CN109021421A - A kind of electromagnetic shielding material and preparation method thereof and cable protection pipe obtained - Google Patents
A kind of electromagnetic shielding material and preparation method thereof and cable protection pipe obtained Download PDFInfo
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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
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
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Abstract
The present invention relates to cable material technical fields; more particularly to a kind of electromagnetic shielding material and preparation method thereof and cable protection pipe obtained; the electromagnetic shielding material includes the raw material of following parts by weight: 75-100 parts of polyvinyl chloride resins, 12-18 parts of electromagnetic shielding materials, 15-20 parts of fire retardants, 8-12 parts of synergistic flame retardants, 10-15 parts of impact modifiers, 12-18 parts of coupling agents, 5-15 parts of compatilizers and 6-10 parts of acrylate fibers, and wherein electromagnetic shielding material is polyaniline-graphene oxide composite material.PVC material of the invention has the performances such as preferable anti-flammability, impact resistance, weatherability, tensile strength, hardness, by being reflected using the high conductivity of polyaniline electromagnetic wave, electromagnetic wave is absorbed in conjunction with the high microwave absorbing property of graphene oxide, the two combines, and PVC material obtained can be made to have excellent electromagnetic shielding action.
Description
Technical field
The present invention relates to cable protection pipe material technical fields, and in particular to a kind of electromagnetic shielding material and preparation method thereof
With cable protection pipe obtained.
Background technique
With wireless communication tool, the high speed development of radio-television industries, the all-round popularization of office computer automation, electronic vapour
The rapid proliferation of vehicle, electromagnetic radiation be it is ubiquitous, all-pervasive, become a kind of novel environmental pollution, meanwhile, with skill
The development of art, cable are also widely used in the fields such as electric system, information transmission, instrument system, and the light weight of PVC material,
Mechanical strength is good, and has the performances such as excellent insulating properties, anti-flammability, corrosion resistance, and Costco Wholesale is low, from a wealth of sources, wide
It is general to be applied to cable protection material.
But electromagnetic radiation is easy to affect human health, wherein the health effect to fetus, child is maximum, it is long
Phase is exposed under electromagnetic radiation, can induce cancer, such as leukaemia, becomes the inducement of a variety of diseases；In addition, electromagnetism wave energy without
It hinders ground to pass through plastic protective cover and generates interference, the electronic devices such as instrument and meter are interfered, the normal of electronic device is made
Function is interfered or hinders, and causes to be unable to normal use, especially in the instruments essence such as field of aviation flight and field of medical device
The high field of density requirements, the electromagnetic interference that cable generates will affect instrument normal work, be easy to influence the flight safety of aviation
With the accuracy of Medical Devices.
Summary of the invention
In order to overcome shortcoming and defect existing in the prior art, the purpose of the present invention is to provide a kind of electromagnetic shielding materials
Material, the PVC material reach preferable by the way that electromagnetic wave is reflected and absorbed using polyaniline-graphene oxide composite material
Effectiveness, and have performances, the mechanical mechanics property such as preferable anti-flammability, impact resistance, weatherability excellent.
Another object of the present invention is to provide a kind of preparation method of electromagnetic shielding material, the preparation method operating procedures
Simply, easy to control, high production efficiency, production cost is low, and PVC material quality obtained is stablized, and is applicable to be mass produced.
A further object of the present invention is to provide cable protection pipe made from a kind of application electromagnetic shielding material, which is protected
Pillar has preferable electromagnetic shielding action, can the electromagnetic wave that cable generates be reflected and be absorbed, avoid electromagnetic wave to electricity
Sub- device interferes or influences human health, and has preferable anti-flammability, impact resistance, weatherability, tensile strength and hard
Performances, the mechanical mechanics properties such as degree are excellent.
The purpose of the invention is achieved by the following technical solution: a kind of electromagnetic shielding material, the original including following parts by weight
Material:
The electromagnetic shielding material is polyaniline-graphene oxide composite material.
The present invention prepares PVC material by using above-mentioned raw materials, and PVC material can be made to have preferable electromagnetic shielding action,
And excellent shock resistance, weatherability are good, polyaniline-graphene oxide composite material of use can be using electromagnetic wave absorption and anti-
Radio magnetic wave and play the role of electromagnetic shielding, wherein graphene oxide have excellent physical property, performance of absorbing electromagnetic wave
Good and at low cost, good with electric conductivity polyaniline phase-polymerization can make PVC material have preferable electric conductivity, can be to electromagnetic wave
It is reflected, plays excellent shielding action；And be mutually used in compounding by using fire retardant with synergistic flame retardant, resistance both can be improved
Fuel efficiency fruit, and smoke suppressing effect can be played；The acrylate fiber of use has splendid heat resistance and bullet as heat proof material
Property, the comprehensive performances such as weatherability, the elasticity of PVC material can be effectively improved.
Preferably, the fire retardant is deca-BDE, tetrabromobisphenol A, decabromodiphenylethane, 2,4,6- tribromo-benzenes
Phenol, 2, in bis- (tetrabromo phthalimide) ethane of 4,6- tribromo phenyl allyl ethers, tetrabromophthalic anhydride, 1,2-
It is at least one；The synergistic flame retardant is at least one in antimony oxide, zinc oxide, zinc stearate, magnesium silicate and zinc borate
Kind.
The present invention by using mentioned kind fire retardant, it is environmentally friendly, can be matched with other raw materials effect, cooperate with it is anti-
It answers, and the flame retardant property of PVC material can be improved, the performance of PVC material is influenced smaller；Wherein, deca-BDE thermal stability
Good, flame-retarded efficiency is high, and when being used in combination with antimony oxide, the apparent synergistic effect of phase mutual makes PVC material tool obtained
There is higher flame-retarded efficiency, thermal stability is more preferable；The tetrabromobisphenol A and decabromodiphenylethane of use to environment and human body without
Evil, bromine content is high, and thermal stability is good, exudative low, improves the stability of PVC material.More preferably, the fire retardant is
By deca-BDE, decabromodiphenylethane and 2,4,6- tribromo phenyl allyl ethers are 2.5-3.5:1.5-2:1 with weight ratio
The mixture of composition.
The present invention can match effect, concerted reaction by using the synergist of mentioned kind with other raw materials, and fire-retardant
Agent, which matches, has preferably synergistic effect, free radical can be captured in the gas phase, and play synergistic effect in condensed phase, in PVC
Material surface forms strong layer of charcoal, and then plays preferable fire-retardant, fireproofing function to PVC material, and play smoke suppressing effect, changes
The color of kind PVC material；Wherein, the antimony oxide additive amount of use is few, and can have completely with the mutual synergistic effect of fire retardant
Effect improves the anti-flammability of PVC material, and the zinc oxide of use can promote into charcoal and react, and reduces the dosage of fire retardant, improves thermostabilization
Property, reduce raw smoke；The zinc borate of use is nontoxic, and thermal stability is high, and good dispersion can effectively improve the resistance of PVC material
Performance is fired, and can be reduced the generation of smog when burning, and the performances such as mechanical performance, electromagnetic shielding performance of adjustable PVC material.
More preferably, the synergistic flame retardant is with weight ratio by antimony oxide, zinc oxide and zinc borate for 2-3:1:1.2-1.8
The mixture of composition.
Preferably, the impact modifier is Methyl Methacrylate-Butadiene-Styrene Copolymer, haloflex, benzene
In ethylene-butadiene-styrene copolymer, ethylene-vinyl acetate copolymer and acrylonitrile-butadiene-styrene copolymer
It is at least one.
