CN106117699A - A kind of preparation method of the Fire retardation electric cable insulation material containing magnesium aluminate spinel - Google Patents
A kind of preparation method of the Fire retardation electric cable insulation material containing magnesium aluminate spinel Download PDFInfo
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- CN106117699A CN106117699A CN201610458503.2A CN201610458503A CN106117699A CN 106117699 A CN106117699 A CN 106117699A CN 201610458503 A CN201610458503 A CN 201610458503A CN 106117699 A CN106117699 A CN 106117699A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/443—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/29—Protection against damage caused by extremes of temperature or by flame
- H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
Abstract
The present invention relates to a kind of preparation method comprising nano magnalium spinelle cable insulation material, described nano magnalium spinelle MgAl2O4There is special structure, can be as the inorganic nanometer oxide material of high-quality, add in polyene material LDPE/EVA/PVC, 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, increase carbon left, LOI loss on ignition index is greatly improved.
Description
Technical field
The present invention relates to the preparation method of a kind of Fire retardation electric cable insulation material comprising nano magnalium spinelle, described magnalium
Spinelle has special structure, can add in polyene LDPE/EVA material as the inorganic material of high-quality, improves insulation
The thermostability of material and intensity, 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..Electrician
Technically, 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 is at the material that electric current electrically can be stoped to pass through.Crosslinked polyethylene has excellent dielectric properties and mechanical performance, oneself
It is widely used in high pressure and supertension plastic insulating power cable.Along with supertension, extra-high voltage direct-current power transmission and transformation system
Development, 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 power equipment worked long hours is exhausted
Edge can cause poplar bundles, reduce cable service life.The high voltage power cable insulant being made up of Low Density Polyethylene,
During Process of Long-term Operation is affected the most aging by various aging actions, is caused under dielectric properties and the mechanical performance of material
Fall.Classification according to aging action can be divided into voltage ageing, heat ageing, mechanical aging and Electrochemical Ageing.Wherein heat ageing is poly-
The main inducing of ethylene cable insulation infringement, different thermal aging time and condition can cause the difference of polyethylene inner molecular structure
Different, and then affect its space charge characteristic.
Research shows, under DC electric field effect, easily forms space charge, and space charge can make in polymer insulation
Electric Field Distribution is distorted, and aggravation polymer insulation is aging, the aging decline that result in material electric property of material.Polymer
Space-charge is mainly by the same polarity space charge entering sunken carrier or transportable current-carrying of electrode injection and insulator
Organic or inorganic impurity ionizes the heteropolarity electricity of generation under electric field action.In order to suppress the formation of space charge, need poly-
Ethylene modified thus change trap energy therein and distribution, change distribution of space charge, lower distortion probability, improve polymer
Dielectric properties, 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.At present for
The fire resistance of insulant is improved, and adding suitable fire retardant is one of major way.Become charcoal that the anti-flammability of polymer is had
Have a significant impact.Therefore, research and development can promote that the fire retardant of the more participation charcoal of polyene material self or carbonized agent have efficiently
Significance.In recent years, in order to improve fire-retardant polyethylene material char yield, improve carbon-coating structure with improve charcoal become quality,
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 insulation breakdown
The major reason of accident.The at present research to the space charge in polymer focuses primarily upon the product of space charge in suppression medium
Life and migration characteristic thereof, generally, the space charge in insulant (such as polyethylene) is mainly made up of 2 parts: one is
High field pretend with under enter sunken carrier or transportable carrier, referred to as same polarity from the electrode injection contacted with medium
Electric charge；Another part is under relatively low field intensity effect, and the impurity in medium ionizes under electric field action and occurs to migrate and shape
The space charge become, referred to as heterocharge.The doping of CNFS orientation successful change of the carrier side of transporting in medium
Formula, reduces trap level, makes carrier be prone to along being perpendicular to thickness direction and transports, effectively inhibits carrier through-thickness
Injection and space charge accumulation in medium. semi-conductive layer weakens outer powering up 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 a small amount of space charge of final residual. 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.Phosphorus series compound fire-retardant
Effect 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
By contacting of combustion 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 polymerization
Thing 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 noninflammability gas such as HCN, N2, NH3, NO2 and NO
Body.The concentration of the imflammable gas produced when oxygen in these gas dilutions air and high polymer decomposes, the most nitrogenous
Fire retardant catabolic process also absorbs a part of heat, and additionally nitrogen can also catch free radical, suppresses the chain reaction of high polymer,
Reach to remove the effect of free radical, thus reach fire-retardant purpose.
