CN105602145A - Polymer-graphene-polyaniline electromagnetic shielding composite and preparing method thereof - Google Patents

Polymer-graphene-polyaniline electromagnetic shielding composite and preparing method thereof Download PDF

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CN105602145A
CN105602145A CN201610059404.7A CN201610059404A CN105602145A CN 105602145 A CN105602145 A CN 105602145A CN 201610059404 A CN201610059404 A CN 201610059404A CN 105602145 A CN105602145 A CN 105602145A
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graphene
polymer
polyaniline
electromagnetic shielding
solution
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CN105602145B (en
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李侃社
汪晓芹
牛红梅
陈创前
康洁
李锦�
闫兰英
梁耀东
朱雪丹
杨小刚
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Xian University of Science and Technology
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Abstract

The invention discloses a polymer-graphene-polyaniline electromagnetic shielding composite. The polymer-graphene-polyaniline electromagnetic shielding composite is mainly prepared from, by weight, 2.5%-15% of thermoplastic elastomers, 2.5%-20% of modified expanded graphite, 5%-20% of phenylamine, 0%-20% of a processing agent and the balance matrix resin, wherein the thermoplastic elastomers are one or more of chlorinated polyethylene, polyurethane and styrene segmented copolymers, and the matrix resin is polyvinyl chloride or polyolefin or polycarbonate or an acrylonitrile-butadiene-styrene copolymer. In addition, the invention discloses a preparing method of the composite. The polymer-graphene-polyaniline electromagnetic shielding composite has the advantages that the using amount of filler is small, the preparing process is simple, and the conductivity and the electromagnetic shielding performance are excellent; the demand for electromagnetic shielding materials in daily life is met, and the composite can also be applied to the military field.

Description

Polymer-Graphene-polyaniline electromagnetic shielding composite material and preparation method thereof
Technical field
The invention belongs to functional high molecule material technical field, be specifically related to a kind of polymer-Graphene-Polyaniline electromagnetic shielding composite material and preparation method thereof.
Background technology
Along with the high speed development of hyundai electronics industry, electronic apparatus and radio communication are generally used,Electromagnetic radiation oneself become continue noise pollution, atmosphere pollution, water pollute, after solid waste pollution againOne large public hazards. Electromagnetic wave is not only disturbing the normal operation of various electronic equipments, threat communication equipmentInformation security, and can produce greatly harm to the healthy of the mankind. Eliminate at present electromagnetic wave harmMain method be adopt electromagnetic shielding material it is shielded. Therefore, explore efficient electromagnetic screenCover material and become problem in the urgent need to address.
Metal and metal composite material, their shield effectiveness is fine, but exists than great, priceThe shortcomings such as expensive, perishable, narrow, the difficult adjusting of shield effectiveness of shielding wave band. Conducting polymer (polyaniline)Also there is the potential that is designed to electromagnetic shielding material, and to have conventional metals be that shielding material is incomparableAdvantage: lightweight, cost is low, easy machine-shaping, electrical conductivity easily regulate, mechanical property is outstanding,Be easy to large area coating, easy construction; New carbon (Graphene, CNT etc.) is good because of itGood electric conductivity is widely used in novel conductive macromolecule electromagnetic shielding material, but in preparation processOften there is new carbon reunite serious, crystal formation poor quality, productive rate is low, cost is high problem, makeObtain in high polymer/new carbon electromagnetic shielding material of preparation at present, Graphene content is low, shielding effectCan be poor; Graphene, electrically conductive polyaniline and polymeric matrix are carried out compound, obtain polymer-graphiteAlkene-polyaniline electromagnetic shielding composite material, will produce good electromagnet shield effect. Problem mainly existsIn Graphene easily reunion in polymeric matrix, dispersed bad; Polyaniline and polymer, GrapheneCompatibility is poor, and then affects the overall performance of composite.
Summary of the invention
Technical problem to be solved by this invention is, for above-mentioned deficiency of the prior art, to provide onePlant polymer-Graphene-polyaniline electromagnetic shielding composite material. This polymer-Graphene-polyaniline electricityIt is few that magnetic screen composite has amount of filler, and preparation process is simple, and conduction and capability of electromagnetic shielding are excellentDifferent feature. In meeting daily life to the demand of electromagnetic shielding material, can also the army of being applied toThing field.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of polymer-Graphene-Polyaniline electromagnetic shielding composite material, is characterized in that, the main raw material by following weight percentageMake: thermoplastic elastomer (TPE) 2.5%～15%, modified expanded graphite 2.5%～20%, aniline 5%～20%, processing aid 0%～20%, surplus is matrix resin; Described thermoplastic elastomer (TPE) is that chlorination is poly-One or more in ethene, polyurethane and styrene block copolymer; Described matrix resin is poly-Vinyl chloride, polyolefin, Merlon or acrylonitrile-butadiene-styrene copolymer; Described modification is swollenSwollen graphite is the expanded graphite after titanate coupling agent interface processing.
Above-mentioned polymer-Graphene-polyaniline electromagnetic shielding composite material, is characterized in that, described inExpanded graphite is expanded and makes through microwave irradiation 3s～15s higher than 220 expansible graphite by expansion multiplying power.
Above-mentioned polymer-Graphene-polyaniline electromagnetic shielding composite material, is characterized in that, described inThe quality of titanate coupling agent is 3%～5% of expanded graphite quality, and the time of interface processing is10min～20min。
Above-mentioned polymer-Graphene-polyaniline electromagnetic shielding composite material, is characterized in that, described inProcessing aid is one or more in stabilizing agent, lubricant and plasticizer, and stabilizing agent is N-phenyl horseCome that acid amides acid group closes lanthanum (III), N-benzyl maleic amide acid group closes lanthanum (III) or N-cetylMaleic amide acid group closes lanthanum (III), and the quality of stabilizing agent is below 5% of matrix resin quality, profitLubrication prescription is stearic acid, calcium stearate or dolomol, and the quality of lubricant is matrix resin qualityBelow 10%, plasticizer is straight chain type polyester plasticizer, and the quality of plasticizer is matrix resin qualityBelow 15%.
In addition, the present invention also provides one to prepare above-mentioned polymer-Graphene-polyaniline electromagnetic shieldingThe method of composite, is characterized in that, comprises the following steps:
Step 1, after being mixed, matrix resin, thermoplastic elastomer (TPE) and processing aid carry out preformedChange, obtain vector resin, then modified expanded graphite and described vector resin are mixed, obtainCompound is milled described compound 20～50 times in pan type physico chemical reactor, is gatheredCompound-graphene composite powder;
Step 2, under stirring condition, polymer-graphene composite powder described in step 1 is addedIn foaming agent solution, leave standstill in confined conditions 20h～30h; Then by leave standstill after system at nitrogenUnder protection, oil bath is incubated 5min～10min after being heated to 110 DEG C～115 DEG C; Again by the body after insulationTie up in ice-water bath coolingly, filtration under diminished pressure obtains filter cake, and it is poly-that filter cake obtains micro-foaming after vacuum dryingCompound-graphene composite powder;
Step 3, by saturated in aniline micro-foamable polymer-graphene composite powder described in step 2Adsorb swelling 20h～30h, the aniline that filtered and recycled is unnecessary, obtain the polymer of saturated adsorption aniline-Graphene composite powder; Under stirring condition, by multiple polymer-the Graphene of described saturated adsorption anilineClosing powder, to add concentration be in the dodecylbenzenesulfonic acid solution of 0.5mol/L～1.0mol/L, mixes allThe even mixed liquor that obtains; Be 0.4mol/L～0.8mol/L's to dripping concentration in described mixed liquor(NH4)2S2O8Solution causes aniline polymerization reaction under stirring condition, and reaction temperature is 3 DEG C～8DEG C, the reaction time is 1h～3h, obtains polymer-Graphene-polyaniline suspension; Described dodecaneThe volume of base benzene sulfonic acid solution is 5～8 times of micro-foamable polymer-graphene composite powder quality,(NH4)2S2O8The volume of solution is 5～8 times of micro-foamable polymer-graphene composite powder quality,Wherein the unit of volume is mL, and the unit of quality is g;
Step 4, in polymer-Graphene described in step 3-polyaniline suspension, drip anhydrous secondThe mixed solution of alcohol and acetone is to breakdown of emulsion, and then filtration under diminished pressure, obtains polymer-Graphene-polyanilineFilter cake, by polymer-Graphene-polyaniline filter cake with deionized water cyclic washing in cleaning solution without sulphurAcid ion;
Step 5, the polymer-Graphene after cyclic washing in step 4-polyaniline filter cake is broken up,After vacuum drying, mill 5～10 times through pan type physico chemical reactor, obtain polymer-Graphene-poly-Aniline electromagnetic shielding composite material.