The present invention can effectively improve the processing performance shock resistance of PVC material by using the impact modifier of mentioned kind
Intensity increases the toughness and flexibility of PVC material；Wherein, the Methyl Methacrylate-Butadiene-Styrene Copolymer of use is strong
Degree is high, and rigidity is big, and good weatherability is still able to maintain preferable rigidity under 85-90 DEG C of high temperature, still has at -40 DEG C excellent
Toughness can effectively improve the mechanical strengths such as intensity, rigidity, toughness, impact resistance, the weatherability of PVC material；The chlorination of use is poly-
Ethylene is non-toxic and tasteless, has the performances such as excellent weatherability, resistance to ozone, chemical-resistant resistance, resistance to ag(e)ing, oil resistivity, anti-flammability,
Toughness is good, -30 DEG C still have excellent flexibility, with other high molecular materials have good compatibility, decomposition temperature compared with
Height can effectively improve impact resistance, weatherability, resistance to ag(e)ing, toughness, anti-flammability of PVC material etc.；Styrene-fourth of use
Diene-styrene copolymer has excellent tensile strength, big surface friction coefficient, low temperature performance well, excellent electrical properties, processing
Excellent performance can effectively improve impact strength, lower temperature resistance of PVC material etc.；The acrylonitrile-butadiene-styrene (ABS) of use is total
Polymers is non-toxic and tasteless, and intensity is high, and good toughness is easily processed into type, and no melting drip phenomenon, acrylonitrile content therein can improve
Performances, the butadiene components such as hardness, heat resistance and the corrosion of acidproof alkali salt of PVC material can improve the low temperature ductility of PVC material
And impact resistance, styrene content can improve hardness, processing fluidity and the surface smoothness of PVC material.More preferably, institute
Stating impact modifier is by Methyl Methacrylate-Butadiene-Styrene Copolymer, haloflex and acrylonitrile-butadiene-benzene
Ethylene copolymer is with the mixture that weight ratio is that 3.5-4:1:2-3 is formed.
Preferably, the coupling agent is vinyltriethoxysilane, anilinomethyl triethoxysilane, γ-methyl-prop
Alkene acryloxypropylethoxysilane trimethoxy silane, methyltriethoxysilane, pyrophosphate titanate esters and (the 'beta '-methoxy second of vinyl three
At least one of oxygroup) silane；The compatilizer is that hydrogenated styrene-butadiene-styrene copolymer is grafted metering system
Acid glycidyl ester, ethylene-acrylic acid-methyl esters graft glycidyl methacrylate and one acrylonitrile copolymer of styrene connect
At least one of branch glycidyl methacrylate.
The present invention can match effect, concerted reaction with other raw materials, effectively mention by using the coupling agent of mentioned kind
Combining closely between high each raw material, can improve polyvinyl chloride resin and electromagnetic shielding material, fire retardant, synergistic flame retardant, impact modifier,
The interface performance of coupling agent, compatilizer and acrylate fiber paper handkerchief improves dispersibility, stickiness, compatibility and the processing of raw material
Performance makes PVC material obtained have the comprehensive performances such as preferable heat resistance, dispersibility, cohesive force, anti-aging property, intensity；
Wherein, the vinyltriethoxysilane of use can effectively improve the affinity between each raw material, the intensity of Reinforced PVC material；
The γ of use-methacryloxypropyl trimethoxy silane improves the mechanical performance of PVC material, electric property, ageing-resistant
Performance and weather resistance, bonding force is good, and durability is strong；The methyltriethoxysilane of use can effectively improve the anti-of PVC material
The performances such as punching performance, rheological characteristic, processability and stability；('beta '-methoxy ethyoxyl) silane of vinyl three and propylene of use
After acid esters fiber (heat proof material) combines, the surface-hydrophobicized of heat proof material can be made, and then improve heat proof material and other raw materials
Compatibility, achieve the effect that good dispersion, melt viscosity be low, excellent processing performance.More preferably, the coupling agent is by second
Alkenyl triethoxysilane, γ-methacryloxypropyl trimethoxy silane and vinyl three ('beta '-methoxy ethyoxyl)
Silane is with the mixture that weight ratio is that 1.5-2:1:2.4-3.2 is formed.
The present invention can match effect, concerted reaction by using the compatilizer of mentioned kind with other raw materials, effectively drop
Low PVC resin intermolecular interfacial tension when being reacted with other raw materials, and then interface cohesive force is improved, make dispersed phase and continuous phase
Uniformly, stable structure is formed, the mutual cooperation reaction of each raw material of PVC material is promoted, the tensile strength of PVC material is improved, resists
The mechanical performances such as impact strength improve rheological performance, improve surface smoothness.More preferably, the compatilizer is by hydrogen
Change styrene-butadiene-styrene graft glycidyl methacrylate and one acrylonitrile copolymer of styrene connects
Branch glycidyl methacrylate is with the mixture that weight ratio is that 2-3:1 is formed.
Preferably, the polyaniline-graphene oxide composite material is made by following steps:
Step (1): taking 1-3 parts of mass fractions is that the graphene oxide water solution of 2-10% is added to 45-55 parts of deionizations
In water, 50-60 parts of stabilizers are then added, mixture A is made after being stirred by ultrasonic；
Step (2): taking 1-3 parts of Bronsted acids and 2-5 parts of aniline monomers to be uniformly mixed, and is then added obtained to step (1)
In mixture A, 3-4h is mixed, mixture B is made；
Step (3): taking 12-15 parts of initiators to be added into mixture B made from step (2), and 50-70min is mixed,
Mixture C is made；
Step (4): mixture C made from step (3) being centrifuged, dried, is pulverized, and polyaniline-oxidation is made
Graphene composite material.
The present invention prepares polyaniline-graphene oxide composite material by using above-mentioned steps, adds graphene oxide into
Into monomer, while initiator is added, home position polymerization reaction can be occurred for graphene oxide and monomer, graphene oxide can be made to exist
Disperse relatively uniform in polymerization system, while aniline monomer polymerization generates polyaniline, graphene oxide and polyaniline it is mutual
Effect can make polyaniline be uniformly coated on the surface of graphene oxide, improve polyaniline-graphene oxide composite material
Stability, and electromagnetic wave is reflected using the high conductivity of polyaniline, in conjunction with the high microwave absorbing property of graphene oxide
Electromagnetic wave is absorbed, the two combines, the polyaniline-coated with reflection electromagnetic wave performance with performance of absorbing electromagnetic wave
Graphene oxide, make composite material first with cladding polyaniline carry out reflection of electromagnetic wave, recycle graphene oxide to not
Fully reflective electromagnetic wave is absorbed, and PVC material obtained is made to have excellent electromagnetic shielding action；And pass through strict control
The dosage of graphene oxide and polyaniline, energy composite material has preferable stability and electromagnetic shielding performance, if graphite oxide
The dosage of alkene is much larger than the dosage of aniline monomer, is easy to reduce multiple so that partial oxidation of graphite is not coated by polyaniline
The stability of condensation material, and the performance of composite material reflection electromagnetic wave is reduced, the electromagnetic shielding performance for reducing PVC material is stablized
Property, reduce the electromagnetic shielding action of PVC material；If the dosage of graphene oxide is much smaller than the dosage of aniline monomer, reduce
The performance of composite material electromagnetic wave absorption, reduces the electromagnetic shielding action of PVC material.
