides Asia
In the aqueous solution of amine, 5~6h is reacted after ultrasonic 20-30min is scattered at 80~100 DEG C, then filtering, with distilled water and anhydrous
Ethanol washs, is dried in vacuo 10~12h at 60~80 DEG C, obtains attapulgite modified.
5. preparation method as claimed in claim 1, it is characterised in that the step(5)Middle melting temperature is 200-280 DEG C,
The injection molding temperature is 120-150 DEG C.
6. preparation method as claimed in claim 1, it is characterised in that the matter of the low density polyethylene (LDPE)/attapulgite modified
It is 20-40 to measure ratio:2-10, nano modification ZnO account for low density polyethylene (LDPE)/attapulgite modified nano composite material mass percent
For 0.5-1.5%.
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CN201711045834.4A Withdrawn CN107603133A (en) | 2016-05-12 | 2016-05-12 | A kind of ageing-resistant cable insulation material Preparation method and use for including low density polyethylene (LDPE)/modified attapulgite |
CN201711045831.0A Withdrawn CN107663355A (en) | 2016-05-12 | 2016-05-12 | A kind of ageing-resistant cable insulation material preparation method for including modified attapulgite |
CN201711048570.8A Withdrawn CN107793696A (en) | 2016-05-12 | 2016-05-12 | A kind of preparation method of the ageing-resistant cable insulation material of super-pressure |
CN201711048569.5A Withdrawn CN107652623A (en) | 2016-05-12 | 2016-05-12 | A kind of ageing-resistant cable insulation material preparation method |
CN201711045833.XA Withdrawn CN107698934A (en) | 2016-05-12 | 2016-05-12 | A kind of ageing-resistant cable insulation material preparation method for including low density polyethylene (LDPE) |
CN201711051354.9A Withdrawn CN107674371A (en) | 2016-05-12 | 2016-05-12 | A kind of preparation method of the ageing-resistant cable insulation material of the super-pressure comprising low density polyethylene (LDPE) |
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CN201610310106.0A Active CN105860427B (en) | 2016-05-12 | 2016-05-12 | A kind of ageing-resistant cable insulation material Preparation method and use for including low density polyethylene (LDPE)/modified attapulgite |
CN201711045834.4A Withdrawn CN107603133A (en) | 2016-05-12 | 2016-05-12 | A kind of ageing-resistant cable insulation material Preparation method and use for including low density polyethylene (LDPE)/modified attapulgite |
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CN107674370A (en) * | 2016-05-12 | 2018-02-09 | 王尧尧 | A kind of cable insulation material preparation method comprising modified alta-mud |
CN106838497B (en) * | 2017-01-13 | 2018-09-11 | 江苏必得科技股份有限公司 | A kind of inner insulation metal soft pipe and its production technology |
CN108329565A (en) * | 2018-03-06 | 2018-07-27 | 江西太平洋电缆集团有限公司 | Cable insulating materials, flexible mineral insulation fireproof cable |
CN113862818B (en) * | 2021-08-31 | 2024-03-29 | 大韩道恩高分子材料(上海)有限公司 | Preparation and application methods of electret material for degradable resin |
CN116631675B (en) * | 2023-06-15 | 2024-03-15 | 安徽远征传导科技股份有限公司 | Mobile abrasion-resistant and drag-resistant shielded cable with large cross section and flame resistance |
CN117624786A (en) * | 2024-01-26 | 2024-03-01 | 广东电缆厂有限公司 | Polypropylene insulation medium-voltage power cable and preparation method thereof |
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CN107652623A (en) | 2018-02-02 |
CN105860427B (en) | 2017-12-15 |
CN107603133A (en) | 2018-01-19 |
CN107663355A (en) | 2018-02-06 |
CN107674371A (en) | 2018-02-09 |
CN107698934A (en) | 2018-02-16 |
CN107698935A (en) | 2018-02-16 |
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