Above-mentioned method, is characterized in that, the method for preplasticizing described in step 1 is for adopting millstones shapeMechanico-chemical reactor is milled 3～6 times.
Above-mentioned method, is characterized in that, foaming agent solution described in step 2 is by with lower volume percentageThe raw material of content mixes to be made: cyclohexanone 10%～20%, acetone 50%～60%, butanone15%～20%, azodiisobutyronitrile 10%～15%; The quality of polymer-graphene composite powder withThe ratio of the volume of foaming agent solution is (1～3): 1, and wherein the unit of quality is g, the unit of volumeFor mL.
Above-mentioned method, is characterized in that, in step 3, in mixed liquor, drips (NH4)2S2O8MoltenThe time of liquid is no more than 30min.
Above-mentioned method, is characterized in that, the mixed solution of absolute ethyl alcohol described in step 4 and acetoneThe volumn concentration of middle absolute ethyl alcohol is 30%～70%.
Above-mentioned method, is characterized in that, vacuum drying temperature described in step 5 is 50 DEG C～80DEG C, the time is 6h～10h.
The preparation method that N-phenyl maleimide acid group in the present invention closes lanthanum (III) refers to " N-benzeneBase maleic amide acid group closes the synthetic of lanthanum (III) and the heat stabilization to PVC, China rare earth journal[J], 2009,27 (4): 460-463 "; N-benzyl maleic amide acid group closes the preparation of lanthanum (III)Method refer to " N-benzyl maleic amide acid group closes the synthetic of lanthanum (III) and the heat stabilization to PVC,Rare earth [J], 2015,36 (3): 47-56 "; N-cetyl maleic amide acid group closes lanthanum (III)Preparation method refer to that " N-straight chained alkyl maleic amide acid group closes the preparation of lanthanum (III) and to PVCHeat stabilization research [D], Xi'an Technology University, 2013 ".
The performance test of polymer-graphene-polyaniline composite material:
Transmission electron microscope (TEM): use LeicaEMFC6 type slicer to polymer-Graphene-polyphenylAmine electromagnetic shielding composite material carries out ultra-thin section, makes the thin slice of the about 30nm～50nm of thickness, orDirectly polymer-Graphene-polyaniline electromagnetic shielding composite granule is invested on copper mesh, and in FEITecnaiG2F20S-TWIN field transmission electron microscope observation graphite alkylene degree and poly-Dispersion effect in compound matrix, and take pictures, accelerating potential is 80kV.
Resistivity measurement: when material resistance is lower than 106When Ω, adopt four probe method to test, surveyAmount system comprises MCH-303D-II type D.C. regulated power supply, KEITHLEY6514SystemElectrometer type measuring appliance, WentworthLaboratoriesPVX400 type microscope and probe.When material resistance is higher than 106When Ω, the ZC46A type of producing with Shanghai Precision Scientific Apparatus Co., LtdMegger is measured, and measuring voltage is 50V, and measurement category is 103Ω～1012Ω。
Electromagnetic shielding test: according to People's Republic of China's electron trade military standard (SJ20524),Adopt AgilentN-5242-A vector network tester, the scope that is 8GHz～18GHz in frequencyInside measure. Specimen size is 22.9mm × 10.2mm, and thickness is not etc.; Input power is 0dBm,Test point 201.
The present invention compared with prior art has the following advantages:
1, polymer-Graphene of the present invention-polyaniline electromagnetic shielding composite material has amount of fillerFew, preparation process is simple, the feature of conduction and capability of electromagnetic shielding excellence. Except meeting in daily lifeOutside the demand of electromagnetic shielding material, can also be applied to military field.
2, the present invention adopts integrated micro irradiation technique, pan-milling solid state mechanochemistry technology, original positionPolymerization technique etc., microwave irradiation can be realized expansible graphite high speed, high power expands; Millstones shape power chemistryThe three-dimensional shearing force field of reactor uniqueness, the viscoplasticity gradient of matrix resin-thermoplastic elastomer (TPE), can lead toCross milling altogether of matrix resin, thermoplastic elastomer (TPE), processing aid and modified expanded graphite realized to stoneChina ink limellar stripping and nanometer, graphite alkylene, and dispersed and compound in matrix resin; Original positionPolymerization has realized dispersed compatible with good interface in polymer-Graphene template of polyaniline.
3, polymer-Graphene of the present invention-polyaniline electromagnetic shielding composite material has been given full play to polymerizationThe viscoplasticity of thing and be convenient to machine-shaping feature, Graphene-layer/polyaniline conductive complementarity, passes through GrapheneWith polyaniline, polymer-thermoplastic elastomer (TPE) polynary compound, form polynary conductive network, make its electricityMagnetic screen usefulness has advantages of adjustable controlled.
Below in conjunction with drawings and Examples, technical scheme of the present invention is described in further detail.
Brief description of the drawings
Fig. 1 is polymer-Graphene-polyaniline electromagnetic shielding composite material of the embodiment of the present invention 1Electromagnet shield effect curve.
Fig. 2 is polymer-Graphene-polyaniline electromagnetic shielding composite material of the embodiment of the present invention 1One position is perpendicular to the TEM photo in the Graphene phenyl ring face visual field.
Fig. 3 is that polymer-Graphene-polyaniline electromagnetic shielding composite material of the embodiment of the present invention 1 is anotherOne position is perpendicular to the TEM photo in the Graphene phenyl ring face visual field.
Fig. 4 is that polymer-Graphene-polyaniline electromagnetic shielding composite material of the embodiment of the present invention 1 is flatRow is in the TEM photo in the Graphene phenyl ring face visual field.
Fig. 5 is the partial enlarged drawing at A position in Fig. 4.
Fig. 6 is polymer-Graphene-polyaniline electromagnetic shielding composite material of the embodiment of the present invention 2Electromagnet shield effect curve.
Fig. 7 is polymer-Graphene-polyaniline electromagnetic shielding composite material of the embodiment of the present invention 3Electromagnet shield effect curve.
Detailed description of the invention
The preparation method that in following examples, N-phenyl maleimide acid group used closes lanthanum (III) refers to" N-phenyl maleimide acid group closes the synthetic of lanthanum (III) and the heat stabilization to PVC, China rare earthJournal [J], 2009,27 (4): 460-463 "; N-benzyl maleic amide acid group closes lanthanum (III)Preparation method refers to that " N-benzyl maleic amide acid group closes the synthetic of lanthanum (III) and the thermally-stabilised work to PVCWith, rare earth [J], 2015,36 (3): 47-56 "; N-cetyl maleic amide acid group closes lanthanum (III)Preparation method refer to that " N-straight chained alkyl maleic amide acid group closes the preparation of lanthanum (III) and to PVCHeat stabilization research [D], Xi'an Technology University, 2013 ".