Dicyandiamide has Halogen, low toxicity, the advantage of low cigarette, and nitrogenous flame ratardant is preferable, especially at the flame retardant effect of polyester plastics
It is to be combined with phosphorus flame retardant, can form Intumscent Flame Retardant System, by the synergism of the two, can be greatly improved poly-
The flame retardant effect of alkene insulant.The application have employed dicyandiamide and is applied in combination with lanthanum orthophosphate, and adjusts the ratio of the two, makes
It plays synergism, forms Intumscent Flame Retardant System, and test shows, dicyandiamide: the optimal mass ratio of lanthanum orthophosphate is 1:1.
Flame retardant effect can be greatly improved.Applicant thinks mainly both to have been contained containing phosphorus component in phosphoric acid lanthanum, possibly together with rare earth element,
Due to the addition of rare earth element, the performance such as fire-retardant, intensity that can increase swelling degree, beneficially polyolefin insulation material further.
Nano inorganic oxide is the good selection of fire retardant, and such as nano magnesia, nano zine oxide etc. can be made
Join in polyene material for nano inorganic oxide fire retardant.Due to nano effect, Preparing Organic-inorganic Nano Hybrid Material has
Having more conventional polymer/filler compound incomparable a little, such as density is little, mechanical strength is high, inspiratory and breathability
Can the, particularly thermostability and anti-flammability can be greatly improved.Further, also have scholar's research attapulgite, montmorillonite,
The fire resistance of the clay class laminated nm-silicate composite materials such as molecular sieve, it is fire-retardant that above-mentioned inorganic material all has in various degree
Effect.Spinel compound has optics, electricity and the magnetic performance of uniqueness, is widely used at biological and ceramic aspect,
There is Heat stability is good, low cost and other advantages.There is presently no the magnesium aluminate spinel composition metal oxygen using structure more excellent
Compound is 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
Compound 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 by adopting
With either physically or chemically stoping burn cycle.
Someone use inorganic material zeolite as the fire retardant of insulant, but zeolite is rigid structure, bridging oxygen key phase
To shorter, and lack flexibility, there is certain defect.It is added polyene material with molecular sieve SBA-15 together with spinelle, mixed
Close and form fire-retardant built agent, moreover it is possible to increase the intensity of complex material further, compensate for the defect of flexible difference in molecular screen material,
Form hard and soft complementation, inorganic material is carried out skeletonizing or intercalation, form spatial stability structure, control the migration of space charge
Speed, improves charge movement speed, is conducive to capture or detrapping, it is to avoid the polymerization of electric charge, thus avoids making it aging, easy
The cable material usually produced problem such as combustion, improve fire resistance, increase intensity, increase carbon left, thus improve LOI index,
Ageing-resistant.
Conductive polymeric composite is by various electroconductive stuffings in a different manner with processing technique (such as dispersion again
Close, lamination is compound, form surface electrolemma etc.) it is filled in polymeric matrix.The matrix resin that conducing composite material is conventional has:
EVA, PS, PE (LDPE, HDPE), PP, PVC, ABS, PA, PBT, PET, PC, PI, PPS, phenolic resin, epoxy
The polymer such as resin, poly-virtue are soughed, polypropylene vinegar, butyronitrile rubber, organic silicon rubber.Conductive polymeric composite is in technology
On than structural conductive macromolecular material, there is more ripe advantage, compared with metal, conductive composite material has processing
The advantage such as property is good, technique is simple, corrosion-resistant, resistivity adjustable extent is big, price is low.EVA is to be obtained by ethene-vinyl acetate copolymerization
The copolymer arrived.The function of the processing characteristics of macromolecular material and the electric conductivity of conductive filler has together decided on macromolecule
Based conductive composite material has can need to regulate its electricity, mechanics and other performances according to use in a big way, and chemistry is steady
Qualitative preferably, with low cost, it is easy 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, as absolutely
Edge body-conductor jumping phenomenon (percolation phenomena), resistivity is to temperature, pressure, gas concentration sensitivity, current-voltage non-linear row
For, current noise etc..
