CN105949581A - Preparation method and application of flame-retardant cable insulating material comprising nano perovskite oxide LaxSr[1-x]CoO3 - Google Patents
Preparation method and application of flame-retardant cable insulating material comprising nano perovskite oxide LaxSr[1-x]CoO3 Download PDFInfo
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Abstract
The invention relates to a preparation method of a flame-retardant cable insulating material comprising nano perovskite oxide LaxSr[1-x]CoO3. Nano perovskite oxide and a metal organic framework UIO material are together added into a three-element polyene ester material (LDPE (low-density polyethylene)/EVA (ethylene-vinyl acetate)/phenolic resin) to enhance the heat resistance and strength of the insulating material and shortening the aging time of the insulating material. The insulating material can keep undegraded for a long time under the action of high temperature, and can keep favorable flame-retardant effect; and the LOI (loss on ignition) index is greatly enhanced.
Description
Technical field
The present invention relates to the preparation method of a kind of Fire retardation electric cable insulation material comprising nano-perovskite granule, described nano-perovskite oxide LaxSr1-xCoO3There is special structure, can be as the inorganic nanometer oxide material of high-quality, it is jointly added in polyalkenylesters material with organometallic skeletal UIO material, improve thermostability and the intensity of insulant, reduce the ageing time of insulant, can keep the most non-degradable under high temperature action, and preferable flame retardant effect can also be kept, LOI loss on ignition index is greatly improved.
Background technology
Insulant conventional in cable has oil-paper, polrvinyl chloride, polyethylene, crosslinked polyethylene, rubber etc..On electrotechnics, by specific insulation more than 109The material that the material of Ω cm is constituted is referred to as insulant, is namely used for making device at the material that electric current electrically can be stoped to pass through.Crosslinked polyethylene has excellent dielectric properties and mechanical performance, and oneself is widely used in high pressure and supertension plastic insulating power cable.Along with supertension, the development of extra-high voltage direct-current power transmission and transformation system, the insulation ageing problem in running is increasingly severe, and oneself becomes the major obstacle that insulated cable develops to supertension.When the working field strength of insulating polymer reach breakdown field strength ten/for the moment, the Electric Power Equipment Insulation worked long hours can cause poplar bundles, reduce cable service life.The high voltage power cable insulant being made up of Low Density Polyethylene, is affected the most aging by various aging actions in During Process of Long-term Operation, causes the dielectric properties of material and the decline of mechanical performance.Classification according to aging action can be divided into voltage ageing, heat ageing, mechanical aging and Electrochemical Ageing.Wherein heat ageing is the main inducing of PE cable insulation infringement, and different thermal aging time and condition can cause the difference of polyethylene inner molecular structure, and then affect its space charge characteristic.
Research shows, under DC electric field effect, easily forms space charge, and space charge can make Electric Field Distribution be distorted in polymer insulation, and aggravation polymer insulation is aging, the aging decline that result in material electric property of material.Space Charge in Polymer is mainly ionized the heteropolarity electricity of generation under electric field action by the same polarity space charge entering sunken carrier or transportable current-carrying of electrode injection and organic or inorganic impurity in insulator.In order to suppress the formation of space charge, need, to PE modified thus change trap energy therein and distribution, to change distribution of space charge, lower distortion probability, improve the dielectric properties of polymer, reduce polymer insulation aging, and do not affect the processing characteristics of polymer simultaneously.
Low Density Polyethylene is cable insulation material commonly used in the art, but fire resistance is unsatisfactory.Fire resistance for insulant is improved at present, and adding suitable fire retardant is one of major way.Become charcoal that the anti-flammability of polymer is had to have a significant impact.Therefore, research and development can promote that the fire retardant of the more participation charcoal of polyalkenylesters material self or carbonized agent are significant efficiently.In recent years, in order to improve the char yield of fire-retardant polyethylene material, improve carbon-coating structure and become quality with improving charcoal, for cooperative flame retardant, siloxanes is fire-retardant, polymer nanocomposite is fire-retardant etc., and there is primary study in aspect.