Embodiment 1
Polymer-Graphene-polyaniline electromagnetic shielding composite material of the present embodiment is mainly by following weightThe raw material of percentage composition is made: polyurethane 5%, modified expanded graphite 15%, aniline 10%, N-benzeneBase maleic amide acid group closes lanthanum (III) 3%, stearic acid 2%, and surplus is polyvinyl chloride; Described modificationExpanded graphite is after titanate coupling agent (as NDZ-311 or NTC-131 etc.) interface processingExpanded graphite, the quality of titanate coupling agent is 4% of expanded graphite quality, the time of interface processingFor 15min, expanded graphite is expanded through microwave irradiation 8s higher than 220 expansible graphite by expansion multiplying powerMake.
The preparation method of polymer-Graphene-polyaniline electromagnetic shielding composite material of the present embodiment comprisesFollowing steps:
Step 1, polyvinyl chloride, polyurethane, N-phenyl maleimide acid group are closed to lanthanum (III) and hardResin acid mixes rear employing pan type physico chemical reactor and mills and carry out preplasticizing 5 times, obtains carrierResin, then mixes modified expanded graphite and described vector resin, obtains compound, by instituteState compound and in pan type physico chemical reactor, mill 20 times, obtain polymer-Graphene composite powderBody;
Step 2, under stirring condition, polymer-graphene composite powder described in step 1 is addedIn foaming agent solution, leave standstill in confined conditions 24h; Then by leave standstill after system in nitrogen protectionUnder, oil bath is incubated 8min after being heated to 112 DEG C; Again by insulation after system cooling in ice-water bath,Filtration under diminished pressure obtains filter cake, and filter cake obtains micro-foamable polymer-Graphene after vacuum drying desolvationComposite granule; Described foaming agent solution is mixed and is made by the raw material of following volumn concentration: ringHexanone 15%, acetone 55%, butanone 18%, azodiisobutyronitrile 12%; Polymer-Graphene is multipleThe ratio that closes the quality of powder and the volume of foaming agent solution is 2:1, and wherein the unit of quality is g, volumeUnit be mL;
Step 3, by saturated in aniline micro-foamable polymer-graphene composite powder described in step 2Adsorb swelling 24h, the aniline that filtered and recycled is unnecessary, obtains the polymer-Graphene of saturated adsorption anilineComposite granule; Under stirring condition, by the polymer-graphene composite powder of described saturated adsorption anilineAdding concentration is in the dodecylbenzenesulfonic acid solution of 0.5mol/L, mixes and obtains mixed liquor; ToIn described mixed liquor, drip (the NH that concentration is 0.5mol/L4)2S2O8Solution, time for adding is no more than30min causes aniline polymerization reaction under stirring condition, and reaction temperature is 5 DEG C, and the reaction time is2h, obtains polymer-Graphene-polyaniline suspension; The volume of described dodecylbenzenesulfonic acid solutionFor 6 times of micro-foamable polymer-graphene composite powder quality, (NH4)2S2O8The volume of solution is micro-6 times of foamable polymer-graphene composite powder quality, wherein the unit of volume is mL, qualityUnit be g;
Step 4, in polymer-Graphene described in step 3-polyaniline suspension, drip anhydrous secondThe mixed solution of alcohol and acetone is to breakdown of emulsion, and then filtration under diminished pressure, obtains polymer-Graphene-polyanilineFilter cake, by polymer-Graphene-polyaniline filter cake with deionized water cyclic washing in cleaning solution without sulphurAcid ion (adopts 0.1mol/LBaCl2Solution detects cleaning solution and generates without precipitation); DescribedIn the mixed solution of absolute ethyl alcohol and acetone, the volumn concentration of absolute ethyl alcohol is 50%;
Step 5, the polymer-Graphene after cyclic washing in step 4-polyaniline filter cake is broken up,At 80 DEG C, after vacuum drying 6h, mill 5 times through pan type physico chemical reactor, obtain polymer-Graphene-polyaniline electromagnetic shielding composite material.
After testing, polymer-Graphene-polyaniline electromagnetic shielding composite material that prepared by the present embodimentSpecific insulation is 20 Ω cm, electromagnet shield effect as shown in Figure 1, as can be seen from the figure,The absorption usefulness of Ku (12.4GHz～18GHz) wave band composite is 35.1～37.9dB, with frequentlyThe increase of rate and increasing. Corresponding reflection performance is 5dB left and right, changes little with the increase of frequency.Total shield effectiveness is 40.2～42.9dB, can meet business application requirements.
The TEM that Fig. 2-Fig. 5 is respectively polymer-Graphene-polyaniline electromagnetic shielding composite material shinesSheet, Fig. 2, Fig. 3 are perpendicular to the Graphene phenyl ring face visual field, Fig. 4 is for being parallel to Graphene phenyl ring faceThe visual field, the partial enlarged drawing that Fig. 5 is Fig. 4. Prove that modified expanded graphite has been stripped from into Graphene,Polyaniline is partially submerged between graphene layer, Fig. 5 explanation, and the regularity of lattice fringe slightly destroys, butLattice fringe thickness, in 0.4nm left and right, illustrates the interaction due to Graphene and polyaniline, realizesControl to graphene sheet layer stability.
Embodiment 2
Polymer-Graphene-polyaniline electromagnetic shielding composite material of the present embodiment is mainly by following weightThe raw material of percentage composition is made: haloflex 10%, and modified expanded graphite 15%, aniline 5%,Surplus is polypropylene; Described modified expanded graphite be through titanate coupling agent (as NDZ-311 orNTC-131 etc.) expanded graphite after interface processing, the quality of titanate coupling agent is expanded graphite matterAmount 3%, the time of interface processing is 20min, expanded graphite by expansion multiplying power higher than 220 canExpanded graphite expands and makes through microwave irradiation 15s.
The preparation method of polymer-Graphene-polyaniline electromagnetic shielding composite material of the present embodiment comprisesFollowing steps:
Step 1, polypropylene and haloflex are mixed to rear employing pan type physico chemical reactorMill and carry out preplasticizing 6 times, obtain vector resin, then by modified expanded graphite and described carrier treeFat mixes, and obtains compound, and described compound is milled to 30 in pan type physico chemical reactorInferior, obtain polymer-graphene composite powder;
Step 2, under stirring condition, polymer-graphene composite powder described in step 1 is addedIn foaming agent solution, leave standstill in confined conditions 30h; Then by leave standstill after system in nitrogen protectionUnder, oil bath is incubated 10min after being heated to 110 DEG C; Again by insulation after system cooling in ice-water bath,Filtration under diminished pressure obtains filter cake, and filter cake obtains micro-foamable polymer-Graphene after vacuum drying desolvationComposite granule; Described foaming agent solution is mixed and is made by the raw material of following volumn concentration: ringHexanone 20%, acetone 50%, butanone 20%, azodiisobutyronitrile 10%; Polymer-Graphene is multipleThe ratio that closes the quality of powder and the volume of foaming agent solution is 3:1, and wherein the unit of quality is g, volumeUnit be mL;
Step 3, by saturated in aniline micro-foamable polymer-graphene composite powder described in step 2Adsorb swelling 30h, the aniline that filtered and recycled is unnecessary, obtains the polymer-Graphene of saturated adsorption anilineComposite granule; Under stirring condition, by the polymer-graphene composite powder of described saturated adsorption anilineAdding concentration is in the dodecylbenzenesulfonic acid solution of 0.8mol/L, mixes and obtains mixed liquor; ToIn described mixed liquor, drip (the NH that concentration is 0.4mol/L4)2S2O8Solution, time for adding is no more than20min causes aniline polymerization reaction under stirring condition, and reaction temperature is 3 DEG C, and the reaction time is3h, obtains polymer-Graphene-polyaniline suspension; The volume of described dodecylbenzenesulfonic acid solutionFor 8 times of micro-foamable polymer-graphene composite powder quality, (NH4)2S2O8The volume of solution is micro-8 times of foamable polymer-graphene composite powder quality, wherein the unit of volume is mL, qualityUnit be g;
Step 4, in polymer-Graphene described in step 3-polyaniline suspension, drip anhydrous secondThe mixed solution of alcohol and acetone is to breakdown of emulsion, and then filtration under diminished pressure, obtains polymer-Graphene-polyanilineFilter cake, by polymer-Graphene-polyaniline filter cake with deionized water cyclic washing in cleaning solution without sulphurAcid ion (adopts 0.1mol/LBaCl2Solution detects cleaning solution and generates without precipitation); DescribedIn the mixed solution of absolute ethyl alcohol and acetone, the volumn concentration of absolute ethyl alcohol is 30%;
Step 5, the polymer-Graphene after cyclic washing in step 4-polyaniline filter cake is broken up,At 70 DEG C, after vacuum drying 8h, mill 8 times through pan type physico chemical reactor, obtain polymer-Graphene-polyaniline electromagnetic shielding composite material.