The present invention uses magnesium aluminate spinel AB2O4 as inorganic nano flame retardant constituent first, joins polyene material
In LDPE/EVA/PVC, due to the addition of magnesium aluminate spinel, thus it is possible to vary carrier transfer ways in medium, reduce trap
Energy level, makes carrier be prone to along being perpendicular to thickness direction and transports, effectively inhibit injection and the space of carrier through-thickness
Electric charge accumulation in medium. semi-conductive layer weakens extra electric field on thickness of sample direction to a certain extent, reduces half
Field intensity at conductive layer and interfacial dielectric layer, decreases the space charge amount that negative electrode injects, and after short circuit, in sample, final residual is few
Quantity space electric charge, reduces the aggregation of electric charge, improves the electricity saving performance of material, improves the aging resistance of insulant, resistance to height
Warm nature energy, plays efficient fire-retardant purpose.The present invention is also added into molybdenum carbide and Firebrake ZB as fire retardant, and the two has preferably
Thermal stability, can play fire-retardant, increase carbon left, form the effect such as effective parcel, preferably the two mass ratio after burning
Example is 1:1.
The application polyene main material is LDPE/EVA/PVC: low density polyethylene, EVA, polyvinylchloride mixing,
Composite high-molecular kind is expanded, and the complementary structure of the most various macromolecular materials, composite flame-proof agent material is direct with polyene
Contact, combines closely, and forms active surface and covers and space invasion and attack, occupies suitable flame retardant activity position, and add sunken
Trap quantity, improves electric charge flowing, adds average breakdown strength, is conducive to improving the service life of insulant.Therefore, originally
The insulant of application both can improve service life, ageing-resistant, impact resistance, and intensity is high, and can also keep the most fire-retardant
Effect, increases the carbon left of polyene material, LOI loss on ignition index is greatly improved.Traditional, PVC has chlorine-containing components, adds thermal capacitance
It is easily generated the toxic gas of hydrogen chloride, in addition it is also necessary to further absorption processes；The present invention addition by magnesium aluminate spinel, permissible
Generate NiCl2, MgCl2 component to a certain extent, and said components is easier to reclaim, and carries out suitable displacement reaction and obtains
Suitable salt can remove the generation of toxic gas from, environmentally friendly.
The present invention relates to the preparation method of a kind of cable insulation material comprising magnesium aluminate spinel/metallic organic framework, institute
Stating cable insulation material is to prepare in accordance with the following steps:
(1) complex magnoferrite MgAl is prepared2O4:
(a)MgAl2O4Preparation: weigh 0.02molMg (NO respectively3)2·6H2O、0.04molAl(NO3)3 ·9H2O is dissolved in 50ml
Deionization edema, joins to obtain mixing salt solution, takes 0.04molNa2CO3, 0.06molNaOH is dissolved in 50ml deionized water, the soonest
Speed stirring, adds aqueous slkali by saline solution, makes PH be maintained at 9-11, mix homogeneously, precipitation is filtered, during deionized water is washed till
Property.80-100 DEG C of baking oven is dried 8-10h.Then at 800-1000 DEG C of Muffle kiln roasting 4-6h.
B prepared by () SBA-15: under conditions of 35-40 DEG C, three block surface activating agent P123 are dissolved in appropriate deionization
Water, is added thereto to tetraethyl orthosilicate (TEOS), hydrochloric acid (HCl), continuing vigorous ground stirring 24h, loads in politef bottle
100-180 DEG C of crystallization 24h, is filtered, washed and dried, and finally calcines 5-8h at 550 DEG C, is then filtered, washed and dried, obtains
White powder be SBA-15.The mol ratio of experiment each raw material used is about 1TEOS:0.017P123:5.88HCl:
136H2O。
(2) LDPE 80-100 part, EVA60-80 part, polyvinylchloride 40-50 part, carborundum 10-20 part, asphalt mixtures modified by epoxy resin are taken
Fat 10-20 part, dicyandiamide 5-15 part, lanthanum orthophosphate 5-15 part, antioxidant 3-5 part, mica sheet 5-15 part, poly-dioxy radical siloxane
10-20 part, meerschaum 5-10 part, Firebrake ZB 5-10 part, molybdenum carbide 5-10 part, SBA 5-10 part and step (1) obtain
MgAl2O410-20 part mixes, and adds in centrifuge, stirs 10-20 minute, mix homogeneously under the conditions of 800-1000r/min
After, entering double screw extruder and be squeezed into molten condition, then by injector, molten mass is rapidly injected in mould, cooling is fixed
Type, after die sinking, finished product enters secondary mould, and cutting obtains finished product.Wherein, in step (2), melt temperature is control temperature 180-220 DEG C.
Wherein said magnoferrite is 2-3:1 with the mass ratio of SBA-15.More select 2:1；Described dicyandiamide: lanthanum orthophosphate
Mass ratio is 1:1；It is furthermore preferred that molybdenum carbide: the mass ratio of Firebrake ZB is 1:1.Described magnesium aluminate spinel mean diameter is 20-
65nm, preferably 25-45nm.