And polyaniline-graphene oxide composite material made from operating procedure of the invention is used, conductivity reaches 1.168-
2.018S/cm can make PVC material have preferable conductivity, can be reflected electromagnetic wave and play the role of electromagnetic shielding,
And by the way that stabilizer is added, the spatial stability of graphene oxide can be improved, convenient for subsequent and polyaniline phase separation
Stable polyaniline-graphene oxide composite material is generated, and graphene oxide can be improved in composite material or PVC material
Electromagnetic wave absorption stability.
And by the way that Bronsted acid is added, regularity, doping rate and the electricity of polyaniline made from aniline monomer can be effectively improved
Performance improves the conductivity of polyaniline, and then improves the reflection electromagnetic wave performance of graphene oxide-polyaniline composite material, mentions
The electromagnetic shielding action of high PVC material；If the dosage of Bronsted acid is excessive, makes the conductivity of composite material excessive, drop instead
The low effectiveness of PVC material；If the dosage of Bronsted acid is very few, make the conductivity of composite material insufficient, electromagnetism
Shield effectiveness is undesirable.
And by the way that initiator is added, it can be effectively facilitated the polymerization reaction of aniline monomer, and promote graphene oxide water
The home position polymerization reaction of solution and polyaniline, improves polyaniline-graphene oxide composite material conductivity and electromagnetic shielding is made
With；And the dosage of strict control initiator, the effective active factor and the degree of polymerization in reaction system can be effectively improved, is improved multiple
The conductivity and electromagnetic shielding action of condensation material；If the dosage of initiator is very few, there was only a small amount of effective work in reaction system
The degree of polymerization of sex factor, the compound reacted is lower, and conductivity is lower, and effectiveness is undesirable；If initiator
Dosage is excessive, then the main chain conjugated structure of polymer is easy to be destroyed, and reduces conductivity and electromagnetic shielding action.
Preferably, in the step (1), the stabilizer is polyvinylpyrrolidone；It is described in the step (2)
The mixture that Bronsted acid is made of sulfosalicylic acid, p-methyl benzenesulfonic acid and perchloric acid with weight ratio for 3-4:2-3:1-1.5；
In the step (3), the initiator is the mixture that forms of 3-4:1 with weight ratio by ammonium persulfate and potassium peroxydisulfate.
For the present invention by using polyvinylpyrrolidone as stabilizer, and strict control its mass fraction can be effective
The spatial stability of graphene oxide is improved, generates stable polyaniline-by home position polymerization reaction with polyaniline convenient for subsequent
Graphene oxide composite material, and electromagnetic wave absorption of the graphene oxide in composite material or PVC material can be improved and stablized
Property.
The present invention by using sulfosalicylic acid, p-methyl benzenesulfonic acid and perchloric acid as Bronsted acid, it is inorganic using small molecule
The sour high conductivity of (perchloric acid) and high conductivity and the surface of macromolecule organic acid (sulfosalicylic acid, p-methyl benzenesulfonic acid)
Activation effectively enhances the solubility of polyaniline obtained, improves polyaniline-graphene oxide composite material heat resistance
And processing performance.Wherein, larger to anion volume present in sulfosalicylic acid and p-methyl benzenesulfonic acid, it reduces obtained poly-
Interaction force between aniline molecule, while existing between polyaniline molecule with intramolecular to stretch chain conformation, chain spacing is increased,
It is delocalized that charge occurs, thus conductivity with higher, simultaneously because increasing the molten of polyaniline to the activation of anion
Xie Xing；And transition and the electricity being arranged with conducive to electronics that perchloric acid is mutual between its molecular chain structure and molecule in doping reaction
The delocalization of sub- cloud, thus conductivity with higher；By by sulfosalicylic acid, p-methyl benzenesulfonic acid and perchloric acid with 3-4:2-3:
The ratio mixing of 1-1.5 is used as Bronsted acid, can effectively improve polyaniline-graphene oxide composite material conductivity, dissolution
Stability, heat resistance and processing performance, make polyaniline-graphene oxide composite material obtained has excellent electromagnetic shielding
Performance.
The present invention, as initiator, can be effectively facilitated the polymerization of aniline monomer by using ammonium persulfate and potassium peroxydisulfate
Reaction, and promote the home position polymerization reaction of graphene oxide water solution and polyaniline, it is compound to improve polyaniline-graphene oxide
The conductivity and electromagnetic shielding action of material.
Preferably, in the step (1), the power of ultrasonic agitation is 150-250W, and the time of ultrasonic agitation is 30-
40min；In the step (2), the temperature of mixing is -5 DEG C~4 DEG C；In the step (3), it is added into mixture B
First controlling the temperature of initiator before initiator is -5 DEG C~4 DEG C, and the temperature of mixing is -5 DEG C~4 DEG C.
Ultrasonic agitation power and time of the present invention by strict control step (1), can make graphene oxide water solution exist
Sufficient spatial stability effect is obtained under the action of stabilizer, passes through the graphene oxide of spatial stability and polyaniline in situ poly-
It closes reaction and generates stable polyaniline-graphene oxide composite material, and graphene oxide can be improved in composite material or PVC material
Electromagnetic wave absorption stability in material；
It is since aniline monomer is under the chanza of Bronsted acid by the mixing temperature of strict control step (2)
The process for aggregating into polyaniline belongs to exothermic reaction, is the oxidation and reduction of free radical, and reaction temperature is excessively high, can be excessively very fast
The rapid polymerization of reaction speed, aniline monomer can make it that selective oxidation only occur, and weaken the oxidizing component of main chain, can make polyphenyl
Amine accelerates hydrolysis in the acid solution of Bronsted acid, destroys the link structure of polyaniline, influences mixing for Bronsted acid and aniline monomer
Miscellaneous effect, and the generation of polyaniline is influenced, the conductivity of polyaniline is reduced, the electromagnetic shielding performance of composite material is reduced；Cause
And by using lower mixing reaction temperature, the regularity of polyaniline chain link can be improved, the time of chain termination is delayed, is increased
Addition polymerization aniline molecule quality promotes its generation, improves the conductivity and reflection of electromagnetic wave performance of polyaniline, improves obtained compound
The electromagnetic shielding action of material.
Similarly, it by the initiator temperature and mixing temperature that are added in strict control step (3), can improve poly-
The chain link regularity of aniline and graphene oxide composite polymeric process, delays the time of chain termination, increases the molecule of composite material
Quality improves the conductivity, reflection electromagnetic wave performance and performance of absorbing electromagnetic wave of composite material, makes polyaniline-oxidation obtained
Graphene composite material has excellent electromagnetic shielding action.
Another object of the present invention is achieved through the following technical solutions: a kind of preparation of electromagnetic shielding material as described above
Method includes the following steps:
Polyvinyl chloride resin, electromagnetic shielding material, coupling agent, compatilizer and acrylate fiber are carried out first according to parts by weight
Then secondary mixing adds remaining raw material, carry out second and be mixed, obtain mixture；Mixture investment is squeezed
Equipment is kneaded, is squeezed out, is granulated out, and electromagnetic shielding material is made.