Summary of the invention
Research proves, space charge is to cause power cable electric field distortion, causes shelf depreciation, electric branch and the major reason of dielectric breakdown accident.The at present research to the space charge in polymer focuses primarily upon the generation of space charge in suppression medium and migrates characteristic, generally, space charge in insulant (such as polyethylene) is mainly made up of 2 parts: one be high field pretend with under enter sunken carrier or transportable carrier, referred to as like charges from the electrode injection contacted with medium；Another part is under relatively low field intensity effect, and the impurity in medium ionizes under electric field action and occurs to migrate and the space charge that formed, referred to as heterocharge.The doping of CNFS orientation successful change of carrier transfer ways in medium, reduce trap level, make carrier be prone to along being perpendicular to thickness direction to transport, effectively inhibiting injection and the space charge accumulation in medium of carrier through-thickness. semi-conductive layer weakens extra electric field on thickness of sample direction to a certain extent, reduce the field intensity at semi-conductive layer and interfacial dielectric layer, decrease the space charge amount that negative electrode injects, after short circuit, in sample, the interpolation of final residual a small amount of space charge .CNFS changes the transfer ways of carrier, inhibit space charge by electrode injection in insulating barrier, contribute to fire-retardant, hinder the electric charge polymerization of polymer, improve the service life of insulant.
Phosphorus and phosphorus-containing compound fire retardant are listed as three big flame-retardant systems with halogen system, inorganic system.The flame retardant effect of phosphorus series compound is preferable, because the Metaphosphoric acid generated during burning can be grouped to stable poly state, becomes the protective layer of burning point, can completely cut off and be fired contacting of thing and oxygen.The phosphoric acid and the poly-Metaphosphoric acid that generate are the most all strong acid, have the strongest dehydration property, it is possible to make polymer dehydration carbonization, and form charring layer at polymer surfaces, reach starvation and stop the purpose of burning.
When nitrogenous flame ratardant burns when breaking out of fire, it is heated and easily releases the non-flammable gases such as HCN, N2, NH3, NO2 and NO.The concentration of the imflammable gas produced when oxygen in these gas dilutions air and high polymer decomposes, nitrogenous flame ratardant catabolic process also absorbs a part of heat simultaneously, additionally nitrogen can also catch free radical, the chain reaction of suppression high polymer, reach to remove the effect of free radical, thus reach fire-retardant purpose.
Tripolycyanamide has Halogen, low toxicity, the advantage of low cigarette, nitrogenous flame ratardant is preferable at the flame retardant effect of polyester plastics, is especially combined with phosphorus flame retardant, can form Intumscent Flame Retardant System, by the synergism of the two, the flame retardant effect of polyalkenylesters hydrocarbon insulant can be greatly improved.The application have employed tripolycyanamide and is applied in combination with triethyl phosphate, hydroxyapatite, and adjust the ratio of three, make three play synergism, form Intumscent Flame Retardant System, test shows, the optimal mass ratio of three's (tripolycyanamide: triethyl phosphate: hydroxyapatite) is 1:1:1.Flame retardant effect can be greatly improved.Applicant thinks that mainly containing phosphorus component is jointly to be acted on Phos form by organophosphor, on the basis of different phosphorus forms, in conjunction with nitrogenated flame retardant, structurally can increase swelling degree, and Phos can also occupy intermediate active position in Intumescent Retardant System, the performances such as fire-retardant, the intensity forming the rock-steady structures such as stable system, such as intercalation, link layer, polyhedron, beneficially polyalkenylesters insulant with organophosphor, organic nitrogen.
Nano inorganic oxide is the good selection of fire retardant, and such as nano magnesia, nano zine oxide etc. can serve as nano inorganic oxide fire retardant and joins in polyalkenylesters material.Due to nano effect, it is incomparable a little that Preparing Organic-inorganic Nano Hybrid Material has more conventional polymer/filler compound, and such as density is little, mechanical strength is high, inspiratory and permeability, and particularly thermostability and anti-flammability can be greatly improved.Further, also having the fire resistance of the clay class laminated nm-silicate composite materials such as scholar's research attapulgite, montmorillonite, above-mentioned inorganic material all has flame retardant effect in various degree.Perovskite structure oxide ABO3 has optics, electricity and the magnetic performance of uniqueness, it is widely used in terms of biological agent pottery, having Heat stability is good, low cost, can carry out adsorbing oxygen according to the selection of B position, A, B atom can mention regulation Lattice Oxygen quantity and activity.There is presently no the more excellent nano-perovskite material of employing structure or similar polymetallic metal composite oxide as fire proofing.
