CN109280341A - A kind of preparation method of epoxy resin base electromagnetic screen material - Google Patents
A kind of preparation method of epoxy resin base electromagnetic screen material Download PDFInfo
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- CN109280341A CN109280341A CN201811103971.3A CN201811103971A CN109280341A CN 109280341 A CN109280341 A CN 109280341A CN 201811103971 A CN201811103971 A CN 201811103971A CN 109280341 A CN109280341 A CN 109280341A
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0856—Iron
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/01—Magnetic additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses a kind of preparation methods of epoxy resin base electromagnetic screen material, belong to composite polymer material technical field.The present invention is first using epoxy resin and adipic acid as raw material, aqueous epoxy resins are generated under the action of catalyst, aqueous epoxy resins, water, n-hexane and polyethyleneimine is recycled to be stirred, and carbon dioxide is continually fed into mixed process, self-control microemulsion is made, after being then stirred self-control microemulsion and copper salt solution, reducing agent is added, after heating stirring reaction, it is concentrated under reduced pressure, obtains concentrate；After then nano iron oxide and gelatin dispersion liquid are mixed; spray drying; high temperature carbonization; carbonized material is made, recycle after carbonized material absorption nanometer iron powder with ring penta 2 is dilute mixes, reacted under inert gas shielding state; self-made fill is made; finally concentrate, self-made fill and curing agent are stirred to get epoxy resin base electromagnetic screen material.
Description
Technical field
The invention discloses a kind of preparation methods of epoxy resin base electromagnetic screen material, belong to composite polymer material skill
Art field.
Background technique
Equipment is interrogated by a large amount of universal uses, and these electronics and communication apparatus are when in use not only to the electromagnetic interference of surrounding
It is very sensitive, and its own also can generate electromagnetic interference to ambient enviroment, and it is strong to influence the other equipment even growth of animals and plants
Health.Therefore, electromagnetic radiation has become the another grand duke after solid waste pollution, atmosphere pollution, water pollution and noise pollution
Evil.Currently, the main path for eliminating hazards of electromagnetic radiation is to be shielded using electromagnetic shielding material to it.Epoxy resin (EP)
Because of its unique physical and chemical performance, such as cohesive strength is high, mechanical strength is good, adhesive force is strong, shrinking percentage is low, dielectricity is good,
Product size stability and excellent corrosion resistance etc., and it is widely used in coating, plastics, material package, insulating materials, gluing
The fields such as agent and aerospace composite material.Electromagnetic shielding composite material is made by EP is introduced with the material of electronic shield function
Research hotspot is had become at present.
Controlling the harm of electromagnetic wave bring can be from the source of electromagnetic wave, electromagnetic wave propagation, electromagnetic wave harm target three
Aspect carries out protection, and controls electromagnetic wave propagation and be undoubtedly most simple direct method.Electromagnetic shielding is then by control electricity
Electromagnetic wave propagation, and then the most common method of electromagnetic protection is completed, electromagnetic shielding is to utilize specific shielding material by electromagnetic wave
It is isolated or limits a kind of method of its direction of propagation.Metal material, ferroelectric material, iron are concentrated on to the research of shielding material now
Oxysome, carbon material etc., however these shielding materials have the shortcomings that its is intrinsic, for example, high density, high thickness, loading capacity it is larger,
Shielding mode is single, these disadvantages all seriously restrict the practical application of shielding material.Therefore, screen efficient, shielding wave band is wide
It is particularly necessary just to seem for electronic protection for the research for covering material.
And boundary of conventional epoxies base electromagnetic screen material during making and using, between resin matrix and filler
Face compatibility is bad, and the filler of single addition cannot achieve the electromagnetic wave shielding in wider frequency range, leads to the electricity of product
The drawbacks of magnetic wave shield effectiveness can not be promoted further.Therefore, how to improve lacking for conventional epoxies base electromagnetic screen material
Point is that it is promoted and is applied to broader field, meets industrial production demand urgently to obtain the promotion of more high combination property
It solves the problems, such as.
Summary of the invention
The present invention solves the technical problem of: it is being made and used for conventional epoxies base electromagnetic screen material
In the process, the interface compatibility between resin matrix and filler is bad, and the filler of single addition cannot achieve wider frequency rate model
The drawbacks of electromagnetic wave shielding in enclosing, leading to the electromagnetic shielding effect of product can not further be promoted, provide a kind of epoxy
The preparation method of resin base electromagnetic screen material.