After testing, polymer-Graphene-polyaniline electromagnetic shielding composite material that prepared by the present embodimentSpecific insulation is 50 Ω cm, electromagnet shield effect as shown in Figure 6, as can be seen from the figure,The absorption usefulness of Ku (12.4GHz～18GHz) wave band composite is 25.1～27.8dB, with frequentlyThe increase of rate and increasing. Corresponding reflection performance is 5dB left and right, changes little with the increase of frequency.Total shield effectiveness is 30.2～32.8dB, can meet business application requirements.
Embodiment 3
Polymer-Graphene-polyaniline electromagnetic shielding composite material of the present embodiment is mainly by following weightThe raw material of percentage composition is made: polyurethane 8%, modified expanded graphite 10%, aniline 20%, surplusFor Merlon; Described modified expanded graphite be through titanate coupling agent (as NDZ-311 orNTC-131 etc.) expanded graphite after interface processing, the quality of titanate coupling agent is expanded graphite matterAmount 5%, the time of interface processing is 10min, expanded graphite by expansion multiplying power higher than 220 canExpanded graphite expands and makes through microwave irradiation 3s.
The preparation method of polymer-Graphene-polyaniline electromagnetic shielding composite material of the present embodiment comprisesFollowing steps:
Step 1, Merlon and polyurethane are mixed to rear employing pan type physico chemical reactor grindGrind and carry out preplasticizing 3 times, obtain vector resin, then by modified expanded graphite and described vector resinMix, obtain compound, described compound is milled to 25 in pan type physico chemical reactorInferior, obtain polymer-graphene composite powder;
Step 2, under stirring condition, polymer-graphene composite powder described in step 1 is addedIn foaming agent solution, leave standstill in confined conditions 20h; Then by leave standstill after system in nitrogen protectionUnder, oil bath is incubated 5min after being heated to 115 DEG C; Again by insulation after system cooling in ice-water bath,Filtration under diminished pressure obtains filter cake, and filter cake obtains micro-foamable polymer-Graphene after vacuum drying desolvationComposite granule; Described foaming agent solution is mixed and is made by the raw material of following volumn concentration: ringHexanone 10%, acetone 60%, butanone 15%, azodiisobutyronitrile 15%; Polymer-Graphene is multipleThe ratio that closes the quality of powder and the volume of foaming agent solution is 1:1, and wherein the unit of quality is g, volumeUnit be mL;
Step 3, by saturated in aniline micro-foamable polymer-graphene composite powder described in step 2Adsorb swelling 20h, the aniline that filtered and recycled is unnecessary, obtains the polymer-Graphene of saturated adsorption anilineComposite granule; Under stirring condition, by the polymer-graphene composite powder of described saturated adsorption anilineAdding concentration is in the dodecylbenzenesulfonic acid solution of 1.0mol/L, mixes and obtains mixed liquor; ToIn described mixed liquor, drip (the NH that concentration is 0.8mol/L4)2S2O8Solution, time for adding is no more than30min causes aniline polymerization reaction under stirring condition, and reaction temperature is 8 DEG C, and the reaction time is1h, obtains polymer-Graphene-polyaniline suspension; The volume of described dodecylbenzenesulfonic acid solutionFor 5 times of micro-foamable polymer-graphene composite powder quality, (NH4)2S2O8The volume of solution is micro-5 times of foamable polymer-graphene composite powder quality, wherein the unit of volume is mL, qualityUnit be g;
Step 4, in polymer-Graphene described in step 3-polyaniline suspension, drip anhydrous secondThe mixed solution of alcohol and acetone is to breakdown of emulsion, and then filtration under diminished pressure, obtains polymer-Graphene-polyanilineFilter cake, by polymer-Graphene-polyaniline filter cake with deionized water cyclic washing in cleaning solution without sulphurAcid ion (adopts 0.1mol/LBaCl2Solution detects cleaning solution and generates without precipitation); DescribedIn the mixed solution of absolute ethyl alcohol and acetone, the volumn concentration of absolute ethyl alcohol is 70%;
Step 5, the polymer-Graphene after cyclic washing in step 4-polyaniline filter cake is broken up,At 50 DEG C, after vacuum drying 10h, mill 10 times through pan type physico chemical reactor, obtain polymer-Graphene-polyaniline electromagnetic shielding composite material.
After testing, polymer-Graphene-polyaniline electromagnetic shielding composite material that prepared by the present embodimentSpecific insulation is 55 Ω cm, electromagnet shield effect as shown in Figure 7, as can be seen from the figure,The absorption usefulness of Ku (12.4GHz～18GHz) wave band composite is 30.1～32.4dB, with frequentlyThe increase of rate and increasing. Corresponding reflection performance is 5dB left and right, changes little with the increase of frequency.Total shield effectiveness is 35.1～37.4dB, can meet business application requirements.
Embodiment 4
Polymer-Graphene-polyaniline electromagnetic shielding composite material of the present embodiment is mainly by following weightThe raw material of percentage composition is made: styrene block copolymer 8%, modified expanded graphite 10%, benzeneAmine 5%, surplus is acrylonitrile-butadiene-styrene copolymer; Described modified expanded graphite is through metatitanic acidExpanded graphite after ester coupling agent (as NDZ-311 or NTC-131 etc.) interface processing, titanate estersThe quality of coupling agent is 3% of expanded graphite quality, and the time of interface processing is 20min, expansion stoneChina ink is expanded and makes through microwave irradiation 15s higher than 220 expansible graphite by expansion multiplying power.