The present invention by using batch mixed mode, using compatilizer and coupling agent first by electromagnetic shielding material, propylene
Acid esters fiber is sufficiently mixed with polyvinyl chloride resin, and electromagnetic shielding material and acrylate fiber in PVC material is made to be uniformly dispersed, tool
There are excellent and uniform electromagnetic shielding performance and heat resistance；Remaining fire retardant, synergistic flame retardant, impact modifier are added,
It is fully mixed in above-mentioned mixture, improves the anti-flammability and shock resistance of PVC material, and preparation method operating procedure letter
Single, easy to control, high production efficiency, production cost is low, and PVC material quality obtained is stablized, and is applicable to be mass produced.
Preferably, the speed of agitator that the first time is mixed is 900-1200r/min, second of mixing
Speed of agitator be 1200-1300r/min；One area's temperature of the extrusion equipment is 270-280 DEG C, and two area's temperature are 280-
290 DEG C, three area's temperature are 295-305 DEG C, and four area's temperature are 305-315 DEG C, and five area's temperature are 290-305 DEG C.
The present invention passes through the revolving speed of strict control raw material being mixed twice and each area's temperature of extruding pelletization, energy
The raw materials such as electromagnetic shielding material, acrylate fiber, fire retardant, synergistic flame retardant, impact modifier are made to be fully mixed to polyvinyl chloride resin
In, make PVC material obtained that there is excellent electromagnetic shielding performance, anti-flammability, heat resistance, impact resistance, tensile strength, hardness
Etc. comprehensive performances, and processability is good, and excellent processing performance is asked.
Another object of the present invention is achieved through the following technical solutions: a kind of cable protection pipe, the cable protection pipe by
Above-mentioned electromagnetic shielding material is made, and the electromagnet shield effect of the cable protection pipe is 21.23-43.87dB；The cable
Protection pipe is made by following steps: electromagnetic shielding material being heated to 300-320 DEG C and is melted, is then added to shaping mould
It is formed in tool, obtains cable protection pipe after cooling.
The present invention can be such that cable protection pipe obtained has excellent by molding, cooling after melting PVC material
The comprehensive performances such as electromagnetic shielding performance, anti-flammability, heat resistance, impact resistance, tensile strength, hardness, the electricity that cable can be generated
Magnetic wave is reflected and is absorbed, and plays the role of electromagnetic shielding, electromagnet shield effect is up to 21.23-43.87dB.
The beneficial effects of the present invention are: PVC materials of the invention to have preferable effectiveness, anti-flammability, anti-
The comprehensive performances such as impact, weatherability, tensile strength, hardness, by using polyaniline high conductivity to electromagnetic wave into
Row reflection, absorbs electromagnetic wave in conjunction with the high microwave absorbing property of graphene oxide, and the two combines, and has reflection electromagnetic wave performance
Polyaniline-coated the graphene oxide with performance of absorbing electromagnetic wave, make composite material first with cladding polyaniline carry out
Reflection of electromagnetic wave recycles graphene oxide to absorb not fully reflective electromagnetic wave, has PVC material obtained excellent
Different electromagnetic shielding action.
The preparation method operating procedure of PVC material of the present invention is simple, and easy to control, high production efficiency, production cost is low, system
The PVC material quality obtained is stablized, and is applicable to be mass produced.
Cable protection pipe made from present invention application electromagnetic shielding material has excellent electromagnetic wave shielding with excellent
The comprehensive performances such as energy, anti-flammability, heat resistance, impact resistance, tensile strength, hardness, the electromagnetic wave that can generate cable carry out anti-
It penetrates and absorbs, play the role of electromagnetic shielding, electromagnet shield effect is avoided that electromagnetic wave to electronics up to 21.23-43.87dB
Device interferes or influences human health.
Specific embodiment
For the ease of the understanding of those skilled in the art, below with reference to embodiment, the present invention is further illustrated, real
The content that the mode of applying refers to not is limitation of the invention.
Embodiment 1
A kind of electromagnetic shielding material, the raw material including following parts by weight:
The electromagnetic shielding material is polyaniline-graphene oxide composite material.
The fire retardant is tetrabromophthalic anhydride；The synergistic flame retardant is zinc stearate.
The impact modifier is Methyl Methacrylate-Butadiene-Styrene Copolymer.
The coupling agent is vinyltriethoxysilane；The compatilizer is total for hydrogenated styrene-butadiene-styrene
Polymers graft glycidyl methacrylate.
Polyaniline-the graphene oxide composite material is made by following steps:
Step (1): taking 1 part of mass fraction is that 10% graphene oxide water solution is added into 45 parts of deionized waters, so
50 parts of stabilizers are added afterwards, mixture A is made after being stirred by ultrasonic；
Step (2): taking 1 part of Bronsted acid and 2 parts of aniline monomers to be uniformly mixed, and is then added to step (1) mixing obtained
Expect in A, 3h is mixed, mixture B is made；
Step (3): taking 12 parts of initiators to be added into mixture B made from step (2), and 50min is mixed, and is made mixed
Close material C；
Step (4): mixture C made from step (3) being centrifuged, dried, is pulverized, and polyaniline-oxidation is made
Graphene composite material.
In the step (1), the stabilizer is polyvinylpyrrolidone；In the step (2), the Bronsted acid is
The mixture being made of sulfosalicylic acid, p-methyl benzenesulfonic acid and perchloric acid with weight ratio for 3:3:1；It is described in the step (3)
The mixture that initiator is made of ammonium persulfate and potassium peroxydisulfate with weight ratio for 3:1.
In the step (1), the power of ultrasonic agitation is 150W, and the time of ultrasonic agitation is 40min；The step (2)
In, the temperature of mixing is -5 DEG C；In the step (3), it is added before initiator into mixture B first by the temperature of initiator
Control is -5 DEG C, and the temperature of mixing is -5 DEG C.
A kind of preparation method of electromagnetic shielding material as described above, includes the following steps:
Polyvinyl chloride resin, electromagnetic shielding material, coupling agent, compatilizer and acrylate fiber are carried out first according to parts by weight
Then secondary mixing adds remaining raw material, carry out second and be mixed, obtain mixture；Mixture investment is squeezed
Equipment is kneaded, is squeezed out, is granulated out, and electromagnetic shielding material is made.
The speed of agitator that the first time is mixed is 900r/min, and the speed of agitator of second of mixing is
1200r/min；One area's temperature of the extrusion equipment is 270 DEG C, and two area's temperature are 280 DEG C, and three area's temperature are 295 DEG C, 4th area
Temperature is 305 DEG C, and five area's temperature are 290 DEG C.
A kind of cable protection pipe, the cable protection pipe are made by above-mentioned electromagnetic shielding material, the cable protection pipe
Electromagnet shield effect be 21.23-43.87dB；The cable protection pipe is made by following steps: electromagnetic shielding material is heated
It is melted to 300 DEG C, is then added and is formed into molding die, obtain cable protection pipe after cooling.
Embodiment 2
A kind of electromagnetic shielding material, the raw material including following parts by weight:
The electromagnetic shielding material is polyaniline-graphene oxide composite material.
The fire retardant is tetrabromobisphenol A or 2,4,6- tribromphenols；The synergistic flame retardant is zinc oxide.
The impact modifier is haloflex.
The coupling agent is anilinomethyl triethoxysilane；The compatilizer is that ethylene-acrylic acid-methyl esters is grafted methyl
Glycidyl acrylate.