In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is that:
A kind of preparation method of epoxy resin base electromagnetic screen material, specific preparation step are as follows:
(1) according to parts by weight, 40~50 parts of epoxy resin are successively taken, 80~120 parts of solvents, 2~4 parts of catalyst, 10~15
Part adipic acid, first epoxy resin, solvent and catalyst are added in reactor, and heating stirring after mixing, is stirred in constant temperature
It is slowly added to adipic acid under state, after being added to adipic acid, is warming up to 130~132 DEG C, after insulation reaction, vacuum distillation
Solvent is removed, aqueous epoxy resins are obtained；
(2) according to parts by weight, 80~100 parts of water are successively taken, 20~30 parts of aqueous epoxy resins, 80~100 parts of n-hexanes, 4
~6 parts of polyethyleneimines, are uniformly mixed, and carbon dioxide gas is continually fed into whipping process, derived from microemulsion processed；
(3) it will be made by oneself after microemulsion and copper salt solution be stirred for 5:1~8:1 in mass ratio, reducing agent, heating stirring is added
After reaction, it is concentrated under reduced pressure, concentrate；
(4) it is in mass ratio after 1:5~1:10 is stirred by nano iron oxide and gelatin dispersion liquid, it is successively spray-dried,
High temperature carbonization obtains carbonized material；
(5) according to parts by weight, 18~20 parts of carbonized materials, 100~200 parts of water, 8~10 parts of nanometer iron powders, first by charcoal are successively taken
Material is dispersed in water, and adds nanometer iron powder, and after being uniformly mixed, filtering washs and dry, obtains supported charcoal material；
(6) by supported charcoal material and ring penta 2 it is dilute in mass ratio for 1:3~1:5 mix after, under inert gas shielding state,
Heating stirring reaction, then through cooling, filtering, washing and dry, self-made fill；
(7) according to parts by weight, 100~120 portions of concentrates, 4~10 parts of self-made fills, 4~8 parts of curing agent, stirring are successively taken
It is uniformly mixed, discharges to get epoxy resin base electromagnetic screen material.
Step (1) epoxy resin is epoxy resin E-42, epoxy resin E-41, any one in epoxy resin E-51
Kind.
Step (1) solvent is dimethylbenzene, acetylacetone,2,4-pentanedione, any one in acetone.
Step (1) catalyst is acetylacetone,2,4-pentanedione chromium complex.
Step (1) is described to be slowly added to are as follows: is added with 3~5g/min rate.
Step (3) described copper salt solution is the copper salt solution that mass fraction is 8~10%；The mantoquita is copper sulphate, chlorination
Any one in copper, copper nitrate.
Step (3) reducing agent is ascorbic acid, formaldehyde, any one in acetaldehyde.
It is that 1:10~1:15 is formulated that step (4) the gelatin dispersion liquid is by gelatin and water in mass ratio.
Step (6) inert gas is nitrogen, helium, any one in argon gas.
Step (7) curing agent is ethylenediamine, in hexamethylene diamine, diethylenetriamine, triethylene tetramine, diethylaminopropylamine
Any one.
The beneficial effects of the present invention are:
(1) technical solution of the present invention is first modified epoxy resin-base using reasonable modified method, in modifying process
In, epoxy resin can be made to occur open loop and to react with adipic acid, be prepared a kind of simultaneously containing carboxyl and epoxy group
Amphipathic epoxy resin, then using water as water phase, n-hexane is oily phase, special using the hydrophilic and oleophylic of amphipathic epoxy resin
Property, microemulsion system is formed during being stirred, and using polyethyleneimine and carbon dioxide cooperation to realize microemulsion
The stabilization of system avoids occurring mutually to separate in subsequent preparation process, while the crosslinking of carbon dioxide and polyethyleneimine building
System can provide the oxidation that an inert reaction environment avoids substance in subsequent process, play a protective role；In subsequent preparation
In the process, by introducing copper salt solution in microemulsion system, mantoquita ionizes first in water solution system generates copper ion, and
The copper ion of generation can be adsorbed by the carboxyl of amphipathic epoxy resin water-wet side and be fixed, so that copper ion be made to be fixed on oil/water
Interface, during sequential reduction, copper ion is wrapped up after being reduced at oil-water interfaces by epoxy resin, to effectively avoid
Copper simple substance is oxidized, and avoids the decline of conductivity, to be conducive to shielding of the product to electromagnetic field of high frequency；
(2) technical solution of the present invention after surface forms one layer of gelatin shell, is carbonized using nano iron oxide as kernel,
In carbonization process, on the one hand, since the difference of the inside and outside coefficient of expansion leads to the contraction for occurring different degrees of, thus nano oxidized
Iron surface forms complicated pleated structure, promotes its specific surface area further, furthermore, carbonaceous skeleton has certain reproducibility
Can, the iron oxide that carbonaceous skeleton touches can be reduced to ferroso-ferric oxide under the high temperature conditions, make it have good magnetism,
And the presence of carbonized material pleated structure, the absorption for being conducive to nanometer iron powder are fixed, and during subsequent reactions, part Nanoscale Iron
Powder can form ferrocene structure with dilute react of ring penta 2, to form protective layer on nanometer iron powder surface, nanometer iron powder be avoided to exist
It is aoxidized during making and using, and ferrocene molecular structure has hydrophobic benzene ring structure, it can be with epoxy resin-base
It is good compatible, efficiently solve the problems, such as that the interface compatibility between epoxy resin-base and filler is bad, furthermore, ferrocene is certainly
Body band is magnetic, and the presence of magnetic fillers has conducive to the shielding of product centering low frequency electromagnetic field.