The aerial burning of macromolecular compound is the fiercest a kind of oxidation reaction, belongs to chain reaction course.Combustion process is bred the most active hydroxyl free radical, when hydroxyl free radical and macromolecular compound meet, generates Hydrocarbon free radical and water, in the presence of oxygen, Hydrocarbon radical decomposition, form again new hydroxyl free radical.So circulation, makes combustion reaction constantly continue.The mechanism of action of fire retardant is more complicated, comprises many factors, but mainly either physically or chemically stops burn cycle by employing.
Someone use inorganic material zeolite as the fire retardant of insulant, but zeolite is rigid structure, bridging oxygen key is relatively short, and lack flexibility, there is certain defect.A kind of MOF with ultrastability, is labeled as UiO-66, and chemical formula is
Zr6O4 (OH) 4 (CO2) 12, its structure collapse temperature is higher than 500 DEG C.Its stability carrys out inorganic metal unit Zr6O4 (OH) 4 of high degree of symmetry, and this Zr6 octahedron core and the strong interaction of carboxyl oxygen O in part.One Zr6 octahedron core and 12 p-phthalic acid ligands, form tetrahedron and octahedron two kinds of hole cage, on eight faces of each octahedra cage, be all connected with a tetrahedron cage, this connected mode constantly extends at three dimensions, thus forms the MOFs with 6 apertures.It addition, chemical stability test shows, UiO-66 has good water-resistance, acid-resisting.
Therefore, the application sounds out UIO-66 material as the material of composite flame-retardant agent, can improve the resistance to elevated temperatures of cable insulation material, thus improve service life.Owing to metal-organic framework materials is the coordination polymer with metal ion as junction point, when being combined with polythene material, both imidazole skeleton and the polythene material compatibility on high molecular chemical characters in polymer can have been utilized, it is formed with efficient construction, utilize the tetrahedral structure can effective dispersion space electric charge, avoid the gathering of space charge, improve high temperature resistant, ageing-resistant performance；On the other hand, containing metal ion in ZIFS, inorganic compound can be formed, and inorganic compound such as nano inorganic magnesium oxide, ferrum oxide etc. are one of fire retardants of this area, the complementary action of inorganic material can be utilized with polythene material after being combined, the charge transport efficiency of heavy insulation material further, improves fire resistance, improves high temperature resistant, the ageing-resistant performance of insulant.
Conductive polymeric composite is to be filled in polymeric matrix with processing technique (as compound in dispersion, lamination is combined, forms surface electrolemma etc.) in a different manner by various electroconductive stuffings.The matrix resin that conducing composite material is conventional has: EVA, PS, PE (LDPE, HDPE), PP, PVC, ABS,
PA, PBT, PET, PC, PI, PPS, the polymer such as phenolic resin, epoxy resin, poly-virtue are soughed, polypropylene vinegar, butyronitrile rubber, organic silicon rubber.Conductive polymeric composite has more ripe advantage than structural conductive macromolecular material technically, and compared with metal, conductive composite material has the advantages such as processability is good, technique is simple, corrosion-resistant, resistivity adjustable extent is big, price is low.The function of the processing characteristics of macromolecular material and the electric conductivity of conductive filler has together decided on polymer-based conducing composite material to be had and can need to regulate its electricity, mechanics and other performances according to use in a big way, chemical stability is preferable, with low cost, it is prone to molding and large-scale production etc., often make antistatic and electromagnetic shielding material, be widely used in the industry such as electronics, electrical equipment, weaving, colliery.Additionally, composite conductive polymer also has many unique physical phenomenons, such as insulator-conductor jumping phenomenon (percolation phenomena), resistivity is to temperature, pressure, gas concentration sensitivity, current-voltage non-linear behavior, current noise etc..
