CN109021450A - A kind of shock resistance high heat resistance material and preparation method thereof and cable protection pipe obtained - Google Patents

A kind of shock resistance high heat resistance material and preparation method thereof and cable protection pipe obtained Download PDF

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CN109021450A
CN109021450A CN201810806126.6A CN201810806126A CN109021450A CN 109021450 A CN109021450 A CN 109021450A CN 201810806126 A CN201810806126 A CN 201810806126A CN 109021450 A CN109021450 A CN 109021450A
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mixture
parts
temperature
shock resistance
high heat
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袁睿
陈文革
张毅力
张绍梅
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Guangdong Anpu Zhixin Electric Co Ltd
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Guangdong Anpu Zhixin Electric Co Ltd
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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
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/387—Borates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/18—Applications used for pipes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

The present invention relates to cable protection pipe material technical fields; more particularly to a kind of shock resistance high heat resistance material and preparation method thereof and cable protection pipe obtained, which includes the raw material of following parts by weight: 75-100 parts of polyvinyl chloride resin, 12-15 parts of TPE resin, 20-25 parts of PP resin, 12-18 parts of electromagnetic shielding material, 10-15 parts of anti-impact modifier, 6-10 parts of heat-resistant filler, 15-20 parts of fire retardant, 12-18 parts of coupling agent and 5-15 parts of compatilizer.Composite material of the invention has excellent high-fire resistance and shock resistance, impact strength 19.81KJ/m2‑23.75KJ/m2, heat distortion temperature is 98-113 DEG C, electromagnet shield effect 19.78-38.16dB；And by the way that electromagnetic wave is reflected and absorbed using electromagnetic shielding material, reach preferable effectiveness, mechanical mechanics property is excellent.