Described antioxidant master can effectively prevent the autoxidation of polymer, mainly uses antioxidant 1024, antioxidant
565, antioxidant 1010 etc., and it is not limited to antioxidant material commonly used in the art.
The cable insulation material of the present invention, owing to using dimension stone of magnesia alumina spinel first, utilizes its advantage space structure, and
Being combined with molecular screen material, a part can produce more inorganic nano flame-retardant composition, removes from and is individually added into inorganic nano oxygen
Changing the inorganic anti-flaming materials such as magnesium, another part can utilize space omission structure, the carbon-forming performance of aggregation thing material, improves
Comprehensive covering of LOI index, beneficially fire proofing, is greatly improved fire resistance.This cable insulation material is high pressure and surpasses
Application in high-pressure plastic insulated power cable, can be substantially reduced aging, improve cable insulation material high temperature resistant, use strong
Degree and resistance to fire resistance.
The application have studied and includes magnesium aluminate spinel MgAl2O4With molecular sieve SBA-5, LDPE/EVA/PVC is combined polyene material
Fire-retardant and the mechanical property of material, by having limited oxygen index, vertical combustion, carbon left and mechanical property tests to measure, it is known that compound
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 a kind of without environment dirt
Dye 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 magnoferrite MgAl is prepared2O4:
(a)MgAl2O4Preparation: weigh 0.02molMg (NO respectively3)2 ·6H2O、0.04molAl(NO3)39H2O is dissolved in
50ml deionization edema, joins to obtain mixing salt solution, takes 0.04molNa2CO3,0.06molNaOH and is dissolved in 50ml deionized water,
The most quickly stirring, saline solution is added aqueous slkali, make PH be maintained at 9-11, mix homogeneously, precipitation filtered, deionization is washed
To neutral.100 DEG C of baking ovens are dried 10h.Then at 1000 DEG C of Muffle kiln roasting 4h.
B prepared by () SBA-15: under conditions of 40 DEG C, three block surface activating agent P123 are dissolved in appropriate amount of deionized water,
It is added thereto to tetraethyl orthosilicate (TEOS), hydrochloric acid (HCl), continuing vigorous ground stirring 24h, load in politef bottle 120
DEG C crystallization 24h, is filtered, washed and dried, and finally calcines 6h at 550 DEG C, is then filtered, washed and dried, the white powder obtained
End is SBA-15.The mol ratio about 1TEOS:0.017P123:5.88HCl:136H2O(of experiment each raw material used also can adopt
Purchase).
(2) LDPE 100 parts, EVA80 part, polyvinylchloride 50 parts, carborundum 20 parts, epoxy resin 10 parts, double cyanogen are taken
Amine 5 parts, lanthanum orthophosphate 5 parts, 3 parts of antioxidant, mica sheet 5 parts, poly-dioxy radical siloxane 10 parts, meerschaum 5 parts, Firebrake ZB 5 parts, carbon
Change the MgAl that molybdenum 5 parts, SBA 10 parts and step (1) obtain2O420 parts of mixing, add in centrifuge, under the conditions of 1000r/min
Stir 20 minutes, after mix homogeneously, enter double screw extruder and be squeezed into molten condition, then by injector, molten mass is quick
Injecting in mould, cooling and shaping, after die sinking, finished product enters secondary mould, and cutting obtains finished product.
Embodiment 2
(1) complex magnoferrite MgAl is prepared2O4:
(a)MgAl2O4Preparation: weigh 0.02molMg (NO3) 2 6H2O, 0.04molAl (NO3) 3 9H2O respectively and be dissolved in 50ml
Deionization edema, joins to obtain mixing salt solution, takes 0.04molNa2CO3,0.06molNaOH and is dissolved in 50ml deionized water, then
Quickly stirring, adds aqueous slkali by saline solution, makes PH be maintained at 9-11, mix homogeneously, precipitation is filtered, during deionized water is washed till
Property.80 DEG C of baking ovens are dried 8h.Then at 800 DEG C of Muffle kiln roasting 4h.
B prepared by () SBA-15: under conditions of 40 DEG C, three block surface activating agent P123 are dissolved in appropriate amount of deionized water,
It is added thereto to tetraethyl orthosilicate (TEOS), hydrochloric acid (HCl), continuing vigorous ground stirring 24h, load in politef bottle 180
DEG C crystallization 24h, is filtered, washed and dried, and finally calcines 8h at 550 DEG C, is then filtered, washed and dried, the white powder obtained
End is SBA-15.The mol ratio about 1TEOS:0.017P123:5.88HCl:136H2O(of experiment each raw material used also can adopt
Purchase).