The present invention uses nano-perovskite oxide La firstxSr1-xCoO3(0.6 < x < 1) is as inorganic nano flame retardant constituent, join in polyalkenylesters material, addition due to nano-perovskite, carrier transfer ways in medium can be changed, reduce trap level, make carrier be prone to along being perpendicular to thickness direction to transport, effectively inhibiting injection and the space charge accumulation in medium of carrier through-thickness. semi-conductive layer weakens extra electric field on thickness of sample direction to a certain extent, reduce the field intensity at semi-conductive layer and interfacial dielectric layer, decrease the space charge amount that negative electrode injects, the a small amount of space charge of final residual in sample after short circuit, reduce the aggregation of electric charge, improve the electricity saving performance of material, improve the aging resistance of insulant, resistance to elevated temperatures, play efficient fire-retardant purpose.
The application polyalkenylesters main material is ternary material (LDPE/EVA/ phenolic resin): low density polyethylene, EVA, phenolic resin mix, composite high-molecular kind is expanded, be conducive to the complementary structure of various macromolecular materials, composite flame-proof agent material directly contacts with polyalkenylesters, combine closely, form active surface to cover and space invasion and attack, occupy suitable flame retardant activity position, and add trap quantity, improve electric charge flowing, add average breakdown strength, be conducive to improving the service life of insulant.Therefore, the insulant of the application both can improve service life, ageing-resistant, impact resistance, and intensity is high, and can also keep preferable flame retardant effect, and LOI loss on ignition index is greatly improved.
The present invention relates to a kind of cable insulation material comprising nano-perovskite oxide particle, described cable insulation material includes LDPE 80-100 part, phenolic resin 50-60 part, EVA60-80 part, white carbon 10-20 part, plasticizer 5-10 part, tripolycyanamide 5-15 part, triethyl phosphate 5-15 part, hydroxyapatite 5-15 part, mica sheet 5-15 part, carbon nano-fiber 5-10 part, LaxSr1-xCoO310-20 part and UIO-66 5-10 part.
Described plasticizer is trioctyl trimellitate (TOTM).Described nano-perovskite oxide LaxSr1-xCoO3Mean diameter be 20-85nm, preferably 20-60nm.Preferably, in cable material, nano-perovskite oxide LaxSr1-xCoO3: the mass ratio of UIO is 2-4:1, preferably 2-3:1；The wherein preferred UIO-66 of UiO material.
Preferably, dicyandiamide in cable material: triethyl phosphate: the mass ratio of hydroxyapatite is 1-3:1:1, most preferably 1:1:1, preferably carbon nano-fiber a length of 10-20 micron.
Described insulant is to prepare in accordance with the following steps:
(1) complex La is preparedxSr1-xCoO3(0.6 < x < 1) and UIO-66:
A () weighs Lanthanum (III) nitrate, cobalt nitrate, strontium nitrate and nitric acid in proportion, be dissolved in deionized water, be configured to nitrate solution, wherein nitric acid: metal ion: the mol ratio of water is (1-4): (2 ~ 4): 70；Separately weighing citric acid to be dissolved in deionized water, be configured to citric acid solution, wherein the mol ratio of citric acid and water is (4 ~ 8): 40；
B nitrate solution is heated to 70 ~ 80 DEG C by (), drip citric acid solution under stirring, and the citric acid amount of addition and the mol ratio of metal ion are 1:1 ~ 1:2；Nitrate solution and citric acid solution adjust pH value of solution to 7 with strong aqua ammonia after being sufficiently mixed uniformly；Gel is obtained after keeping 2 ~ 3 hours at 75 ~ 80 DEG C；
C () is dried into xerogel gained gel at 90 ~ 100 DEG C, then process 0.5 ~ 1 hour at 350 ~ 400 DEG C, obtain nano-perovskite catalyst La1-XSrXCoO3。
Prepared by UIO-66: weigh 0.932g ZrC14 and 1.32 respectively
G p-phthalic acid, in polytetrafluoroethylliner liner, add 24 mL DMF solvent and dissolved, be subsequently adding 0.665 mL concentrated hydrochloric acid, mix homogeneously, supersound process 5 min, seals inner bag, puts in baking oven in 120 DEG C of reacting by heating 16h, then room temperature is reduced the temperature to, by mixture after reaction is centrifuged, bottom centrifuge tube, obtains white precipitate, be UiO-66.