Polyaniline-the graphene oxide composite material is made by following steps:
Step (1): taking 1.5 parts of mass fractions is that 8% graphene oxide water solution is added into 48 parts of deionized waters, so
52 parts of stabilizers are added afterwards, mixture A is made after being stirred by ultrasonic；
Step (2): it takes 1.5 parts of Bronsted acids and 3 parts of aniline monomers to be uniformly mixed, is then added to made from step (1) and mixes
It closes in material A, 3.2h is mixed, mixture B is made；
Step (3): taking 13 parts of initiators to be added into mixture B made from step (2), and 55min is mixed, and is made mixed
Close material C；
Step (4): mixture C made from step (3) being centrifuged, dried, is pulverized, and polyaniline-oxidation is made
Graphene composite material.
In the step (1), the stabilizer is polyvinylpyrrolidone；In the step (2), the Bronsted acid is
The mixture being made of sulfosalicylic acid, p-methyl benzenesulfonic acid and perchloric acid with weight ratio for 3.2:2.8:1.1；The step (3)
In, the initiator is the mixture that forms of 3.2:1 with weight ratio by ammonium persulfate and potassium peroxydisulfate.
In the step (1), the power of ultrasonic agitation is 180W, and the time of ultrasonic agitation is 38min；The step (2)
In, the temperature of mixing is -3 DEG C；In the step (3), it is added before initiator into mixture B first by the temperature of initiator
Control is -3 DEG C, and the temperature of mixing is -3 DEG C.
A kind of preparation method of electromagnetic shielding material as described above, includes the following steps:
Polyvinyl chloride resin, electromagnetic shielding material, coupling agent, compatilizer and acrylate fiber are carried out first according to parts by weight
Then secondary mixing adds remaining raw material, carry out second and be mixed, obtain mixture；Mixture investment is squeezed
Equipment is kneaded, is squeezed out, is granulated out, and electromagnetic shielding material is made.
The speed of agitator that the first time is mixed is 1000r/min, second of speed of agitator being mixed
For 1220r/min；One area's temperature of the extrusion equipment be 272 DEG C, two area's temperature be 282 DEG C, three area's temperature be 298 DEG C, four
Area's temperature is 308 DEG C, and five area's temperature are 293 DEG C.
A kind of cable protection pipe, the cable protection pipe are made by above-mentioned electromagnetic shielding material, the cable protection pipe
Electromagnet shield effect be 21.23-43.87dB；The cable protection pipe is made by following steps: electromagnetic shielding material is heated
It is melted to 305 DEG C, is then added and is formed into molding die, obtain cable protection pipe after cooling.
Embodiment 3
A kind of electromagnetic shielding material, the raw material including following parts by weight:
The electromagnetic shielding material is polyaniline-graphene oxide composite material.
The fire retardant is deca-BDE；The synergistic flame retardant is antimony oxide.
The impact modifier is styrene-butadiene-styrene.
The coupling agent is γ-methacryloxypropyl trimethoxy silane or methyltriethoxysilane；It is described
Compatilizer is hydrogenated styrene-butadiene-styrene copolymer grafted glycidyl methacrylate.
Polyaniline-the graphene oxide composite material is made by following steps:
Step (1): taking 2 parts of mass fractions is that 6% graphene oxide water solution is added into 50 parts of deionized waters, then
55 parts of stabilizers are added, mixture A is made after being stirred by ultrasonic；
Step (2): taking 2 parts of Bronsted acids and 3 parts of aniline monomers to be uniformly mixed, and is then added to step (1) mixing obtained
Expect in A, 3.5h is mixed, mixture B is made；
Step (3): taking 13 parts of initiators to be added into mixture B made from step (2), and 60min is mixed, and is made mixed
Close material C；
Step (4): mixture C made from step (3) being centrifuged, dried, is pulverized, and polyaniline-oxidation is made
Graphene composite material.
In the step (1), the stabilizer is polyvinylpyrrolidone；In the step (2), the Bronsted acid is
The mixture being made of sulfosalicylic acid, p-methyl benzenesulfonic acid and perchloric acid with weight ratio for 3.5:2.5:1.2；The step (3)
In, the initiator is the mixture that forms of 3.5:1 with weight ratio by ammonium persulfate and potassium peroxydisulfate.
In the step (1), the power of ultrasonic agitation is 200W, and the time of ultrasonic agitation is 35min；The step (2)
In, the temperature of mixing is 0 DEG C；In the step (3), it is added before initiator into mixture B first by the temperature of initiator
Control is 0 DEG C, and the temperature of mixing is 0 DEG C.
A kind of preparation method of electromagnetic shielding material as described above, includes the following steps:
Polyvinyl chloride resin, electromagnetic shielding material, coupling agent, compatilizer and acrylate fiber are carried out first according to parts by weight
Then secondary mixing adds remaining raw material, carry out second and be mixed, obtain mixture；Mixture investment is squeezed
Equipment is kneaded, is squeezed out, is granulated out, and electromagnetic shielding material is made.
The speed of agitator that the first time is mixed is 1100r/min, second of speed of agitator being mixed
For 1250r/min；One area's temperature of the extrusion equipment be 275 DEG C, two area's temperature be 285 DEG C, three area's temperature be 300 DEG C, four
Area's temperature is 310 DEG C, and five area's temperature are 297 DEG C.
A kind of cable protection pipe, the cable protection pipe are made by above-mentioned electromagnetic shielding material, the cable protection pipe
Electromagnet shield effect be 21.23-43.87dB；The cable protection pipe is made by following steps: electromagnetic shielding material is heated
It is melted to 310 DEG C, is then added and is formed into molding die, obtain cable protection pipe after cooling.
Embodiment 4
A kind of electromagnetic shielding material, the raw material including following parts by weight:
The electromagnetic shielding material is polyaniline-graphene oxide composite material.
The fire retardant is decabromodiphenylethane or 2,4,6- tribromo phenyl allyl ethers；The synergistic flame retardant is silicon
Sour magnesium.
The impact modifier is ethylene-vinyl acetate copolymer.
The coupling agent is pyrophosphate titanate esters；The compatilizer is that one acrylonitrile copolymer of styrene is grafted methyl-prop
Olefin(e) acid ethylene oxidic ester.
Polyaniline-the graphene oxide composite material is made by following steps:
Step (1): taking 2.5 parts of mass fractions is that 4% graphene oxide water solution is added into 53 parts of deionized waters, so
58 parts of stabilizers are added afterwards, mixture A is made after being stirred by ultrasonic；
Step (2): it takes 2.5 parts of Bronsted acids and 4 parts of aniline monomers to be uniformly mixed, is then added to made from step (1) and mixes
It closes in material A, 3.8h is mixed, mixture B is made；
Step (3): taking 12-15 parts of initiators to be added into mixture B made from step (2), and 65min, system is mixed
Obtain mixture C；
Step (4): mixture C made from step (3) being centrifuged, dried, is pulverized, and polyaniline-oxidation is made
Graphene composite material.
In the step (1), the stabilizer is polyvinylpyrrolidone；In the step (2), the Bronsted acid is
The mixture being made of sulfosalicylic acid, p-methyl benzenesulfonic acid and perchloric acid with weight ratio for 3.8:2.2:1.3；The step (3)
In, the initiator is the mixture that forms of 3.8:1 with weight ratio by ammonium persulfate and potassium peroxydisulfate.
In the step (1), the power of ultrasonic agitation is 230W, and the time of ultrasonic agitation is 32min；The step (2)
In, the temperature of mixing is 2 DEG C；In the step (3), it is added before initiator into mixture B first by the temperature of initiator
Control is 2 DEG C, and the temperature of mixing is 2 DEG C.