(2) LDPE100 part, EVA60 part, polyvinylchloride 40 parts, carborundum 10 parts, epoxy resin 20 parts, dicyandiamide are taken
15 parts, lanthanum orthophosphate 15 parts, 5 parts of antioxidant, mica sheet 5 parts, poly-dioxy radical siloxane 10 parts, meerschaum 10 parts, Firebrake ZB 10 parts,
The MgAl that molybdenum carbide 10 parts, SBA 10 parts and step (1) obtain2O420 parts of mixing, add in centrifuge, in 800r/min condition
Lower stirring 20 minutes, after mix homogeneously, enters double screw extruder and is squeezed into molten condition, then by injector, molten mass is fast
Speed is injected in mould, cooling and shaping, and after die sinking, finished product enters secondary mould, and cutting obtains finished product.
Embodiment 3
(1) complex magnoferrite MgAl is prepared2O4:
(a)MgAl2O4Preparation: weigh 0.02molMg (NO respectively3)2·6H2O、0.04molAl(NO3)39H2O is dissolved in 50ml
Deionization edema, joins to obtain mixing salt solution, takes 0.04molNa2CO3,0.06molNaOH and is dissolved in 50ml deionized water, then
Quickly stirring, adds aqueous slkali by saline solution, makes PH be maintained at 9-11, mix homogeneously, precipitation is filtered, during deionized water is washed till
Property.80 DEG C of baking ovens are dried 8h.Then at 1000 DEG C of Muffle kiln roasting 6h.
B prepared by () SBA-15: under conditions of 40 DEG C, three block surface activating agent P123 are dissolved in appropriate amount of deionized water,
It is added thereto to tetraethyl orthosilicate (TEOS), hydrochloric acid (HCl), continuing vigorous ground stirring 24h, load in politef bottle 160
DEG C crystallization 24h, is filtered, washed and dried, and finally calcines 8h at 550 DEG C, is then filtered, washed and dried, the white powder obtained
End is SBA-15.The mol ratio about 1TEOS:0.017P123:5.88HCl:136H2O(of experiment each raw material used also can adopt
Purchase).
(2) LDPE 80 parts, EVA60 part, polyvinylchloride 40 parts, carborundum 10 parts, epoxy resin 10 parts, dicyandiamide are taken
5 parts, lanthanum orthophosphate 5 parts, 5 parts of antioxidant, mica sheet 5 parts, poly-dioxy radical siloxane 20 parts, meerschaum 5 parts, Firebrake ZB 10 parts, carbon
Change the MgAl that molybdenum 10 parts, SBA 8 parts and step (1) obtain2O416 parts of mixing, add in centrifuge, under the conditions of 1000r/min
Stir 20 minutes, after mix homogeneously, enter double screw extruder and be squeezed into molten condition, then by injector, molten mass is quick
Injecting in mould, cooling and shaping, after die sinking, finished product enters secondary mould, and cutting obtains finished product.
Comparative example 1
Being added without nano spinel, other experiment parameters are with embodiment 1.
Comparative example 2
Being added without SBA-15 molecular sieve, other experiment parameters are with embodiment 1.
Comparative example 3
Not adding lanthanum orthophosphate and molybdenum carbide, other experiment parameters are with embodiment 1.
Comparative example 4
Not adding Firebrake ZB and molybdenum carbide, 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, hard
Then above-mentioned aging resistance cable insulation material is carried out hot air aging through 250 DEG C × 30 by degree, LOI index all over the world, then examines
Survey 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 left, wt% | 20.9 | 19.9 | 19.7 | 10.2 | 12.2 | 14.3 | 12.7 |
| Hardness, ShoreA | 90 | 93 | 90 | 81 | 80 | 78 | 73 |
| Hot strength, MPa | 50 | 51 | 49 | 40 | 37 | 42 | 40 |
| Elongation at break % | 530 | 520 | 520 | 390 | 393 | 400 | 410 |
| LOI | 29.5 | 30.2 | 31.1 | 19.2 | 20.1 | 25.9 | 22.9 |
| 250 DEG C × 30 days, LOI | 32.3 | 32.4 | 33.1 | 24.6 | 21.9 | 20.7 | 22.8 |
| 250 DEG C × 30 days, E1/ % | 92.5 | 92.8 | 92.0 | 80.0 | 81.0 | 81.3 | 81.1 |
| 250 DEG C × 30 days, E2/ % | 90.4 | 90.8 | 90.4 | 69.9 | 69.8 | 69.7 | 70.7 |
There is the above results it can be seen that by adding magnesium aluminate spinel and molecular sieve SBA-15, advantageously reduce insulant
The density of LDPE/EVA/PVC system, improves thermostability and the intensity of insulant, reduces the ageing time of insulant, improve
LOI index, has good anti-flammability, improves carbon left, long-time (250 DEG C × 30 days) under high temperature action can be kept not drop
Solving, and still have higher LOI index through long-time (250 DEG C × 30 days), fire resistance is preferable.