(2) La that LDPE 80-100 part, phenolic resin 50-60 part, EVA60-80 part, white carbon 10-20 part, plasticizer 5-10 part, tripolycyanamide 5-15 part, triethyl phosphate 5-15 part, hydroxyapatite 5-15 part, mica sheet 5-15 part and carbon nano-fiber 5-10 part and above-mentioned steps obtainxSr1-xCoO310-20 part, the mixing of UIO-66 5-10 part, pour homogenizer into, the speed first using 1100 revs/min under room temperature stirs 30 minutes, then 30min is stirred at 60 DEG C with the speed of 4000 revs/min, the batch mixing stirred is discharged, then melt, injection mo(u)lding, obtain described cable insulation material.
Preferably, in described step (2), melt temperature is 200-260 DEG C, and described injection mo(u)lding temperature is 120-150 DEG C, preferably 130-150 DEG C.
Further, present invention employs the carbon nano-fiber that nitrogen is modified, add nitrogenous flame retardance element, and optimize specific surface area and the pore structure of carbon nano-fiber, be beneficial to the anti-flammability to cable material further and improve.
Wherein, in described nitrogen modified carbon nano tube fiber NCNFS, the content of N is 1-5wt%, based on NCNFS overall calculation.Concrete preparation method is: being immersed by carbon nano-fiber in the solution containing ammonia, 120-180 DEG C of hydro-thermal reaction in politef hydrothermal reaction kettle, retention time 0.5-5h, obtain N-CNFS, the doping controlling N is 1-5wt%.
The cable insulation material of the present invention is owing to using nano-perovskite oxide material first, utilize its advantage space structure, and with UIO Material cladding, a part can produce more inorganic nano flame-retardant composition, and another part can utilize the vacant framing structure with ZIF in space, the carbon-forming performance of aggregation thing material, improve LOI index, and the organic backbone in UIO can be combined further with polyalkenylesters material, beneficially comprehensive covering of fire proofing, is greatly improved fire resistance.This cable insulation material is the application in high pressure and supertension plastic insulating power cable, can be substantially reduced aging, improves high temperature resistant, the use intensity of cable insulation material and resistance to fire resistance.
The application have studied and includes composite L axSr1-xCoO3With metallic organic framework UIO-66 to the fire-retardant of LDPE/EVA/ phenolic resin composite and mechanical property, by having limited oxygen index, vertical combustion and mechanical property tests to measure, understand composite cable material high comprehensive performance, stable performance, oxygen index (OI) height, good flame retardation effect, effect are persistently, cheap;By non-volatile, smog is little, avirulence, this composite flame-proof material have concurrently fire-retardant, press down cigarette and reduce the function of toxic gas, be that a kind of non-environmental-pollution fire proofing has prospects for commercial application.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is further detailed explanation.
Embodiment
1
(1) complex La is prepared0.7Sr0.3CoO3With UIO-66:
A () weighs Lanthanum (III) nitrate, cobalt nitrate, strontium nitrate and nitric acid in proportion, be dissolved in deionized water, be configured to nitrate solution, wherein nitric acid: metal ion: the mol ratio of water is 1:4:70；Separately weighing citric acid to be dissolved in deionized water, be configured to citric acid solution, wherein the mol ratio of citric acid and water is 6:40；
B mixed nitrate solution is heated to 70 DEG C by (), drip citric acid solution under stirring, and the citric acid amount of addition and the mol ratio of metal ion are 1:1；Nitrate solution and citric acid solution adjust pH value of solution to 7 with strong aqua ammonia after being sufficiently mixed uniformly；Gel is obtained after keeping 2 hours at 80 DEG C；
C () is dried into xerogel gained gel at 100 DEG C, then process 1 hour at 400 DEG C, obtain nano-perovskite catalyst La0.7Sr0.3CoO3。
Prepared by UIO-66: weigh 0.932gZrC14 and 1.32 respectively
G p-phthalic acid, in polytetrafluoroethylliner liner, add 24 mL DMF solvent and dissolved, be subsequently adding 0.665 mL concentrated hydrochloric acid, mix homogeneously, supersound process 5 min, seals inner bag, puts in baking oven in 120 DEG C of reacting by heating 16h, then room temperature is reduced the temperature to, by mixture after reaction is centrifuged, bottom centrifuge tube, obtains white precipitate, be UiO-66.