The application forms nanometer iron powder bulge-structure in filler surface by improving the fold degree of filler surface, has
It in the winding of filler surface and is affiliated to conducive to epoxy molecule chain, so that the machinery improved between filler and resin matrix is stung
With joint efforts, it avoids storing in product and occurs mutually to separate in use process, making product, filler and resin matrix are good in use
Good compatible, mutual binding force is stronger, long-acting can play good effectiveness.
Specific embodiment
According to parts by weight, 40~50 parts of epoxy resin are successively taken, 80~120 parts of solvents, 2~4 parts of catalyst, 10~15
First epoxy resin, solvent and catalyst are added in reactor for part adipic acid, are 85~90 DEG C in temperature, and revolving speed is 300~
Under the conditions of 500r/min, after heating stirring mixes 1~2h, it is slowly added under constant temperature stirring with 3~5g/min rate
Adipic acid is continuously heating to 130~132 DEG C after being added to adipic acid, and after 2~4h of insulation reaction, vacuum distillation removing is molten
Agent obtains aqueous epoxy resins；According to parts by weight, 80~100 parts of water are successively taken, 20~30 parts of aqueous epoxy resins, 80~100
Part n-hexane, 4~6 parts of polyethyleneimines pour into beaker, 30 are stirred with blender with 400~500r/min revolving speed~
60min, and with 30~40mL/min rate, into beaker, material is passed through carbon dioxide gas in whipping process, derived from micro emulsion processed
Liquid；Microemulsion will be made by oneself for 5:1~8:1 in mass ratio and copper salt solution is mixed and poured into three-necked flask, and three-necked flask is moved
It tests the speed constant temperature blender with magnetic force to digital display, is 55~60 DEG C in temperature, under the conditions of revolving speed is 400~600r/min, side constant temperature is stirred
It mixes side addition reducing agent and material in three-necked flask is transferred to Rotary Evaporators, in temperature after heating stirring reacts 45~60min
It is 75~80 DEG C, under the conditions of pressure is 400~450mmHg, 1~2h is concentrated under reduced pressure, obtains concentrate；By nano iron oxide and gelatin
Dispersion liquid is after 1:5~1:10 is stirred, to be delivered in spray dryer by screw pump in mass ratio, controls feed rate
For 18~30g/min, it is 120~140 DEG C in inlet air temperature, under the conditions of leaving air temp is 75~80 DEG C, is spray-dried, is obtained
Powder, then gained powder is transferred in retort, argon gas protection is passed through into furnace with 600~800mL/min rate, is protected in argon gas
Under shield states, 600~800 DEG C are warming up to 2~4 DEG C/min rate program, after heat preservation carbonizes 3~5h, cools to room temperature with the furnace,
Discharging, obtains carbonized material；According to parts by weight, 18~20 parts of carbonized materials are successively taken, 100~200 parts of water, 8~10 parts of nanometer iron powders,
After first mixing carbonized material and water, 30~60min of ultrasonic disperse is carried out under the conditions of supersonic frequency is 55~60kHz, to ultrasound
After dispersion, nanometer iron powder is added, continues to be stirred 30~50min, mistake with blender with 400~500r/min revolving speed
Filter, obtains filter cake, and be washed with deionized filter cake 3~5 times, then the filter cake after washing is transferred in vacuum oven, in temperature
It is 95~100 DEG C, under the conditions of pressure is 60~80Pa, is dried under vacuum to constant weight, obtains supported charcoal material；By supported charcoal material
It is poured into reaction kettle with dilute mixed in mass ratio for 1:3~1:5 of ring penta 2, then is passed through inert gas into reaction kettle, until setting
Swap out all air, then in temperature be 300~320 DEG C, revolving speed be 200~300r/min under the conditions of, heating stirring reaction 2~
4h is cooled to room temperature, by material filtering in reaction kettle, obtains filter cake, and after washing filter cake 3~5 times with dehydrated alcohol, then spends
Ion water washing 3~5 times, the filter cake after then washing deionized water is transferred in vacuum oven, in temperature be 95~105
DEG C, under the conditions of pressure is 100~120Pa, it is dried under vacuum to constant weight, discharges, obtains self-made fill；According to parts by weight, it successively takes
100~120 portions of concentrates, 4~10 parts of self-made fills, 4~8 parts of curing agent are added in batch mixer, with blender with 600~
After 800r/min revolving speed is stirred 1~2h, discharge to get epoxy resin base electromagnetic screen material.The epoxy resin is ring
Oxygen resin E-42, epoxy resin E-41, any one in epoxy resin E-51.The solvent is dimethylbenzene, acetylacetone,2,4-pentanedione, third
Any one in ketone.The catalyst is acetylacetone,2,4-pentanedione chromium complex.The copper salt solution is that mass fraction is 8~10%
Copper salt solution；The mantoquita is copper sulphate, copper chloride, any one in copper nitrate.The reducing agent is ascorbic acid, first
Any one in aldehyde, acetaldehyde.It is that 1:10~1:15 is formulated that the gelatin dispersion liquid is by gelatin and water in mass ratio.Institute
Inert gas is stated as any one in nitrogen, helium, argon gas.The curing agent be ethylenediamine, hexamethylene diamine, diethylenetriamine,
Any one in triethylene tetramine, diethylaminopropylamine.