The preparation method of polymer-Graphene-polyaniline electromagnetic shielding composite material of the present embodiment comprisesFollowing steps:
Step 1, acrylonitrile-butadiene-styrene copolymer and styrene block copolymer are mixedEvenly, adopt pan type physico chemical reactor to mill and carry out preplasticizing 5 times, obtain vector resin, soAfter modified expanded graphite and described vector resin are mixed, obtain compound, by described compoundIn pan type physico chemical reactor, mill 30 times, obtain polymer-graphene composite powder;
Step 2, under stirring condition, polymer-graphene composite powder described in step 1 is addedIn foaming agent solution, leave standstill in confined conditions 24h; Then by leave standstill after system in nitrogen protectionUnder, oil bath is incubated 8min after being heated to 112 DEG C; Again by insulation after system cooling in ice-water bath,Filtration under diminished pressure obtains filter cake, and filter cake obtains micro-foamable polymer-Graphene after vacuum drying desolvationComposite granule; Described foaming agent solution is mixed and is made by the raw material of following volumn concentration: ringHexanone 15%, acetone 55%, butanone 18%, azodiisobutyronitrile 12%; Polymer-Graphene is multipleThe ratio that closes the quality of powder and the volume of foaming agent solution is 2:1, and wherein the unit of quality is g, volumeUnit be mL;
Step 3, by saturated in aniline micro-foamable polymer-graphene composite powder described in step 2Adsorb swelling 24h, the aniline that filtered and recycled is unnecessary, obtains the polymer-Graphene of saturated adsorption anilineComposite granule; Under stirring condition, by the polymer-graphene composite powder of described saturated adsorption anilineAdding concentration is in the dodecylbenzenesulfonic acid solution of 0.5mol/L, mixes and obtains mixed liquor; ToIn described mixed liquor, drip (the NH that concentration is 0.5mol/L4)2S2O8Solution, time for adding is no more than30min causes aniline polymerization reaction under stirring condition, and reaction temperature is 5 DEG C, and the reaction time is2h, obtains polymer-Graphene-polyaniline suspension; The volume of described dodecylbenzenesulfonic acid solutionFor 6 times of micro-foamable polymer-graphene composite powder quality, (NH4)2S2O8The volume of solution is micro-6 times of foamable polymer-graphene composite powder quality, wherein the unit of volume is mL, qualityUnit be g;
Step 4, in polymer-Graphene described in step 3-polyaniline suspension, drip anhydrous secondThe mixed solution of alcohol and acetone is to breakdown of emulsion, and then filtration under diminished pressure, obtains polymer-Graphene-polyanilineFilter cake, by polymer-Graphene-polyaniline filter cake with deionized water cyclic washing in cleaning solution without sulphurAcid ion (adopts 0.1mol/LBaCl2Solution detects cleaning solution and generates without precipitation); DescribedIn the mixed solution of absolute ethyl alcohol and acetone, the volumn concentration of absolute ethyl alcohol is 50%;
Step 5, the polymer-Graphene after cyclic washing in step 4-polyaniline filter cake is broken up,At 80 DEG C, after vacuum drying 6h, mill 5 times through pan type physico chemical reactor, obtain polymer-Graphene-polyaniline electromagnetic shielding composite material.
After testing, polymer-Graphene-polyaniline electromagnetic shielding composite material that prepared by the present embodimentSpecific insulation is 100 Ω cm, electromagnet shield effect: at X-band (8.3GHz～12.4GHz)The about 5.5dB of reflection performance, absorb usefulness 22.5～30.3dB, total shield effectiveness 28～35.8dB;At the about 5.1dB of reflection performance of Ku (12.4GHz～18GHz), absorb usefulness 32.5～45.2dB,Total shield effectiveness 37.5～50.3dB.
Embodiment 5
Polymer-Graphene-polyaniline electromagnetic shielding composite material of the present embodiment is mainly by following weightThe raw material of percentage composition is made: polyurethane 2.5%, modified expanded graphite 2.5%, aniline 20%, N-Benzyl maleic amide acid group closes lanthanum (III) 3%, calcium stearate (also can adopt dolomol or stearic acid)6%, straight chain type polyester plasticizer 6%, surplus is polyvinyl chloride; Described modified expanded graphite is through titaniumExpanded graphite after acid esters coupling agent (as NDZ-311 or NTC-131 etc.) interface processing, metatitanic acidThe quality of ester coupling agent is 4% of expanded graphite quality, and the time of interface processing is 15min, expandsGraphite is expanded and makes through microwave irradiation 8s higher than 220 expansible graphite by expansion multiplying power.
The preparation method of polymer-Graphene-polyaniline electromagnetic shielding composite material of the present embodiment comprisesFollowing steps:
Step 1, polyvinyl chloride, polyurethane, N-benzyl maleic amide acid group are closed to lanthanum (III), hardResin acid calcium and straight chain type polyester plasticizer mix rear employing pan type physico chemical reactor and mill 5 timesCarry out preplasticizing, obtain vector resin, then modified expanded graphite and described vector resin are mixed allEven, obtain compound, described compound is milled 20 times in pan type physico chemical reactor,To polymer-graphene composite powder;
Step 2, under stirring condition, polymer-graphene composite powder described in step 1 is addedIn foaming agent solution, leave standstill in confined conditions 24h; Then by leave standstill after system in nitrogen protectionUnder, oil bath is incubated 8min after being heated to 112 DEG C; Again by insulation after system cooling in ice-water bath,Filtration under diminished pressure obtains filter cake, and filter cake obtains micro-foamable polymer-Graphene after vacuum drying desolvationComposite granule; Described foaming agent solution is mixed and is made by the raw material of following volumn concentration: ringHexanone 15%, acetone 55%, butanone 18%, azodiisobutyronitrile 12%; Polymer-Graphene is multipleThe ratio that closes the quality of powder and the volume of foaming agent solution is 2:1, and wherein the unit of quality is g, volumeUnit be mL;
Step 3, by saturated in aniline micro-foamable polymer-graphene composite powder described in step 2Adsorb swelling 24h, the aniline that filtered and recycled is unnecessary, obtains the polymer-Graphene of saturated adsorption anilineComposite granule; Under stirring condition, by the polymer-graphene composite powder of described saturated adsorption anilineAdding concentration is in the dodecylbenzenesulfonic acid solution of 0.5mol/L, mixes and obtains mixed liquor; ToIn described mixed liquor, drip (the NH that concentration is 0.5mol/L4)2S2O8Solution, time for adding is no more than25min causes aniline polymerization reaction under stirring condition, and reaction temperature is 5 DEG C, and the reaction time is2h, obtains polymer-Graphene-polyaniline suspension; The volume of described dodecylbenzenesulfonic acid solutionFor 6 times of micro-foamable polymer-graphene composite powder quality, (NH4)2S2O8The volume of solution is micro-6 times of foamable polymer-graphene composite powder quality, wherein the unit of volume is mL, qualityUnit be g;
Step 4, in polymer-Graphene described in step 3-polyaniline suspension, drip anhydrous secondThe mixed solution of alcohol and acetone is to breakdown of emulsion, and then filtration under diminished pressure, obtains polymer-Graphene-polyanilineFilter cake, by polymer-Graphene-polyaniline filter cake with deionized water cyclic washing in cleaning solution without sulphurAcid ion (adopts 0.1mol/LBaCl2Solution detects cleaning solution and generates without precipitation); DescribedIn the mixed solution of absolute ethyl alcohol and acetone, the volumn concentration of absolute ethyl alcohol is 50%;
Step 5, the polymer-Graphene after cyclic washing in step 4-polyaniline filter cake is broken up,At 80 DEG C, after vacuum drying 6h, mill 5 times through pan type physico chemical reactor, obtain polymer-Graphene-polyaniline electromagnetic shielding composite material.
After testing, polymer-Graphene-polyaniline electromagnetic shielding composite material that prepared by the present embodimentSpecific insulation is 20 Ω cm, electromagnet shield effect: at X-band (8.3GHz～12.4GHz)The about 5.5dB of reflection performance, absorb usefulness 2.5～7.3dB, total shield effectiveness 8～12.8dB; ?The about 5.2dB of reflection performance of Ku (12.4GHz～18GHz), absorbs usefulness 30.5～35.2dB, totalShield effectiveness 35.7～40.4dB.
Embodiment 6
Polymer-Graphene-polyaniline electromagnetic shielding composite material of the present embodiment is mainly by following weightThe raw material of percentage composition is made: polyurethane 8%, and haloflex 2%, modified expanded graphite 20%,Aniline 5%, surplus is polyethylene; Described modified expanded graphite be through titanate coupling agent (asNDZ-311 or NTC-131 etc.) expanded graphite after interface processing, the quality of titanate coupling agentFor 3% of expanded graphite quality, the time of interface processing is 20min, and expanded graphite is by expansion multiplying powerExpansible graphite higher than 220 expands and makes through microwave irradiation 15s.