A kind of preparation method of electromagnetic shielding material as described above, includes the following steps:
Polyvinyl chloride resin, electromagnetic shielding material, coupling agent, compatilizer and acrylate fiber are carried out first according to parts by weight
Then secondary mixing adds remaining raw material, carry out second and be mixed, obtain mixture；Mixture investment is squeezed
Equipment is kneaded, is squeezed out, is granulated out, and electromagnetic shielding material is made.
The speed of agitator that the first time is mixed is 1100r/min, second of speed of agitator being mixed
For 1280r/min；One area's temperature of the extrusion equipment be 278 DEG C, two area's temperature be 288 DEG C, three area's temperature be 303 DEG C, four
Area's temperature is 313 DEG C, and five area's temperature are 301 DEG C.
A kind of cable protection pipe, the cable protection pipe are made by above-mentioned electromagnetic shielding material, the cable protection pipe
Electromagnet shield effect be 21.23-43.87dB；The cable protection pipe is made by following steps: electromagnetic shielding material is heated
It is melted to 315 DEG C, is then added and is formed into molding die, obtain cable protection pipe after cooling.
Embodiment 5
A kind of electromagnetic shielding material, the raw material including following parts by weight:
The electromagnetic shielding material is polyaniline-graphene oxide composite material.
The fire retardant is bis- (tetrabromo phthalimide) ethane of 1,2-；The synergistic flame retardant is zinc borate.
The impact modifier is acrylonitrile-butadiene-styrene copolymer.
The coupling agent is vinyl three ('beta '-methoxy ethyoxyl) silane；The compatilizer is total for one acrylonitrile of styrene
Polymers graft glycidyl methacrylate.
Polyaniline-the graphene oxide composite material is made by following steps:
Step (1): taking 3 parts of mass fractions is that 2% graphene oxide water solution is added into 55 parts of deionized waters, then
60 parts of stabilizers are added, mixture A is made after being stirred by ultrasonic；
Step (2): taking 3 parts of Bronsted acids and 5 parts of aniline monomers to be uniformly mixed, and is then added to step (1) mixing obtained
Expect in A, 4h is mixed, mixture B is made；
Step (3): taking 12-15 parts of initiators to be added into mixture B made from step (2), and 70min, system is mixed
Obtain mixture C；
Step (4): mixture C made from step (3) being centrifuged, dried, is pulverized, and polyaniline-oxidation is made
Graphene composite material.
In the step (1), the stabilizer is polyvinylpyrrolidone；In the step (2), the Bronsted acid is
The mixture being made of sulfosalicylic acid, p-methyl benzenesulfonic acid and perchloric acid with weight ratio for 4:2:1.5；In the step (3), institute
State the mixture that initiator is made of ammonium persulfate and potassium peroxydisulfate with weight ratio for 4:1.
In the step (1), the power of ultrasonic agitation is 250W, and the time of ultrasonic agitation is 30min；The step (2)
In, the temperature of mixing is 4 DEG C；In the step (3), it is added before initiator into mixture B first by the temperature of initiator
Control is 4 DEG C, and the temperature of mixing is 4 DEG C.
A kind of preparation method of electromagnetic shielding material as described above, includes the following steps:
Polyvinyl chloride resin, electromagnetic shielding material, coupling agent, compatilizer and acrylate fiber are carried out first according to parts by weight
Then secondary mixing adds remaining raw material, carry out second and be mixed, obtain mixture；Mixture investment is squeezed
Equipment is kneaded, is squeezed out, is granulated out, and electromagnetic shielding material is made.
The speed of agitator that the first time is mixed is 1200r/min, second of speed of agitator being mixed
For 1300r/min；One area's temperature of the extrusion equipment be 280 DEG C, two area's temperature be 290 DEG C, three area's temperature be 305 DEG C, four
Area's temperature is 315 DEG C, and five area's temperature are 305 DEG C.
A kind of cable protection pipe, the cable protection pipe are made by above-mentioned electromagnetic shielding material, the cable protection pipe
Electromagnet shield effect be 21.23-43.87dB；The cable protection pipe is made by following steps: electromagnetic shielding material is heated
It is melted to 320 DEG C, is then added and is formed into molding die, obtain cable protection pipe after cooling.
Embodiment 6
The difference of the present embodiment and above-described embodiment 3 is:
Polyaniline-the graphene oxide composite material is made by following steps:
Step (1): taking 2 parts of mass fractions is that 6% graphene oxide water solution is added into 50 parts of deionized waters, then
55 parts of stabilizers are added, mixture A is made after being stirred by ultrasonic；
Step (2): taking 3 parts of aniline monomers to be added into mixture A made from step (1), and 3.5h is mixed, and is made
Mixture B；
Step (3): taking 13 parts of initiators to be added into mixture B made from step (2), and 60min is mixed, and is made mixed
Close material C；
Step (4): mixture C made from step (3) being centrifuged, dried, is pulverized, and polyaniline-oxidation is made
Graphene composite material.
In the step (1), the stabilizer is polyvinylpyrrolidone；In the step (3), the initiator is
The mixture being made of ammonium persulfate and potassium peroxydisulfate with weight ratio for 3.5:1.
In the step (1), the power of ultrasonic agitation is 200W, and the time of ultrasonic agitation is 35min；The step (2)
In, the temperature of mixing is 0 DEG C；In the step (3), it is added before initiator into mixture B first by the temperature of initiator
Control is 0 DEG C, and the temperature of mixing is 0 DEG C.
Embodiment 7
The difference of the present embodiment and above-described embodiment 1 is:
The fire retardant is by deca-BDE, decabromodiphenylethane and 2, and 4,6- tribromo phenyl allyl ethers are with weight
Than the mixture formed for 2.5:1.5:1.
The synergistic flame retardant is made of antimony oxide, zinc oxide and zinc borate with weight ratio for 2:1:1.2 mixed
Close object.
The impact modifier is by Methyl Methacrylate-Butadiene-Styrene Copolymer, haloflex and propylene
Nitrile-butadiene-styrene copolymer is with the mixture that weight ratio is that 3.5:1:3 is formed.
The coupling agent be by vinyltriethoxysilane, γ-methacryloxypropyl trimethoxy silane and
('beta '-methoxy ethyoxyl) silane of vinyl three is with the mixture that weight ratio is that 1.5:1:3.2 is formed.
The compatilizer is by hydrogenated styrene-butadiene-styrene copolymer grafted glycidyl methacrylate
The mixture formed with one acrylonitrile copolymer graft glycidyl methacrylate of styrene with weight ratio for 2:1.
Embodiment 8
The difference of the present embodiment and above-described embodiment 2 is:
The fire retardant is by deca-BDE, decabromodiphenylethane and 2, and 4,6- tribromo phenyl allyl ethers are with weight
Than the mixture formed for 2.8:1.6:1.
The synergistic flame retardant is what 2.2:1:1.4 was formed with weight ratio by antimony oxide, zinc oxide and zinc borate
Mixture.
The impact modifier is by Methyl Methacrylate-Butadiene-Styrene Copolymer, haloflex and propylene
Nitrile-butadiene-styrene copolymer is with the mixture that weight ratio is that 3.6:1:2.8 is formed.
The coupling agent be by vinyltriethoxysilane, γ-methacryloxypropyl trimethoxy silane and
('beta '-methoxy ethyoxyl) silane of vinyl three is with the mixture that weight ratio is that 1.6:1:3 is formed.