According to parts by weight, 50 parts of epoxy resin, 120 parts of solvents, 4 parts of catalyst, 15 parts of adipic acids, first by ring are successively taken
Oxygen resin, solvent and catalyst are added in reactor, are 90 DEG C in temperature, under the conditions of revolving speed is 500r/min, heating stirring is mixed
After closing 2h, adipic acid is slowly added to 5g/min rate under constant temperature stirring, after being added to adipic acid, after of continuing rising
Temperature is to 132 DEG C, and after insulation reaction 4h, vacuum distillation removing solvent obtains aqueous epoxy resins；According to parts by weight, 100 are successively taken
Part water, 30 parts of aqueous epoxy resins, 100 parts of n-hexanes, 6 parts of polyethyleneimines pour into beaker, with blender with 500r/min
Revolving speed is stirred 60min, and with 40mL/min rate, into beaker, material is passed through carbon dioxide gas in whipping process, obtains
Make microemulsion by oneself；Microemulsion and copper salt solution will be made by oneself for 8:1 in mass ratio mix and pour into three-necked flask, and by three-necked flask
It moves to digital display to test the speed constant temperature blender with magnetic force, is 60 DEG C in temperature, under the conditions of revolving speed is 600r/min, is added in constant temperature stirring
Material in three-necked flask is transferred to Rotary Evaporators after heating stirring reacts 60min by reducing agent, is 80 DEG C in temperature, pressure is
Under the conditions of 450mmHg, 2h is concentrated under reduced pressure, obtains concentrate；It is in mass ratio 1:10 stirring by nano iron oxide and gelatin dispersion liquid
After mixing, be delivered in spray dryer by screw pump, control feed rate be 30g/min, in inlet air temperature be 140 DEG C,
Under the conditions of leaving air temp is 80 DEG C, it is spray-dried, powder is obtained, then gained powder is transferred in retort, with 800mL/min
Rate is passed through argon gas protection into furnace, under argon gas guard mode, is warming up to 800 DEG C with 4 DEG C/min rate program, heat preservation charing
After 5h, room temperature is cooled to the furnace, discharge, obtain carbonized material；According to parts by weight, 20 parts of carbonized materials are successively taken, 200 parts of water, 10 parts
Nanometer iron powder after first mixing carbonized material and water, carries out ultrasonic disperse 60min under the conditions of supersonic frequency is 60kHz, to ultrasound
After dispersion, nanometer iron powder is added, continues to be stirred 50min with blender with 500r/min revolving speed, filters, must filter
Cake, and be washed with deionized filter cake 5 times, then the filter cake after washing is transferred in vacuum oven, it is 100 DEG C in temperature, presses
Under the conditions of power is 80Pa, it is dried under vacuum to constant weight, obtains supported charcoal material；Supported charcoal material and ring penta 2 is dilute in mass ratio
It is poured into reaction kettle for 1:5 mixing, then is passed through inert gas into reaction kettle, until all air are displaced, then in temperature
It is 320 DEG C, under the conditions of revolving speed is 300r/min, heating stirring reacts 4h, it is cooled to room temperature, by material filtering in reaction kettle,
Filter cake, and after washing filter cake 5 times with dehydrated alcohol, then be washed with deionized 5 times, the filter after then washing deionized water
Cake is transferred in vacuum oven, is 105 DEG C in temperature, under the conditions of pressure is 120Pa, is dried under vacuum to constant weight, discharges, derive from system
Filler；According to parts by weight, 120 portions of concentrates are successively taken, 10 parts of self-made fills, 8 parts of curing agent are added in batch mixer, with stirring
It mixes after device is stirred 2h with 800r/min revolving speed, discharges to get epoxy resin base electromagnetic screen material.The epoxy resin is
Epoxy resin E-42.The solvent is dimethylbenzene.The catalyst is acetylacetone,2,4-pentanedione chromium complex.The copper salt solution is quality
The copper salt solution that score is 10%；The mantoquita is copper sulphate.The reducing agent is ascorbic acid.The gelatin dispersion liquid be by
Gelatin and water are formulated in mass ratio for 1:15.The inert gas is nitrogen.The curing agent is ethylenediamine.