The preparation method of polymer-Graphene-polyaniline electromagnetic shielding composite material of the present embodiment comprisesFollowing steps:
Step 1, polyethylene, polyurethane and haloflex are mixed to rear employing millstones shape powerReactor is milled and is carried out preplasticizing 6 times, obtains vector resin, then by modified expanded graphite and instituteState vector resin and mix, obtain compound, by described compound at pan type physico chemical reactorIn mill 30 times, obtain polymer-graphene composite powder;
Step 2, under stirring condition, polymer-graphene composite powder described in step 1 is addedIn foaming agent solution, leave standstill in confined conditions 30h; Then by leave standstill after system in nitrogen protectionUnder, oil bath is incubated 10min after being heated to 110 DEG C; Again by insulation after system cooling in ice-water bath,Filtration under diminished pressure obtains filter cake, and filter cake obtains micro-foamable polymer-Graphene after vacuum drying desolvationComposite granule; Described foaming agent solution is mixed and is made by the raw material of following volumn concentration: ringHexanone 20%, acetone 50%, butanone 20%, azodiisobutyronitrile 10%; Polymer-Graphene is multipleThe ratio that closes the quality of powder and the volume of foaming agent solution is 3:1, and wherein the unit of quality is g, volumeUnit be mL;
Step 3, by saturated in aniline micro-foamable polymer-graphene composite powder described in step 2Adsorb swelling 24h, the aniline that filtered and recycled is unnecessary, obtains the polymer-Graphene of saturated adsorption anilineComposite granule; Under stirring condition, by the polymer-graphene composite powder of described saturated adsorption anilineAdding concentration is in the dodecylbenzenesulfonic acid solution of 0.8mol/L, mixes and obtains mixed liquor; ToIn described mixed liquor, drip (the NH that concentration is 0.4mol/L4)2S2O8Solution, time for adding is no more than30min causes aniline polymerization reaction under stirring condition, and reaction temperature is 3 DEG C, and the reaction time is3h, obtains polymer-Graphene-polyaniline suspension; The volume of described dodecylbenzenesulfonic acid solutionFor 8 times of micro-foamable polymer-graphene composite powder quality, (NH4)2S2O8The volume of solution is micro-8 times of foamable polymer-graphene composite powder quality, wherein the unit of volume is mL, qualityUnit be g;
Step 4, in polymer-Graphene described in step 3-polyaniline suspension, drip anhydrous secondThe mixed solution of alcohol and acetone is to breakdown of emulsion, and then filtration under diminished pressure, obtains polymer-Graphene-polyanilineFilter cake, by polymer-Graphene-polyaniline filter cake with deionized water cyclic washing in cleaning solution without sulphurAcid ion (adopts 0.1mol/LBaCl2Solution detects cleaning solution and generates without precipitation); DescribedIn the mixed solution of absolute ethyl alcohol and acetone, the volumn concentration of absolute ethyl alcohol is 30%;
Step 5, the polymer-Graphene after cyclic washing in step 4-polyaniline filter cake is broken up,At 70 DEG C, after vacuum drying 8h, mill 8 times through pan type physico chemical reactor, obtain polymer-Graphene-polyaniline electromagnetic shielding composite material.
After testing, polymer-Graphene-polyaniline electromagnetic shielding composite material that prepared by the present embodimentSpecific insulation is 50 Ω cm, electromagnet shield effect: at X-band (8.3GHz～12.4GHz)The about 5.5dB of reflection performance, absorb usefulness 12.5～18.3dB, total shield effectiveness 18～23.8dB;At the about 5.1dB of reflection performance of Ku (12.4GHz～18GHz), absorb usefulness 32.5～43.2dB,Total shield effectiveness 37.6～48.4dB.
Embodiment 7
Polymer-Graphene-polyaniline electromagnetic shielding composite material of the present embodiment is mainly by following weightThe raw material of percentage composition is made: styrene block copolymer 2.5%, modified expanded graphite 5%, benzeneAmine 5%, N-cetyl maleic amide acid group closes lanthanum (III) 3%, straight chain type polyester plasticizer 11%,Surplus is polyvinyl chloride; Described modified expanded graphite be through titanate coupling agent (as NDZ-311 orNTC-131 etc.) expanded graphite after interface processing, the quality of titanate coupling agent is expanded graphite matterAmount 3%, the time of interface processing is 20min, expanded graphite by expansion multiplying power higher than 220 canExpanded graphite expands and makes through microwave irradiation 15s.
The preparation method of polymer-Graphene-polyaniline electromagnetic shielding composite material of the present embodiment comprisesFollowing steps:
Step 1, by polyvinyl chloride, styrene block copolymer, N-cetyl maleamic acidRoot closes lanthanum (III) and straight chain type polyester plasticizer mixes rear employing pan type physico chemical reactor stone rollerGrind and carry out preplasticizing 5 times, obtain vector resin, then by modified expanded graphite and described vector resinMix, obtain compound, described compound is milled to 30 in pan type physico chemical reactorInferior, obtain polymer-graphene composite powder;
Step 2, under stirring condition, polymer-graphene composite powder described in step 1 is addedIn foaming agent solution, leave standstill in confined conditions 24h; Then by leave standstill after system in nitrogen protectionUnder, oil bath is incubated 8min after being heated to 112 DEG C; Again by insulation after system cooling in ice-water bath,Filtration under diminished pressure obtains filter cake, and filter cake obtains micro-foamable polymer-Graphene after vacuum drying desolvationComposite granule; Described foaming agent solution is mixed and is made by the raw material of following volumn concentration: ringHexanone 15%, acetone 55%, butanone 18%, azodiisobutyronitrile 12%; Polymer-Graphene is multipleThe ratio that closes the quality of powder and the volume of foaming agent solution is 2:1, and wherein the unit of quality is g, volumeUnit be mL;
Step 3, by saturated in aniline micro-foamable polymer-graphene composite powder described in step 2Adsorb swelling 24h, the aniline that filtered and recycled is unnecessary, obtains the polymer-Graphene of saturated adsorption anilineComposite granule; Under stirring condition, by the polymer-graphene composite powder of described saturated adsorption anilineAdding concentration is in the dodecylbenzenesulfonic acid solution of 0.5mol/L, mixes and obtains mixed liquor; ToIn described mixed liquor, drip (the NH that concentration is 0.5mol/L4)2S2O8Solution, time for adding is no more than30min causes aniline polymerization reaction under stirring condition, and reaction temperature is 5 DEG C, and the reaction time is2h, obtains polymer-Graphene-polyaniline suspension; The volume of described dodecylbenzenesulfonic acid solutionFor 6 times of micro-foamable polymer-graphene composite powder quality, (NH4)2S2O8The volume of solution is micro-6 times of foamable polymer-graphene composite powder quality, wherein the unit of volume is mL, qualityUnit be g;
Step 4, in polymer-Graphene described in step 3-polyaniline suspension, drip anhydrous secondThe mixed solution of alcohol and acetone is to breakdown of emulsion, and then filtration under diminished pressure, obtains polymer-Graphene-polyanilineFilter cake, by polymer-Graphene-polyaniline filter cake with deionized water cyclic washing in cleaning solution without sulphurAcid ion (adopts 0.1mol/LBaCl2Solution detects cleaning solution and generates without precipitation); DescribedIn the mixed solution of absolute ethyl alcohol and acetone, the volumn concentration of absolute ethyl alcohol is 50%;
Step 5, the polymer-Graphene after cyclic washing in step 4-polyaniline filter cake is broken up,At 80 DEG C, after vacuum drying 6h, mill 5 times through pan type physico chemical reactor, obtain polymer-Graphene-polyaniline electromagnetic shielding composite material.
After testing, polymer-Graphene-polyaniline electromagnetic shielding composite material that prepared by the present embodimentSpecific insulation is 100 Ω cm, electromagnet shield effect: at X-band (8.3GHz～12.4GHz)The about 5.5dB of reflection performance, absorb usefulness 22.5～30.3dB, total shield effectiveness 28～35.8dB;At the about 5.1dB of reflection performance of Ku (12.4GHz～18GHz), absorb usefulness 32.5～40.2dB,Total shield effectiveness 37.5～45.3dB.