The compatilizer is by hydrogenated styrene-butadiene-styrene copolymer grafted glycidyl methacrylate
The mixture formed with one acrylonitrile copolymer graft glycidyl methacrylate of styrene with weight ratio for 2.2:1.
Embodiment 9
The difference of the present embodiment and above-described embodiment 3 is:
The fire retardant is by deca-BDE, decabromodiphenylethane and 2, and 4,6- tribromo phenyl allyl ethers are with weight
Than the mixture formed for 3:1.7:1.
The synergistic flame retardant is what 2.5:1:1.5 was formed with weight ratio by antimony oxide, zinc oxide and zinc borate
Mixture.
The impact modifier is by Methyl Methacrylate-Butadiene-Styrene Copolymer, haloflex and propylene
Nitrile-butadiene-styrene copolymer is with the mixture that weight ratio is that 3.7:1:2.5 is formed.
The coupling agent be by vinyltriethoxysilane, γ-methacryloxypropyl trimethoxy silane and
('beta '-methoxy ethyoxyl) silane of vinyl three is with the mixture that weight ratio is that 1.7:1:2.8 is formed.
The compatilizer is by hydrogenated styrene-butadiene-styrene copolymer grafted glycidyl methacrylate
The mixture formed with one acrylonitrile copolymer graft glycidyl methacrylate of styrene with weight ratio for 2.5:1.
Embodiment 10
The difference of the present embodiment and above-described embodiment 4 is:
The fire retardant is by deca-BDE, decabromodiphenylethane and 2, and 4,6- tribromo phenyl allyl ethers are with weight
Than the mixture formed for 3.2:1.8:1.
The synergistic flame retardant is what 2.8:1:1.6 was formed with weight ratio by antimony oxide, zinc oxide and zinc borate
Mixture.
The impact modifier is by Methyl Methacrylate-Butadiene-Styrene Copolymer, haloflex and propylene
Nitrile-butadiene-styrene copolymer is with the mixture that weight ratio is that 3.8:1:2.2 is formed.
The coupling agent be by vinyltriethoxysilane, γ-methacryloxypropyl trimethoxy silane and
('beta '-methoxy ethyoxyl) silane of vinyl three is with the mixture that weight ratio is that 1.8:1:2.6 is formed.
The compatilizer is by hydrogenated styrene-butadiene-styrene copolymer grafted glycidyl methacrylate
The mixture formed with one acrylonitrile copolymer graft glycidyl methacrylate of styrene with weight ratio for 2.8:1.
Embodiment 11
The difference of the present embodiment and above-described embodiment 5 is:
The fire retardant is by deca-BDE, decabromodiphenylethane and 2, and 4,6- tribromo phenyl allyl ethers are with weight
Than the mixture formed for 3.5:2:1.
The synergistic flame retardant is made of antimony oxide, zinc oxide and zinc borate with weight ratio for 3:1:1.8 mixed
Close object.
The impact modifier is by Methyl Methacrylate-Butadiene-Styrene Copolymer, haloflex and propylene
Nitrile-butadiene-styrene copolymer is with the mixture that weight ratio is that 4:1:2 is formed.
The coupling agent be by vinyltriethoxysilane, γ-methacryloxypropyl trimethoxy silane and
('beta '-methoxy ethyoxyl) silane of vinyl three is with the mixture that weight ratio is that 2:1:2.4 is formed.
The compatilizer is by hydrogenated styrene-butadiene-styrene copolymer grafted glycidyl methacrylate
The mixture formed with one acrylonitrile copolymer graft glycidyl methacrylate of styrene with weight ratio for 3:1.
Comparative example 1
A kind of PVC material, the raw material including following parts by weight:
The fire retardant is deca-BDE；The synergistic flame retardant is antimony oxide.
The impact modifier is styrene-butadiene-styrene.
The coupling agent is γ-methacryloxypropyl trimethoxy silane or methyltriethoxysilane；It is described
Compatilizer is hydrogenated styrene-butadiene-styrene copolymer grafted glycidyl methacrylate.
A kind of preparation method of PVC material as described above, includes the following steps:
Polyvinyl chloride resin, coupling agent, compatilizer and acrylate fiber are subjected to first time mixing according to parts by weight, so
After add remaining raw material, carry out second and be mixed, obtain mixture；Mixture investment extrusion equipment is mixed
Refining is squeezed out, is granulated, and PVC material is made.
The speed of agitator that the first time is mixed is 1100r/min, second of speed of agitator being mixed
For 1250r/min；One area's temperature of the extrusion equipment be 275 DEG C, two area's temperature be 285 DEG C, three area's temperature be 300 DEG C, four
Area's temperature is 310 DEG C, and five area's temperature are 297 DEG C.
A kind of cable protection pipe, the cable protection pipe are made by above-mentioned PVC material, and the cable protection pipe by walking as follows
It is rapid to be made: PVC material being heated to 310 DEG C and is melted, is then added and is formed into molding die, cable guarantor is obtained after cooling
Pillar.
Comparative example 2
A kind of electromagnetic shielding material, the raw material including following parts by weight:
The electromagnetic shielding material is polyaniline.
The fire retardant is deca-BDE；The synergistic flame retardant is antimony oxide.
The impact modifier is styrene-butadiene-styrene.
The coupling agent is γ-methacryloxypropyl trimethoxy silane or methyltriethoxysilane；It is described
Compatilizer is hydrogenated styrene-butadiene-styrene copolymer grafted glycidyl methacrylate.
A kind of preparation method of electromagnetic shielding material as described above, includes the following steps:
Polyvinyl chloride resin, electromagnetic shielding material, coupling agent, compatilizer and acrylate fiber are carried out first according to parts by weight
Then secondary mixing adds remaining raw material, carry out second and be mixed, obtain mixture；Mixture investment is squeezed
Equipment is kneaded, is squeezed out, is granulated out, and electromagnetic shielding material is made.
The speed of agitator that the first time is mixed is 1100r/min, second of speed of agitator being mixed
For 1250r/min；One area's temperature of the extrusion equipment be 275 DEG C, two area's temperature be 285 DEG C, three area's temperature be 300 DEG C, four
Area's temperature is 310 DEG C, and five area's temperature are 297 DEG C.
A kind of cable protection pipe, the cable protection pipe are made by above-mentioned electromagnetic shielding material, the cable protection pipe
It is made by following steps: electromagnetic shielding material being heated to 310 DEG C and is melted, is then added and is formed into molding die, it is cold
But cable protection pipe is obtained afterwards.
Comparative example 3
A kind of electromagnetic shielding material, the raw material including following parts by weight:
The electromagnetic shielding material is graphene oxide composite material.
The fire retardant is deca-BDE；The synergistic flame retardant is antimony oxide.
The impact modifier is styrene-butadiene-styrene.
The coupling agent is γ-methacryloxypropyl trimethoxy silane or methyltriethoxysilane；It is described
Compatilizer is hydrogenated styrene-butadiene-styrene copolymer grafted glycidyl methacrylate.
A kind of preparation method of electromagnetic shielding material as described above, includes the following steps:
Polyvinyl chloride resin, electromagnetic shielding material, coupling agent, compatilizer and acrylate fiber are carried out first according to parts by weight
Then secondary mixing adds remaining raw material, carry out second and be mixed, obtain mixture；Mixture investment is squeezed
Equipment is kneaded, is squeezed out, is granulated out, and electromagnetic shielding material is made.