According to parts by weight, 100 parts of water are successively taken, 30 parts of epoxy resin, 5 parts of emulsifier op-10s, 100 parts of n-hexanes, 6
Part polyethyleneimine, pours into beaker, is stirred 60min with blender with 500r/min revolving speed, and in whipping process with
40mL/min rate material into beaker is passed through carbon dioxide gas, derived from microemulsion processed；Micro emulsion will be made by oneself in mass ratio for 8:1
Liquid and copper salt solution mixing are poured into three-necked flask, and three-necked flask is moved to digital display and is tested the speed constant temperature blender with magnetic force, in temperature
It is 60 DEG C, under the conditions of revolving speed is 600r/min, reducing agent is added in constant temperature stirring, after heating stirring reacts 60min, Jiang Sankou
Material is transferred to Rotary Evaporators in flask, is 80 DEG C in temperature, under the conditions of pressure is 450mmHg, 2h is concentrated under reduced pressure, must be concentrated
Liquid；It is in mass ratio that spray drying is delivered to by screw pump after 1:10 is stirred by nano iron oxide and gelatin dispersion liquid
In device, control feed rate is 30g/min, is 140 DEG C in inlet air temperature, under the conditions of leaving air temp is 80 DEG C, is done by spraying
It is dry, powder is obtained, then gained powder is transferred in retort, argon gas protection is passed through into furnace with 800mL/min rate, is protected in argon gas
Under shield state, 800 DEG C are warming up to 4 DEG C/min rate program, after heat preservation carbonizes 5h, room temperature is cooled to the furnace, discharges, must carbonize
Material；According to parts by weight, 20 parts of carbonized materials are successively taken, 200 parts of water, 10 parts of nanometer iron powders, after first carbonized material and water are mixed, in
Supersonic frequency be 60kHz under the conditions of carry out ultrasonic disperse 60min, to ultrasonic disperse after, add nanometer iron powder, continue to use
Blender is stirred 50min with 500r/min revolving speed, and filtering obtains filter cake, and be washed with deionized filter cake 5 times, then will wash
Filter cake after washing is transferred in vacuum oven, is 100 DEG C in temperature, under the conditions of pressure is 80Pa, is dried under vacuum to constant weight, obtains negative
Load type carbonized material；Dilute mix in mass ratio for 1:5 of supported charcoal material and ring penta 2 is poured into reaction kettle, then into reaction kettle
It is passed through inert gas, is then 320 DEG C in temperature, under the conditions of revolving speed is 300r/min, heating is stirred until displacing all air
Reaction 4h is mixed, room temperature is cooled to, by material filtering in reaction kettle, obtains filter cake, and after washing filter cake 5 times with dehydrated alcohol, then
It is washed with deionized 5 times, the filter cake after then washing deionized water is transferred in vacuum oven, is 105 DEG C in temperature, is pressed
Under the conditions of power is 120Pa, it is dried under vacuum to constant weight, discharges, obtains self-made fill；According to parts by weight, 120 parts of concentrations are successively taken
Liquid, 10 parts of self-made fills, 8 parts of curing agent are added in batch mixer, after being stirred 2h with blender with 800r/min revolving speed, out
Material is to get epoxy resin base electromagnetic screen material.The epoxy resin is epoxy resin E-42.The copper salt solution is quality point
The copper salt solution that number is 10%；The mantoquita is copper sulphate.The reducing agent is ascorbic acid.The gelatin dispersion liquid is by bright
Glue and water are formulated in mass ratio for 1:15.The inert gas is nitrogen.The curing agent is ethylenediamine.
According to parts by weight, 50 parts of epoxy resin, 120 parts of solvents, 4 parts of catalyst, 15 parts of adipic acids, first by ring are successively taken
Oxygen resin, solvent and catalyst are added in reactor, are 90 DEG C in temperature, under the conditions of revolving speed is 500r/min, heating stirring is mixed
After closing 2h, adipic acid is slowly added to 5g/min rate under constant temperature stirring, after being added to adipic acid, after of continuing rising
Temperature is to 132 DEG C, and after insulation reaction 4h, vacuum distillation removing solvent obtains aqueous epoxy resins；According to parts by weight, 100 are successively taken
Part water, 30 parts of aqueous epoxy resins, 100 parts of n-hexanes are poured into beaker, are stirred with blender with 500r/min revolving speed
60min, and with 40mL/min rate, into beaker, material is passed through carbon dioxide gas in whipping process, derived from microemulsion processed；
Microemulsion will be made by oneself for 8:1 in mass ratio and copper salt solution is mixed and poured into three-necked flask, and three-necked flask is moved into digital display and is surveyed
Fast constant temperature blender with magnetic force is 60 DEG C in temperature, under the conditions of revolving speed is 600r/min, reducing agent is added in constant temperature stirring, adds
After 60min is reacted in thermal agitation, material in three-necked flask is transferred to Rotary Evaporators, is 80 DEG C in temperature, pressure is 450mmHg item
Under part, 2h is concentrated under reduced pressure, obtains concentrate；It is in mass ratio to lead to after 1:10 is stirred by nano iron oxide and gelatin dispersion liquid
It crosses screw pump to be delivered in spray dryer, control feed rate is 30g/min, is 140 DEG C in inlet air temperature, leaving air temp is
It under the conditions of 80 DEG C, is spray-dried, powder is obtained, then gained powder is transferred in retort, with 800mL/min rate into furnace