Embodiment 8
Polymer-Graphene-polyaniline electromagnetic shielding composite material of the present embodiment is mainly by following weightThe raw material of percentage composition is made: polyurethane 10%, haloflex 3%, polystyrene block copolymerizationThing 2%, modified expanded graphite 10%, aniline 5%, surplus is ethylene-propylene copolymer; Described changingProperty expanded graphite is after titanate coupling agent (as NDZ-311 or NTC-131 etc.) interface processingExpanded graphite, the quality of titanate coupling agent is 3% of expanded graphite quality, interface processing timeBetween be 20min, expanded graphite by expansion multiplying power higher than 220 expansible graphite through microwave irradiation 15sExpansion is made.
The preparation method of polymer-Graphene-polyaniline electromagnetic shielding composite material of the present embodiment comprisesFollowing steps:
Step 1, ethylene-propylene copolymer, polyurethane, haloflex and polystyrene block is commonPolymers mixes rear employing pan type physico chemical reactor and mills and carry out preplasticizing 5 times, obtains carrierResin, then mixes modified expanded graphite and described vector resin, obtains compound, by instituteState compound and in pan type physico chemical reactor, mill 30 times, obtain polymer-Graphene composite powderBody;
Step 2, under stirring condition, polymer-graphene composite powder described in step 1 is addedIn foaming agent solution, leave standstill in confined conditions 24h; Then by leave standstill after system in nitrogen protectionUnder, oil bath is incubated 8min after being heated to 112 DEG C; Again by insulation after system cooling in ice-water bath,Filtration under diminished pressure obtains filter cake, and filter cake obtains micro-foamable polymer-Graphene after vacuum drying desolvationComposite granule; Described foaming agent solution is mixed and is made by the raw material of following volumn concentration: ringHexanone 15%, acetone 55%, butanone 18%, azodiisobutyronitrile 12%; Polymer-Graphene is multipleThe ratio that closes the quality of powder and the volume of foaming agent solution is 2:1, and wherein the unit of quality is g, volumeUnit be mL;
Step 3, by saturated in aniline micro-foamable polymer-graphene composite powder described in step 2Adsorb swelling 24h, the aniline that filtered and recycled is unnecessary, obtains the polymer-Graphene of saturated adsorption anilineComposite granule; Under stirring condition, by the polymer-graphene composite powder of described saturated adsorption anilineAdding concentration is in the dodecylbenzenesulfonic acid solution of 0.5mol/L, mixes and obtains mixed liquor; ToIn described mixed liquor, drip (the NH that concentration is 0.5mol/L4)2S2O8Solution, time for adding is no more than30min causes aniline polymerization reaction under stirring condition, and reaction temperature is 5 DEG C, and the reaction time is2h, obtains polymer-Graphene-polyaniline suspension; The volume of described dodecylbenzenesulfonic acid solutionFor 6 times of micro-foamable polymer-graphene composite powder quality, (NH4)2S2O8The volume of solution is micro-6 times of foamable polymer-graphene composite powder quality, wherein the unit of volume is mL, qualityUnit be g;
Step 4, in polymer-Graphene described in step 3-polyaniline suspension, drip anhydrous secondThe mixed solution of alcohol and acetone is to breakdown of emulsion, and then filtration under diminished pressure, obtains polymer-Graphene-polyanilineFilter cake, by polymer-Graphene-polyaniline filter cake with deionized water cyclic washing in cleaning solution without sulphurAcid ion (adopts 0.1mol/LBaCl2Solution detects cleaning solution and generates without precipitation); DescribedIn the mixed solution of absolute ethyl alcohol and acetone, the volumn concentration of absolute ethyl alcohol is 50%;
Step 5, the polymer-Graphene after cyclic washing in step 4-polyaniline filter cake is broken up,At 80 DEG C, after vacuum drying 6h, mill 5 times through pan type physico chemical reactor, obtain polymer-Graphene-polyaniline electromagnetic shielding composite material.
After testing, polymer-Graphene-polyaniline electromagnetic shielding composite material that prepared by the present embodimentSpecific insulation is 100 Ω cm, electromagnet shield effect: anti-at Ku (12.4GHz～18GHz)Penetrate the about 5.5dB of usefulness, absorb usefulness 32.4～44.2dB, total shield effectiveness 37.9～49.7dB.
Embodiment 9
Polymer-Graphene-polyaniline electromagnetic shielding composite material of the present embodiment is mainly by following weightThe raw material of percentage composition is made: haloflex 2.5%, and modified expanded graphite 2.5%, aniline 5%,Surplus is polystyrene; Described modified expanded graphite be through titanate coupling agent (as NDZ-311 orNTC-131 etc.) expanded graphite after interface processing, the quality of titanate coupling agent is expanded graphite matterAmount 5%, the time of interface processing is 10min, expanded graphite by expansion multiplying power higher than 220 canExpanded graphite expands and makes through microwave irradiation 10s.
The preparation method of polymer-Graphene-polyaniline electromagnetic shielding composite material of the present embodiment comprisesFollowing steps:
Step 1, polystyrene and haloflex are mixed to rear employing millstones shape force-chemical reactionDevice is milled and is carried out preplasticizing 6 times, obtains vector resin, then by modified expanded graphite and described carrierMixed with resin is even, obtains compound, and described compound is milled in pan type physico chemical reactor50 times, obtain polymer-graphene composite powder;
Step 2, under stirring condition, polymer-graphene composite powder described in step 1 is addedIn foaming agent solution, leave standstill in confined conditions 20h; Then by leave standstill after system in nitrogen protectionUnder, oil bath is incubated 8min after being heated to 112 DEG C; Again by insulation after system cooling in ice-water bath,Filtration under diminished pressure obtains filter cake, and filter cake obtains micro-foamable polymer-Graphene after vacuum drying desolvationComposite granule; Described foaming agent solution is mixed and is made by the raw material of following volumn concentration: ringHexanone 15%, acetone 55%, butanone 18%, azodiisobutyronitrile 12%; Polymer-Graphene is multipleThe ratio that closes the quality of powder and the volume of foaming agent solution is 2:1, and wherein the unit of quality is g, volumeUnit be mL;
Step 3, by saturated in aniline micro-foamable polymer-graphene composite powder described in step 2Adsorb swelling 30h, the aniline that filtered and recycled is unnecessary, obtains the polymer-Graphene of saturated adsorption anilineComposite granule; Under stirring condition, by the polymer-graphene composite powder of described saturated adsorption anilineAdding concentration is in the dodecylbenzenesulfonic acid solution of 0.8mol/L, mixes and obtains mixed liquor; ToIn described mixed liquor, drip (the NH that concentration is 0.5mol/L4)2S2O8Solution, time for adding is no more than20min causes aniline polymerization reaction under stirring condition, and reaction temperature is 6 DEG C, and the reaction time is2h, obtains polymer-Graphene-polyaniline suspension; The volume of described dodecylbenzenesulfonic acid solutionFor 7 times of micro-foamable polymer-graphene composite powder quality, (NH4)2S2O8The volume of solution is micro-5 times of foamable polymer-graphene composite powder quality, wherein the unit of volume is mL, qualityUnit be g;
Step 4, in polymer-Graphene described in step 3-polyaniline suspension, drip anhydrous secondThe mixed solution of alcohol and acetone is to breakdown of emulsion, and then filtration under diminished pressure, obtains polymer-Graphene-polyanilineFilter cake, by polymer-Graphene-polyaniline filter cake with deionized water cyclic washing in cleaning solution without sulphurAcid ion (adopts 0.1mol/LBaCl2Solution detects cleaning solution and generates without precipitation); DescribedIn the mixed solution of absolute ethyl alcohol and acetone, the volumn concentration of absolute ethyl alcohol is 60%;
Step 5, the polymer-Graphene after cyclic washing in step 4-polyaniline filter cake is broken up,At 60 DEG C, after vacuum drying 10h, mill 10 times through pan type physico chemical reactor, obtain polymer-Graphene-polyaniline electromagnetic shielding composite material.