The above, the only detailed description of the invention of the present invention, but protection scope of the present invention is not limited thereto, and any
Those of ordinary skill in the art in the technical scope that disclosed herein, the change that can expect without creative work or
Replace, all should contain within protection scope of the present invention.Therefore, protection scope of the present invention should be limited with claims
Fixed protection domain is as the criterion.
Claims (8)
1. the preparation method of the Fire retardation electric cable insulation material containing magnesium aluminate spinel, it is characterised in that described cable insulation material
Material is to prepare in accordance with the following steps:
(1) magnesium aluminate spinel MgAl is prepared2O4:
(2) LDPE 80-100 part, EVA60-80 part, polyvinylchloride 40-50 part, carborundum 10-20 part, epoxy resin are taken
10-20 part, dicyandiamide 5-15 part, lanthanum orthophosphate 5-15 part, antioxidant 3-5 part, mica sheet 5-15 part, poly-dioxy radical siloxane 10-
Prepared by 20 parts, meerschaum 5-10 part, Firebrake ZB 5-10 part, molybdenum carbide 5-10 part, molecular sieve SBA-15 5-10 part and step (1)
MgAl2O410-20 part mixes, and adds in centrifuge, stirs 10-20 minute, mix homogeneously under the conditions of 800-1000r/min
After, entering double screw extruder and be squeezed into molten condition, then by injector, molten mass is rapidly injected in mould, cooling is fixed
Type, after die sinking, finished product enters secondary mould, cutting.
2. preparation method as claimed in claim 1, it is characterised in that described MgAl2O4Preparation method is: weigh respectively
0.02molMg(NO3)2 ·6H2O、0.04molAl(NO3)39H2O is dissolved in 50ml deionization edema, joins to obtain mixing salt solution,
Take 0.04molNa2CO3, 0.06molNaOH be dissolved in 50ml deionized water, the most quickly stir, saline solution added aqueous slkali,
Making pH be maintained at 9-11, mix homogeneously, precipitation filtered, deionized water is washed till neutrality, dries 8-10h in 80-100 DEG C of baking oven,
Then at 800-1000 DEG C of Muffle kiln roasting 4-6h.
3. preparation method as claimed in claim 2, it is characterised in that the preparation process of described SBA-15 molecular sieve is: at 35-
Under conditions of 40 DEG C, three block surface activating agent P123 are dissolved in appropriate amount of deionized water, are added thereto to tetraethyl orthosilicate
(TEOS), hydrochloric acid (HCl), continuing vigorous ground stirring 24h, load 100-180 DEG C of crystallization 24h in politef bottle, filter, wash
Washing and be dried, finally calcine 5-8h at 550 DEG C, be then filtered, washed and dried, the white powder obtained is SBA-15, respectively
The mol ratio of raw material is about TEOS:P123:HCl:H2O=1:0.017:5.88:136.
4. preparation method as claimed in claim 1, it is characterised in that in step (2), melt temperature is 180-220 DEG C.
5. preparation method as claimed in claim 3, it is characterised in that dicyandiamide in insulant: lanthanum orthophosphate mass ratio is 1:
1。
6. the preparation method as described in claim 1 or 5, it is characterised in that MgAl2O4: the mass ratio of SBA-15 is 2:1.
7. preparation method as claimed in claim 1, it is characterised in that described magnesium aluminate spinel mean diameter is 20-65nm, excellent
Select 25-45nm.
8. the insulant that the preparation method as described in any one of claim 1-7 obtains is at high pressure or supertension plastic insulation electricity
Application in power cable.
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| CN115043418B (en) * | 2022-07-18 | 2024-03-26 | 大连交通大学 | Preparation method of magnesia-alumina spinel mesoporous carrier material |
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