It is passed through argon gas protection, under argon gas guard mode, 800 DEG C are warming up to 4 DEG C/min rate program, after heat preservation carbonizes 5h, with furnace
It is cooled to room temperature, discharges, obtain carbonized material；According to parts by weight, 20 parts of carbonized materials are successively taken, 200 parts of water, 10 parts of nanometer iron powders,
After first mixing carbonized material and water, ultrasonic disperse 60min is carried out under the conditions of supersonic frequency is 60kHz, to the end of ultrasonic disperse
Afterwards, nanometer iron powder is added, continues to be stirred 50min with blender with 500r/min revolving speed, filters, obtains filter cake, and spend
Ion water washing filter cake 5 times, then the filter cake after washing is transferred in vacuum oven, it is 100 DEG C in temperature, pressure is 80Pa item
Under part, it is dried under vacuum to constant weight, obtains supported charcoal material；By supported charcoal material and ring penta 2 it is dilute in mass ratio for 1:5 mix
It pours into reaction kettle, then is passed through inert gas into reaction kettle, until displacing all air, be then 320 DEG C in temperature, turn
Under the conditions of speed is 300r/min, heating stirring reacts 4h, is cooled to room temperature, by material filtering in reaction kettle, obtains filter cake, be used in combination
It after dehydrated alcohol washs filter cake 5 times, then is washed with deionized 5 times, the filter cake after then washing deionized water is transferred to vacuum
In drying box, it is 105 DEG C in temperature, under the conditions of pressure is 120Pa, is dried under vacuum to constant weight, discharges, obtain self-made fill；By weight
Measure number meter, successively take 120 portions of concentrates, 10 parts of self-made fills, 8 parts of curing agent are added in batch mixer, with blender with
After 800r/min revolving speed is stirred 2h, discharge to get epoxy resin base electromagnetic screen material.The epoxy resin is asphalt mixtures modified by epoxy resin
Rouge E-42.The solvent is dimethylbenzene.The catalyst is acetylacetone,2,4-pentanedione chromium complex.The copper salt solution is that mass fraction is
10% copper salt solution；The mantoquita is copper sulphate.The reducing agent is ascorbic acid.The gelatin dispersion liquid be by gelatin and
Water is formulated in mass ratio for 1:15.The inert gas is nitrogen.The curing agent is ethylenediamine.
According to parts by weight, 50 parts of epoxy resin, 120 parts of solvents, 4 parts of catalyst, 15 parts of adipic acids, first by ring are successively taken
Oxygen resin, solvent and catalyst are added in reactor, are 90 DEG C in temperature, under the conditions of revolving speed is 500r/min, heating stirring is mixed
After closing 2h, adipic acid is slowly added to 5g/min rate under constant temperature stirring, after being added to adipic acid, after of continuing rising
Temperature is to 132 DEG C, and after insulation reaction 4h, vacuum distillation removing solvent obtains aqueous epoxy resins；According to parts by weight, 100 are successively taken
Part water, 30 parts of aqueous epoxy resins, 100 parts of n-hexanes, 6 parts of polyethyleneimines pour into beaker, with blender with 500r/min
Revolving speed is stirred 60min, and with 40mL/min rate, into beaker, material is passed through carbon dioxide gas in whipping process, obtains
Make microemulsion by oneself；Microemulsion and copper salt solution will be made by oneself for 8:1 in mass ratio mix and pour into three-necked flask, and by three-necked flask
It moves to digital display to test the speed constant temperature blender with magnetic force, is 60 DEG C in temperature, under the conditions of revolving speed is 600r/min, is added in constant temperature stirring
Material in three-necked flask is transferred to Rotary Evaporators after heating stirring reacts 60min by reducing agent, is 80 DEG C in temperature, pressure is
Under the conditions of 450mmHg, 2h is concentrated under reduced pressure, obtains concentrate；It is in mass ratio 1:10 stirring by nano iron oxide and gelatin dispersion liquid
After mixing, be delivered in spray dryer by screw pump, control feed rate be 30g/min, in inlet air temperature be 140 DEG C,
Under the conditions of leaving air temp is 80 DEG C, it is spray-dried, powder is obtained, then gained powder is transferred in retort, with 800mL/min
Rate is passed through argon gas protection into furnace, under argon gas guard mode, is warming up to 800 DEG C with 4 DEG C/min rate program, heat preservation charing
After 5h, room temperature is cooled to the furnace, discharge, obtain carbonized material；According to parts by weight, 20 parts of carbonized materials are successively taken, 200 parts of water, 10 parts
Nanometer iron powder after first mixing carbonized material and water, carries out ultrasonic disperse 60min under the conditions of supersonic frequency is 60kHz, to ultrasound
After dispersion, nanometer iron powder is added, continues to be stirred 50min with blender with 500r/min revolving speed, filters, must filter
Cake, and be washed with deionized filter cake 5 times, then the filter cake after washing is transferred in vacuum oven, it is 100 DEG C in temperature, presses
Under the conditions of power is 80Pa, it is dried under vacuum to constant weight, obtains supported charcoal material；According to parts by weight, 120 portions of concentrates are successively taken,
10 parts of carbonized materials, 8 parts of curing agent are added in batch mixer, after being stirred 2h with blender with 800r/min revolving speed, discharging, i.e.,
Obtain epoxy resin base electromagnetic screen material.The epoxy resin is epoxy resin E-42.The solvent is dimethylbenzene.The catalysis
Agent is acetylacetone,2,4-pentanedione chromium complex.The copper salt solution is the copper salt solution that mass fraction is 10%；The mantoquita is copper sulphate.