(2) La that LDPE 80 parts, 50 parts of phenolic resin, EVA60 part, white carbon 10 parts, plasticizer 5 parts, tripolycyanamide 5 parts, triethyl phosphate 5 parts, hydroxyapatite 5 parts, mica sheet 5 parts and carbon nano-fiber 5 parts and above-mentioned steps obtainxSr1-xCoO310 parts, UIO-66 5 parts mixing, pour homogenizer into, first uses the speed of 1100 revs/min to stir under room temperature 30 minutes, then stir 30min at 60 DEG C with the speed of 4000 revs/min, the batch mixing stirred is discharged, then melts, injection mo(u)lding, obtains described cable insulation material.
Embodiment
2
(1) complex La is prepared0.8Sr0.2CoO3With UIO-66:
A () weighs Lanthanum (III) nitrate, cobalt nitrate, strontium nitrate and nitric acid in proportion, be dissolved in deionized water, be configured to mixed nitrate solution, wherein nitric acid: metal ion: the mol ratio of water is 2:4:70；Separately weighing citric acid to be dissolved in deionized water, be configured to citric acid solution, wherein the mol ratio of citric acid and water is 8:40；
B mixed nitrate solution is heated to 70 DEG C by (), drip citric acid solution under stirring, and the citric acid amount of addition and the mol ratio of metal ion are 1:2；Nitrate solution and citric acid solution adjust pH value of solution to 7 with strong aqua ammonia after being sufficiently mixed uniformly；Gel is obtained after keeping 3 hours at 75 DEG C；
C () is dried into xerogel gained gel at 100 DEG C, then process 1 hour at 350 DEG C, obtain nano-perovskite catalyst La0.8Sr0.2CoO3。
Prepared by UIO-66: weigh 0.932g ZrC14 and 1.32 respectively
G p-phthalic acid, in polytetrafluoroethylliner liner, add 24 mL DMF solvent and dissolved, be subsequently adding 0.665 mL concentrated hydrochloric acid, mix homogeneously, supersound process 5 min, seals inner bag, puts in baking oven in 120 DEG C of reacting by heating 16h, then room temperature is reduced the temperature to, by mixture after reaction is centrifuged, bottom centrifuge tube, obtains white precipitate, be UiO-66.
(2) La that LDPE 80 parts, 50 parts of phenolic resin, EVA60 part, white carbon 20 parts, plasticizer 10 parts, tripolycyanamide 5 parts, triethyl phosphate 5 parts, hydroxyapatite 5 parts, mica sheet 10 parts and carbon nano-fiber 10 parts and above-mentioned steps obtainxSr1-xCoO3
20 parts, UIO-66 10 parts mixing, pour homogenizer into, first uses the speed of 1100 revs/min to stir under room temperature 30 minutes, then stir 30min at 60 DEG C with the speed of 4000 revs/min, the batch mixing stirred is discharged, then melts, injection mo(u)lding, obtains described cable insulation material.