After testing, polymer-Graphene-polyaniline electromagnetic shielding composite material that prepared by the present embodimentSpecific insulation is 100 Ω cm, electromagnet shield effect: in the reflection of Ku (12.4GHz～18GHz)The about 5.3dB of usefulness, absorbs usefulness 33.2～41.7dB, total shield effectiveness 38.1～47.5dB.
The above, be only preferred embodiment of the present invention, not the present invention imposed any restrictions, allAny simple modification, change and the equivalence of above embodiment being done according to the technology of the present invention essenceChange, all still belong in the protection domain of technical solution of the present invention.

Claims (10)

1. polymer-Graphene-polyaniline electromagnetic shielding composite material, is characterized in that, mainRaw material by following weight percentage is made: thermoplastic elastomer (TPE) 2.5%～15%, modified expanded stoneChina ink 2.5%～20%, aniline 5%～20%, processing aid 0%～20%, surplus is matrix resin;Described thermoplastic elastomer (TPE) is the one in haloflex, polyurethane and styrene block copolymerOr several; Described matrix resin be polyvinyl chloride, polyolefin, Merlon or acrylonitrile-butadiene-Styrol copolymer; Described modified expanded graphite is the expansion stone after titanate coupling agent interface processingChina ink.
2. polymer-Graphene according to claim 1-polyaniline electromagnetic shielding composite material,It is characterized in that, described expanded graphite by expansion multiplying power higher than 220 expansible graphite through microwave irradiation3s～15s expands and makes.
3. polymer-Graphene according to claim 1-polyaniline electromagnetic shielding composite material,It is characterized in that, the quality of described titanate coupling agent is 3%～5% of expanded graphite quality, interfaceThe time of processing is 10min～20min.
4. polymer-Graphene according to claim 1-polyaniline electromagnetic shielding composite material,It is characterized in that, described processing aid is one or more in stabilizing agent, lubricant and plasticizer,Stabilizing agent is that N-phenyl maleimide acid group closes lanthanum (III), N-benzyl maleic amide acid group closes lanthanum (III)Or N-cetyl maleic amide acid group closes lanthanum (III), the quality of stabilizing agent is matrix resin qualityBelow 5%, lubricant is stearic acid, calcium stearate or dolomol, and the quality of lubricant is matrix treeBelow 10% of lipid amount, plasticizer is straight chain type polyester plasticizer, the quality of plasticizer is matrix treeBelow 15% of lipid amount.
One kind prepare polymer-Graphene as described in arbitrary claim in claim 1 to 4-The method of polyaniline electromagnetic shielding composite material, is characterized in that, comprises the following steps:
Step 1, after being mixed, matrix resin, thermoplastic elastomer (TPE) and processing aid carry out preformedChange, obtain vector resin, then modified expanded graphite and described vector resin are mixed, obtainCompound is milled described compound 20～50 times in pan type physico chemical reactor, is gatheredCompound-graphene composite powder;
Step 2, under stirring condition, polymer-graphene composite powder described in step 1 is addedIn foaming agent solution, leave standstill in confined conditions 20h～30h; Then by leave standstill after system at nitrogenUnder protection, oil bath is incubated 5min～10min after being heated to 110 DEG C～115 DEG C; Again by the body after insulationTie up in ice-water bath coolingly, filtration under diminished pressure obtains filter cake, and it is poly-that filter cake obtains micro-foaming after vacuum dryingCompound-graphene composite powder;
Step 3, by saturated in aniline micro-foamable polymer-graphene composite powder described in step 2Adsorb swelling 20h～30h, the aniline that filtered and recycled is unnecessary, obtain the polymer of saturated adsorption aniline-Graphene composite powder; Under stirring condition, by multiple polymer-the Graphene of described saturated adsorption anilineClosing powder, to add concentration be in the dodecylbenzenesulfonic acid solution of 0.5mol/L～1.0mol/L, mixes allThe even mixed liquor that obtains; Be 0.4mol/L～0.8mol/L's to dripping concentration in described mixed liquor(NH4)2S2O8Solution causes aniline polymerization reaction under stirring condition, and reaction temperature is 3 DEG C～8DEG C, the reaction time is 1h～3h, obtains polymer-Graphene-polyaniline suspension; Described dodecaneThe volume of base benzene sulfonic acid solution is 5～8 times of micro-foamable polymer-graphene composite powder quality,(NH4)2S2O8The volume of solution is 5～8 times of micro-foamable polymer-graphene composite powder quality,Wherein the unit of volume is mL, and the unit of quality is g;
Step 4, in polymer-Graphene described in step 3-polyaniline suspension, drip anhydrous secondThe mixed solution of alcohol and acetone is to breakdown of emulsion, and then filtration under diminished pressure, obtains polymer-Graphene-polyanilineFilter cake, by polymer-Graphene-polyaniline filter cake with deionized water cyclic washing in cleaning solution without sulphurAcid ion;
Step 5, the polymer-Graphene after cyclic washing in step 4-polyaniline filter cake is broken up,After vacuum drying, mill 5～10 times through pan type physico chemical reactor, obtain polymer-Graphene-poly-Aniline electromagnetic shielding composite material.
6. method according to claim 5, is characterized in that, preplasticizing described in step 1Method for adopt pan type physico chemical reactor mill 3～6 times.
7. method according to claim 5, is characterized in that, blowing agent described in step 2Solution is mixed and is made by the raw material of following volumn concentration: cyclohexanone 10%～20%, acetone50%～60%, butanone 15%～20%, azodiisobutyronitrile 10%～15%; Polymer-GrapheneThe quality of composite granule is (1～3) with the ratio of the volume of foaming agent solution: 1, and the wherein unit of qualityFor g, the unit of volume is mL.
8. method according to claim 5, is characterized in that, in step 3 in mixed liquorDrip (NH4)2S2O8The time of solution is no more than 30min.
9. method according to claim 5, is characterized in that, anhydrous second described in step 4In the mixed solution of alcohol and acetone, the volumn concentration of absolute ethyl alcohol is 30%～70%.
10. method according to claim 5, is characterized in that, vacuum described in step 5 is dryDry temperature is 50 DEG C～80 DEG C, and the time is 6h～10h.
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CN106317516A (en) * 2016-08-31 2017-01-11 青岛大学 Graphene modification based antistatic rubber composite material and preparation method thereof
CN106690478A (en) * 2016-11-17 2017-05-24 无锡市长安曙光手套厂 Detachable inserting-plate anti-radiation garment
CN109021421A (en) * 2018-05-31 2018-12-18 广东安普智信电气有限公司 A kind of electromagnetic shielding material and preparation method thereof and cable protection pipe obtained
CN109021450A (en) * 2018-07-20 2018-12-18 广东安普智信电气有限公司 A kind of shock resistance high heat resistance material and preparation method thereof and cable protection pipe obtained
CN111002674A (en) * 2019-12-19 2020-04-14 横店集团东磁股份有限公司 Composite electromagnetic shielding material and preparation method thereof
CN111002674B (en) * 2019-12-19 2021-06-25 横店集团东磁股份有限公司 Composite electromagnetic shielding material and preparation method thereof
CN112250966A (en) * 2020-10-19 2021-01-22 陕西科技大学 Polyvinyl chloride-graphene composite material and preparation method and application thereof
CN114015137A (en) * 2021-11-15 2022-02-08 成都先进金属材料产业技术研究院股份有限公司 Polyaniline-doped conductive plastic for all-vanadium redox flow battery and preparation method thereof
CN114907701A (en) * 2022-06-23 2022-08-16 扬州本来生物科技有限公司 Low-odor electromagnetic shielding thermoplastic elastomer material and preparation method thereof

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