The speed of agitator that the first time is mixed is 1100r/min, second of speed of agitator being mixed
For 1250r/min；One area's temperature of the extrusion equipment be 275 DEG C, two area's temperature be 285 DEG C, three area's temperature be 300 DEG C, four
Area's temperature is 310 DEG C, and five area's temperature are 297 DEG C.
A kind of cable protection pipe, the cable protection pipe are made by above-mentioned electromagnetic shielding material, the cable protection pipe
It is made by following steps: electromagnetic shielding material being heated to 310 DEG C and is melted, is then added and is formed into molding die, it is cold
But cable protection pipe is obtained afterwards.
Cable protection pipe made from above-described embodiment 1-11 and comparative example 1-3 is subjected to electromagnet shield effect, fire prevention respectively
The performance tests such as performance, impact strength, tensile strength, it is shown that test result is as follows:
By upper table data it is found that cable protection pipe electromagnet shield effect produced by the present invention is good, up to 21.23-
The electromagnetic wave that cable generates can be reflected and be absorbed, electromagnetic wave is avoided to interfere or influence electronic device by 43.87dB
Human health, while there are the comprehensive performances such as preferable anti-flammability, impact resistance, tensile strength, hardness, heat resistance；With comparison
Example 1 is compared, and the present invention can improve the electromagnetic shielding action of cable protection pipe using electromagnetic shielding material significantly, is avoided that cable
The electromagnetic wave of generation interferes other electronic devices or unhealthful；And compared with comparative example 2-3, the present invention by using
Conductivity is polyaniline-graphene oxide composite material of 1.168-2.018S/cm as electromagnetic shielding material, utilizes polyphenyl
The high conductivity of amine reflects electromagnetic wave, absorbs in conjunction with the high microwave absorbing property of graphene oxide to electromagnetic wave,
The two combine, the polyaniline-coated with reflection electromagnetic wave performance the graphene oxide with performance of absorbing electromagnetic wave, make answer
Condensation material first with cladding polyaniline carry out reflection of electromagnetic wave, recycle graphene oxide to not fully reflective electromagnetic wave into
Row absorbs, and so that cable protection pipe obtained is had excellent electromagnet shield effect, effectiveness is than homogenous material (polyphenyl
Amine or polyaniline) more preferably, illustrate the present invention using polyaniline-graphene oxide composite material can effectively shielded cable generate
Electromagnetic wave.
Above-described embodiment is the preferable implementation of the present invention, and in addition to this, the present invention can be realized with other way,
Do not depart under the premise of present inventive concept it is any obviously replace it is within the scope of the present invention.
Claims (10)
1. a kind of electromagnetic shielding material, it is characterised in that: the raw material including following parts by weight:
The electromagnetic shielding material is polyaniline-graphene oxide composite material.
2. a kind of electromagnetic shielding material according to claim 1, it is characterised in that: the fire retardant be deca-BDE,
Tetrabromobisphenol A, decabromodiphenylethane, 2,4,6- tribromphenols, 2,4,6- tribromo phenyl allyl ethers, tetrabromophthalate
At least one of bis- (tetrabromo phthalimide) ethane of acid anhydride, 1,2-；The synergistic flame retardant is antimony oxide, oxidation
At least one of zinc, zinc stearate, magnesium silicate and zinc borate.
3. a kind of electromagnetic shielding material according to claim 1, it is characterised in that: the impact modifier is methacrylic acid
Methyl esters-butadiene-styrene copolymer, haloflex, styrene-butadiene-styrene, ethene-vinyl acetate
At least one of copolymer and acrylonitrile-butadiene-styrene copolymer.
4. a kind of electromagnetic shielding material according to claim 1, it is characterised in that: the coupling agent is three ethoxy of vinyl
Base silane, anilinomethyl triethoxysilane, γ-methacryloxypropyl trimethoxy silane, methyltriethoxy silane
At least one of alkane, pyrophosphate titanate esters and vinyl three ('beta '-methoxy ethyoxyl) silane；The compatilizer is hydrogenation
Styrene-butadiene-styrene graft glycidyl methacrylate, ethylene-acrylic acid-methyl esters are grafted methyl-prop
At least one of one acrylonitrile copolymer graft glycidyl methacrylate of olefin(e) acid ethylene oxidic ester and styrene.
5. a kind of electromagnetic shielding material according to claim 1, it is characterised in that: the polyaniline-graphene oxide is multiple
Condensation material is made by following steps:
Step (1): taking 1-3 parts of mass fractions is that the graphene oxide water solution of 2-10% is added into 45-55 parts of deionized waters,
Then 50-60 parts of stabilizers are added, mixture A is made after being stirred by ultrasonic；
Step (2): taking 1-3 parts of Bronsted acids and 2-5 parts of aniline monomers to be uniformly mixed, and is then added to step (1) mixing obtained
Expect in A, 3-4h is mixed, mixture B is made；
Step (3): taking 12-15 parts of initiators to be added into mixture B made from step (2), and 50-70min is mixed, and is made
Mixture C；
Step (4): mixture C made from step (3) being centrifuged, dried, is pulverized, and polyaniline-graphite oxide is made
Alkene composite material.
6. a kind of electromagnetic shielding material according to claim 5, it is characterised in that: in the step (1), the stabilizer
For polyvinylpyrrolidone；In the step (2), the Bronsted acid is by sulfosalicylic acid, p-methyl benzenesulfonic acid and perchloric acid
It is the mixture that 3-4:2-3:1-1.5 is formed with weight ratio；In the step (3), the initiator is by ammonium persulfate and mistake
Potassium sulfate is with the mixture that weight ratio is that 3-4:1 is formed.
7. a kind of electromagnetic shielding material according to claim 5, it is characterised in that: in the step (1), ultrasonic agitation
Power is 150-250W, and the time of ultrasonic agitation is 30-40min；In the step (2), the temperature of mixing is -5 DEG C~4
℃；In the step (3), being added before initiator into mixture B first is -5 DEG C~4 DEG C by the temperature control of initiator, mixing
The temperature of stirring is -5 DEG C~4 DEG C.
8. a kind of preparation method of such as described in any item electromagnetic shielding materials of claim 1-7, it is characterised in that: including as follows
Step:
Polyvinyl chloride resin, electromagnetic shielding material, coupling agent, compatilizer and acrylate fiber mix for the first time according to parts by weight
Stirring is closed, remaining raw material is then added, second is carried out and is mixed, obtain mixture；Mixture investment is squeezed out and is set
It is standby to be kneaded, squeezed out, is granulated, electromagnetic shielding material is made.
9. the preparation method of electromagnetic shielding material according to claim 8, it is characterised in that: the first time is mixed
Speed of agitator be 900-1200r/min, described second speed of agitator being mixed is 1200-1300r/min；It is described to squeeze
Area's temperature of equipment is 270-280 DEG C out, and two area's temperature are 280-290 DEG C, and three area's temperature are 295-305 DEG C, four area's temperature
It is 305-315 DEG C, five area's temperature are 290-305 DEG C.
10. a kind of cable protection pipe, it is characterised in that: the cable protection pipe is by the described in any item electromagnetism of claim 1-7
Shielding material is made, and the electromagnet shield effect of the cable protection pipe is 21.23-43.87dB；The cable protection pipe is by as follows
Step is made: electromagnetic shielding material is heated to 300-320 DEG C and is melted, is then added and is formed into molding die, it is cooling
After obtain cable protection pipe.
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Application publication date: 20181218 |