Embodiment
3
(1) complex La is prepared0.9Sr0.1CoO3With UIO-66:
A () weighs Lanthanum (III) nitrate, cobalt nitrate, strontium nitrate and nitric acid in proportion, be dissolved in deionized water, be configured to nitrate solution, wherein nitric acid: metal ion: the mol ratio of water is 1:3:70；Separately weighing citric acid to be dissolved in deionized water, be configured to citric acid solution, wherein the mol ratio of citric acid and water is 5:40；
B mixed nitrate solution is heated to 80 DEG C by (), drip citric acid solution under stirring, and the citric acid amount of addition and the mol ratio of metal ion are 1:1；Nitrate solution and citric acid solution adjust pH value of solution to 7 with strong aqua ammonia after being sufficiently mixed uniformly；Gel is obtained after keeping 2 hours at 80 DEG C；
C () is dried into xerogel gained gel at 90 DEG C, then process 1 hour at 400 DEG C, obtain nano-perovskite catalyst La0.9Sr0.1CoO3。
Prepared by UIO-66: weigh 0.932g ZrC14 and 1.32 respectively
G p-phthalic acid, in polytetrafluoroethylliner liner, add 24 mL DMF solvent and dissolved, be subsequently adding 0.665 mL concentrated hydrochloric acid, mix homogeneously, supersound process 5 min, seals inner bag, puts in baking oven in 120 DEG C of reacting by heating 16h, then room temperature is reduced the temperature to, by mixture after reaction is centrifuged, bottom centrifuge tube, obtains white precipitate, be UiO-66.
(2) La that the carbon nano-fiber 10 parts of LDPE 80 parts, 50 parts of phenolic resin, EVA80 part, white carbon 20 parts, plasticizer 8 parts, tripolycyanamide 10 parts, triethyl phosphate 10 parts, hydroxyapatite 10 parts, mica sheet 5 parts and N doping and above-mentioned steps obtainxSr1-xCoO3
15 parts, UIO-66 5 parts mixing, pour homogenizer into, first uses the speed of 1100 revs/min to stir under room temperature 30 minutes, then stir 30min at 60 DEG C with the speed of 4000 revs/min, the batch mixing stirred is discharged, then melts, injection mo(u)lding, obtains described cable insulation material.Wherein N doping amount is 3wt%.
Comparative example
1
It is added without nano-perovskite LaxSr1-xCoO3, other experiment parameters are with embodiment 1.
Comparative example
2
Being added without UIO material, other experiment parameters are with embodiment 1.
Comparative example
3
Attapulgite is used to replace the La of the present inventionxSr1-xCoO3, other experiment parameters are with embodiment 1.
Comparative example
4
Using 4A molecular sieve to replace the UIO-66 of the present invention, other experiment parameters are with embodiment 1.
Concrete detection
Detect the hot strength (σ t/MPa) of above-mentioned aging resistance cable insulation material, elongation at break (δ/ %), carbon left, hardness, LOI index then above-mentioned aging resistance cable insulation material is all over the world carried out hot air aging through 200 DEG C × 30, then detect stretching strength retentivity (E1/ %) and elongation at break conservation rate (E2/ %), concrete outcome is shown in Table 1.
Table 1 each Testing index of Electric insulation material
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Carbon residue, wt% | 22 | 23 | 25 | 5.8 | 7.7 | 3.9 | 6.6 |
| Hardness, ShoreA | 91 | 90 | 88 | 77 | 72 | 70 | 69 |
| Hot strength, MPa | 50 | 51 | 49 | 40 | 37 | 42 | 40 |
| Elongation at break % | 540 | 520 | 550 | 390 | 389 | 338 | 360 |
| LOI | 35.5 | 35.2 | 38.1 | 19.2 | 14.1 | 17.9 | 16.9 |
| 200 DEG C × 30 days, LOI | 33.3 | 34.4 | 33.1 | 14.6 | 11.9 | 10.7 | 12.8 |
| 200 DEG C × 30 days, E1/ % | 95.5 | 93.8 | 93.0 | 66.0 | 63.0 | 65 | 70.1 |
| 200 DEG C × 30 days, E2/ % | 90.4 | 90.8 | 91.4 | 60.9 | 60.8 | 52.7 | 57.7 |
There is the above results it can be seen that LaxSr1-xCoO3With metallic organic framework UIO-66 modified polyolefin material LDPE/PP, advantageously reduce the density of insulant, improve thermostability and the intensity of insulant, reduce the ageing time of insulant, improve LOI index, there is good anti-flammability, long-time (200 DEG C × 30 days) under high temperature action can be kept non-degradable, and through long-time (200 DEG C × 30 days), still there is higher LOI index, fire resistance is preferable.