The reducing agent is ascorbic acid.The gelatin dispersion liquid is formulated in mass ratio for 1:15 by gelatin and water.
According to parts by weight, 50 parts of epoxy resin, 120 parts of solvents, 4 parts of catalyst, 15 parts of adipic acids, first by ring are successively taken
Oxygen resin, solvent and catalyst are added in reactor, are 90 DEG C in temperature, under the conditions of revolving speed is 500r/min, heating stirring is mixed
After closing 2h, adipic acid is slowly added to 5g/min rate under constant temperature stirring, after being added to adipic acid, after of continuing rising
Temperature is to 132 DEG C, and after insulation reaction 4h, vacuum distillation removing solvent obtains aqueous epoxy resins；According to parts by weight, 100 are successively taken
Part water, 30 parts of aqueous epoxy resins, 100 parts of n-hexanes, 6 parts of polyethyleneimines pour into beaker, with blender with 500r/min
Revolving speed is stirred 60min, and with 40mL/min rate, into beaker, material is passed through carbon dioxide gas in whipping process, obtains
Make microemulsion by oneself；Microemulsion and copper salt solution will be made by oneself for 8:1 in mass ratio mix and pour into three-necked flask, and by three-necked flask
It moves to digital display to test the speed constant temperature blender with magnetic force, is 60 DEG C in temperature, under the conditions of revolving speed is 600r/min, is added in constant temperature stirring
Material in three-necked flask is transferred to Rotary Evaporators after heating stirring reacts 60min by reducing agent, is 80 DEG C in temperature, pressure is
Under the conditions of 450mmHg, 2h is concentrated under reduced pressure, obtains concentrate；It is in mass ratio 1:10 stirring by nano iron oxide and gelatin dispersion liquid
After mixing, be delivered in spray dryer by screw pump, control feed rate be 30g/min, in inlet air temperature be 140 DEG C,
Under the conditions of leaving air temp is 80 DEG C, it is spray-dried, powder is obtained, then gained powder is transferred in retort, with 800mL/min
Rate is passed through argon gas protection into furnace, under argon gas guard mode, is warming up to 800 DEG C with 4 DEG C/min rate program, heat preservation charing
After 5h, room temperature is cooled to the furnace, discharge, obtain carbonized material；According to parts by weight, 20 parts of carbonized materials are successively taken, 200 parts of water, 10 parts
Nanometer iron powder after first mixing carbonized material and water, carries out ultrasonic disperse 60min under the conditions of supersonic frequency is 60kHz, to ultrasound
After dispersion, nanometer iron powder is added, continues to be stirred 50min with blender with 500r/min revolving speed, filters, must filter
Cake, and be washed with deionized filter cake 5 times, then the filter cake after washing is transferred in vacuum oven, it is 100 DEG C in temperature, presses
Under the conditions of power is 80Pa, it is dried under vacuum to constant weight, obtains supported charcoal material；According to parts by weight, 120 portions of concentrates are successively taken,
10 parts of supported charcoal materials, 8 parts of curing agent are added in batch mixer, after being stirred 2h with blender with 800r/min revolving speed, out
Material is to get epoxy resin base electromagnetic screen material.The epoxy resin is epoxy resin E-42.The solvent is dimethylbenzene.Institute
Stating catalyst is acetylacetone,2,4-pentanedione chromium complex.The copper salt solution is the copper salt solution that mass fraction is 10%；The mantoquita is sulphur
Sour copper.The reducing agent is ascorbic acid.The gelatin dispersion liquid is formulated in mass ratio for 1:15 by gelatin and water.Institute
Stating curing agent is ethylenediamine.
Comparative example: the epoxy resin base electromagnetic screen material of Wuxi new material Co., Ltd production.