The above; it is only the detailed description of the invention of the present invention; but protection scope of the present invention is not limited thereto; any those of ordinary skill in the art are in the technical scope that disclosed herein; the change can expected without creative work or replacement, all should contain within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain that claims are limited.
Claims (8)
1. one kind comprises nano-perovskite oxide LaxSr1-xCoO3The preparation method of Fire retardation electric cable insulation material, it is characterised in that concrete preparation process includes:
(1) La is preparedxSr1-xCoO3With UIO-66,
(2) La that LDPE 80-100 part, phenolic resin 50-60 part, EVA60-80 part, white carbon 10-20 part, plasticizer 5-10 part, tripolycyanamide 5-15 part, triethyl phosphate 5-15 part, hydroxyapatite 5-15 part, mica sheet 5-15 part, carbon nano-fiber 5-10 part and above-mentioned steps are obtainedxSr1-xCoO310-20 part, the mixing of UIO-66 5-10 part, pour homogenizer into, the speed first using 1100 revs/min under room temperature stirs 30 minutes, then 30min is stirred at 60 DEG C with the speed of 4000 revs/min, the batch mixing stirred is discharged, then melt, injection mo(u)lding, obtain described cable insulation material；Wherein nano-perovskite oxide LaxSr1-xCoO3In, 0.6 < x < 1.
2. the preparation method of insulant as claimed in claim 1, it is characterised in that nano-perovskite La in step (1)xSr1-xCoO3Preparation method be:
A () weighs Lanthanum (III) nitrate, cobalt nitrate, strontium nitrate and nitric acid in proportion, be dissolved in deionized water, be configured to mixed nitrate solution, wherein nitric acid: metal ion: the mol ratio of water is (1-4): (2 ~ 4): 70；Separately weighing citric acid to be dissolved in deionized water, be configured to citric acid solution, wherein the mol ratio of citric acid and water is (4 ~ 8): 40；
B nitrate solution is heated to 70 ~ 80 DEG C by (), drip citric acid solution under stirring, and the citric acid amount of addition and the mol ratio of metal ion are 1:1 ~ 1:2；Nitrate solution and citric acid solution adjust pH value of solution to 7 with strong aqua ammonia after being sufficiently mixed uniformly；Gel is obtained after keeping 2 ~ 3 hours at 75 ~ 80 DEG C；
C () is dried into xerogel gained gel at 90 ~ 100 DEG C, then process 0.5 ~ 1 hour at 350 ~ 400 DEG C, obtain nano-perovskite oxide La1-XSrXCoO3。
3. the preparation method of insulant as claimed in claim 1 or 2, it is characterised in that in step (1), the preparation method of UIO-66 is: weigh 0.932g ZrC1 respectively4With 1.32 g p-phthalic acids, in polytetrafluoroethylliner liner, add 24 mL DMF solvent and dissolved, be subsequently adding 0.665 mL concentrated hydrochloric acid, mix homogeneously, supersound process 5 min, inner bag sealed, puts in baking oven in 120
DEG C reacting by heating 16h, then reduces the temperature to room temperature, by being centrifuged mixture after reaction, obtains white precipitate, be UiO-66 bottom centrifuge tube.
4. the preparation method of insulant as claimed in claim 1, it is characterised in that in step (2), melt temperature is 200-280 DEG C, and described injection mo(u)lding temperature is 120-150 DEG C, preferably 130-150 DEG C.
5. the preparation method of insulant as claimed in claim 1, it is characterised in that described plasticizer is trioctyl trimellitate (TOTM)；Described nano-perovskite oxide LaxSr1-xCoO3Mean diameter be 20-85nm, preferably 20-60nm.
6. the preparation method of insulant as claimed in claim 1, it is characterised in that tripolycyanamide: triethyl phosphate: the mass ratio of hydroxyapatite is 1-3:1:1, most preferably 1:1:1.
7. the preparation method of insulant as claimed in claim 1, it is characterised in that carbon nano-fiber a length of 10-20 micron, it is preferred that carbon nano-fiber can also use nitrogen modified, and nitrogen content is 1-5wt%.
8. the cable insulation material that the preparation method as described in any one of claim 1-7 obtains application in high pressure or supertension plastic insulating power cable.
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