Example 1 to the resulting epoxy resin base electromagnetic screen material of example 5 and comparative example product are subjected to performance detection, tool
Body detecting method is as follows:
The AV3620 of the DN1015A type shield effectiveness test equipment and Shanghai Shuan Xu Electronics Co., Ltd. developed using Southeast China University
Type vector network analyzer carries out analysis test to the electromagnet shield effect of material, standard of instruments test frequency be 30kHz~
The electromagnet shield effect in the section 6GHz sets test scope as 20MHz~1500MHz in this test process.
Specific testing result is as shown in table 1:
The 1 specific testing result of epoxy resin base electromagnetic screen material of table
| Detection project | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example |
| Shield effectiveness/dB | 62~60 | 48~39 | 33~30 | 27~25 | 24~21 | 19~17 |
By 1 testing result of table it is found that the epoxy resin base electromagnetic screen material of technical solution of the present invention preparation has shielding wave band
It the characteristics of wide and excellent electromagnetic shielding performance, has broad prospects in the development of composite polymer material technology industry.
Claims (10)
1. a kind of preparation method of epoxy resin base electromagnetic screen material, it is characterised in that specific preparation step are as follows:
(1) according to parts by weight, 40~50 parts of epoxy resin are successively taken, 80~120 parts of solvents, 2~4 parts of catalyst, 10~15
Part adipic acid, first epoxy resin, solvent and catalyst are added in reactor, and heating stirring after mixing, is stirred in constant temperature
It is slowly added to adipic acid under state, after being added to adipic acid, is warming up to 130~132 DEG C, after insulation reaction, vacuum distillation
Solvent is removed, aqueous epoxy resins are obtained；
(2) according to parts by weight, 80~100 parts of water are successively taken, 20~30 parts of aqueous epoxy resins, 80~100 parts of n-hexanes, 4
~6 parts of polyethyleneimines, are uniformly mixed, and carbon dioxide gas is continually fed into whipping process, derived from microemulsion processed；
(3) it will be made by oneself after microemulsion and copper salt solution be stirred for 5:1~8:1 in mass ratio, reducing agent, heating stirring is added
After reaction, it is concentrated under reduced pressure, concentrate；
(4) it is in mass ratio after 1:5~1:10 is stirred by nano iron oxide and gelatin dispersion liquid, it is successively spray-dried,
High temperature carbonization obtains carbonized material；
(5) according to parts by weight, 18~20 parts of carbonized materials, 100~200 parts of water, 8~10 parts of nanometer iron powders, first by charcoal are successively taken
Material is dispersed in water, and adds nanometer iron powder, and after being uniformly mixed, filtering washs and dry, obtains supported charcoal material；
(6) by supported charcoal material and ring penta 2 it is dilute in mass ratio for 1:3~1:5 mix after, under inert gas shielding state,
Heating stirring reaction, then through cooling, filtering, washing and dry, self-made fill；
(7) according to parts by weight, 100~120 portions of concentrates, 4~10 parts of self-made fills, 4~8 parts of curing agent, stirring are successively taken
It is uniformly mixed, discharges to get epoxy resin base electromagnetic screen material.
2. a kind of preparation method of epoxy resin base electromagnetic screen material according to claim 1, it is characterised in that step
(1) epoxy resin be epoxy resin E-42, epoxy resin E-41, any one in epoxy resin E-51.
3. a kind of preparation method of epoxy resin base electromagnetic screen material according to claim 1, it is characterised in that step
(1) solvent is dimethylbenzene, acetylacetone,2,4-pentanedione, any one in acetone.
4. a kind of preparation method of epoxy resin base electromagnetic screen material according to claim 1, it is characterised in that step
(1) catalyst is acetylacetone,2,4-pentanedione chromium complex.
5. a kind of preparation method of epoxy resin base electromagnetic screen material according to claim 1, it is characterised in that step
(1) described to be slowly added to are as follows: to be added with 3~5g/min rate.
6. a kind of preparation method of epoxy resin base electromagnetic screen material according to claim 1, it is characterised in that step
(3) copper salt solution is the copper salt solution that mass fraction is 8~10%；The mantoquita is copper sulphate, in copper chloride, copper nitrate
Any one.
7. a kind of preparation method of epoxy resin base electromagnetic screen material according to claim 1, it is characterised in that step
(3) reducing agent is ascorbic acid, formaldehyde, any one in acetaldehyde.
8. a kind of preparation method of epoxy resin base electromagnetic screen material according to claim 1, it is characterised in that step
(4) it is that 1:10~1:15 is formulated that the gelatin dispersion liquid is by gelatin and water in mass ratio.
9. a kind of preparation method of epoxy resin base electromagnetic screen material according to claim 1, it is characterised in that step
(6) inert gas is nitrogen, helium, any one in argon gas.
10. a kind of preparation method of epoxy resin base electromagnetic screen material according to claim 1, it is characterised in that step
(7) curing agent is ethylenediamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine, any one in diethylaminopropylamine.
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| CN113930158A (en) * | 2021-10-15 | 2022-01-14 | 中国铁路设计集团有限公司 | Modified epoxy resin, preparation method thereof, epoxy resin emulsion and anticorrosive paint |
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