Description

A kind of shock resistance high heat resistance material and preparation method thereof and cable protection pipe obtained
Technical field
The present invention relates to cable protection pipe material technical fields, and in particular to a kind of shock resistance high heat resistance material and its preparation Method and 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.Simultaneously as the application environment of cable protection pipe is severe, performance need to be carried out to cable material and changed Property, the service life of cable protection pipe is improved, avoids being damaged due to cable protection pipe and causes internal wire leakage or electric wire Broken string occurs leaking electricity or short circuit accident.
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 shock resistance height is resistance to Hot material, the material have excellent high-fire resistance and shock resistance, and by utilizing polyaniline-graphene oxide composite wood Material is reflected and is absorbed to electromagnetic wave, reaches preferable effectiveness, mechanical mechanics property is excellent.
Another object of the present invention is to provide a kind of preparation method of shock resistance high heat resistance material, preparation method operations Step is simple, easy to control, and high production efficiency, production cost is low, and composite material quality obtained is stablized, and is applicable to extensive Production.
A further object of the present invention is to provide cable protection pipes made from a kind of application shock resistance high heat resistance material, should Cable protection pipe has excellent high-fire resistance and shock resistance, and electromagnetic shielding performance is good, the electromagnetism that can generate cable Wave is reflected and is absorbed, and avoids electromagnetic wave that human health is interfered or influenced on electronic device, have preferable anti-flammability, The comprehensive performances such as tensile strength and hardness, mechanical mechanics property are excellent.
The purpose of the invention is achieved by the following technical solution: a kind of shock resistance high heat resistance material, including following parts by weight Raw material:
The anti-impact modifier is with weight ratio by silica filler and acrylic acid esters co-polymer for 1-2:3-5 group At mixture；
The heat-resistant filler is made of calcium carbonate, lignocellulosic and magnesium silicide with weight ratio for 3-8:2-6:1.5-2 Mixture.
The present invention prepares composite material by using above-mentioned raw materials, and PVC-TPE-PP composite material can be made to have excellent resist The TPE resin of impact property, weatherability and flame retardant property, good mechanical performance, use is environment-protecting and non-poisonous, with excellent weather-proof Property, resistance to ag(e)ing and fatigue resistance, there is the molding plastics performance of plasticization at normal temperature with the elasticity of rubber, under high temperature, The dual property for having both rubber and plastics, acting on PVC can have and can be modified to polyvinyl chloride resin, improve the weather-proof of polyvinyl chloride resin Property, impact resistance and processing forming；The PP Resin crystallization degree of use is high, and compound with regular structure, toughness is high, heat-resist, and chemistry is steady Qualitative height, reactance voltage excellent performance, it can be modified by acting on polyvinyl chloride resin, improve the weatherability of polyvinyl chloride resin, toughness, heat-resisting Property and stability, the effect of three's resin phase-polymerization, can make composite material obtained that there is excellent weatherability, impact resistance, anti- The comprehensive performances such as voltage endurance, processing forming.
And polyaniline-the graphene oxide composite material used can play electricity using electromagnetic wave absorption and reflection electromagnetic wave The effect of magnetic screen improves the anti-electromagnetic wave performance of composite material, wherein graphene oxide has excellent physical property, inhales Good and at low cost, good with the electric conductivity polyaniline phase-polymerization of Electromagnetic performance is received, can make composite material that there is preferably shielding Conductivity can reflect electromagnetic wave, play excellent shielding action；And composite wood can be effectively improved by using fire retardant The flame retardant effect and smoke suppressing effect of material, the compatilizer of use can effectively facilitate polyvinyl chloride resin, TPE resin and three kinds of PP resin polymerizations Object is incorporated in one, and then obtains stable blend system；The coupling agent of use can be effectively facilitated resinous polymer and resist The crosslinking of the auxiliary agents such as impact modifying agent, heat-resistant filler, fire retardant is coupled, and improves the comprehensive performance of resinous polymer, and is formed steady Fixed blend system；By using calcium carbonate, lignocellulosic and magnesium silicide as heat-resistant filler, and strict control three Mixed proportion can effectively improve heat resistance, the processing flowability of composite material, reduce surface gloss.
Preferably, the silica filler is SiO2At least two in glass powder, glass flake and glass fibre.
The present invention is by by SiO2Glass powder, glass flake, at least two mixing in glass fibre are added to system In, the bending property of composite material can also be improved while enhancing composite material shock resistance, be that composite material has height Impact resistance and good toughness；Wherein, the glass flake of use is in the palace formula structure of parallel overlapping arrangement in resin, is formed Fine and close structure, can significantly improve the shock resistance of composite material.More preferably, the SiO2Glass powder is using upper The RQ-B P series glass powder of Hai Renqian Chemical Industry Science Co., Ltd.
Preferably, the electromagnetic shielding material is polyaniline-graphene oxide composite material；The fire retardant is ten bromines two Phenylate, decabromodiphenylethane, 2, in 4,6- tribromo phenyl allyl ethers, antimony oxide, zinc oxide and zinc borate at least It is a kind of.
The present invention by using polyaniline-graphene oxide composite material can using electromagnetic wave absorption and reflection electromagnetic wave and Play the role of electromagnetic shielding, improves composite material and shield electromagnetic wave, graphene oxide therein has excellent object Rationality energy, performance of absorbing electromagnetic wave is good, and at low cost, and the polyaniline phase-polymerization good with electric conductivity can be such that composite material has Preferably shielding conductivity, can reflect electromagnetic wave, improve the electromagnetic shielding action of composite material.
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 composite material can be improved, the performance of composite material is influenced smaller；Wherein, deca-BDE thermostabilization Property it is good, flame-retarded efficiency is high, and when being used in combination with antimony oxide, the apparent synergistic effect of phase mutual makes composite wood obtained Material has higher flame-retarded efficiency, and thermal stability is more preferable；Antimony oxide, zinc oxide and zinc borate therein play fire-retardant synergistic Effect, free radical can be captured in the gas phase, and play synergistic effect in condensed phase, in PVC-TPE-PP composite material surface shape Preferable fire-retardant, fireproofing function is played at strong layer of charcoal, and then to composite material, and plays smoke suppressing effect, improves composite wood The color of material；The antimony oxide additive amount of use is few, and can effectively improve composite wood completely with the mutual synergistic effect of fire retardant The anti-flammability of material, the zinc oxide of use can promote into charcoal and react, and reduce the dosage of fire retardant, improve thermal stability, reduce raw cigarette Amount；The zinc borate of use is nontoxic, and thermal stability is high, and good dispersion can effectively improve the flame retardant property of composite material, and energy It reduces smog when burning to generate, and the mechanical performance of adjustable composite material.More preferably, the fire retardant is by ten bromines Diphenyl ether, 2,4,6- tribromo phenyl allyl ethers and zinc borate are with the mixture that weight ratio is that 2-3:1.2-1.8:1 is formed.
Preferably, the coupling agent is methyltriethoxysilane, pyrophosphate titanate esters, vinyl triethoxyl silicon At least one of alkane, anilinomethyl triethoxysilane and vinyl three ('beta '-methoxy ethyoxyl) silane；The compatilizer For hydrogenated styrene-butadiene-styrene copolymer grafted glycidyl methacrylate, ethylene-acrylic acid-methyl esters grafting At least one in one acrylonitrile copolymer graft glycidyl methacrylate of glycidyl methacrylate and styrene Kind.
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, TPE resin, PP resin and fire retardant, impact modifier, heat-resistant filler, Interface performance between coupling agent, compatilizer improves dispersibility, stickiness, compatibility and the processing performance of raw material, makes obtained multiple Condensation material has the comprehensive performances such as preferable dispersibility, cohesive force, anti-aging property, intensity；Wherein, three second of vinyl of use Oxysilane can effectively improve the affinity between each raw material, the intensity of Reinforced PVC-TPE-PP composite material；The methyl of use Triethoxysilane can effectively improve the performances such as erosion-resisting characteristics, rheological characteristic, processability and the stability of composite material.It is more highly preferred to , the coupling agent is by methyltriethoxysilane, pyrophosphate titanate esters and anilinomethyl triethoxysilane with weight Than the mixture formed for 1-2:1:2-3.
The present invention can match effect, concerted reaction by using the compatilizer of mentioned kind with other raw materials, effectively drop Interfacial tension between low PVC resin, TPE resin, PP molecular resin, and then interface cohesive force is improved, make dispersed phase and continuous phase Uniformly, stable structure is formed, promotes resinous polymer to react with the mutual cooperation of other raw materials, improves the stretching of composite material The mechanical performances such as intensity, impact strength improve rheological performance, improve surface smoothness.More preferably, the compatilizer It is by hydrogenated styrene-butadiene-styrene copolymer grafted glycidyl methacrylate and ethylene-acrylic acid-methyl esters Graft glycidyl methacrylate is with the mixture that weight ratio is that 2.4-3.2:1 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, aniline monomer polymerization can be made to generate polyaniline, simultaneous oxidation graphene and monomer occur former Position polymerization reaction, can make graphene oxide disperse in polymerization system relatively uniform, 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 is made obtained compound with excellent electromagnetic shielding action；And pass through strict control oxygen The dosage of graphite alkene and polyaniline, energy composite material has preferable stability and electromagnetic shielding performance, if graphene oxide Dosage be much larger than the dosage of aniline monomer, be easy to reduce compound so that partial oxidation of graphite is not coated by polyaniline The stability of material, and the performance of composite material reflection electromagnetic wave is reduced, compound electromagnetic wave shielding stabilizability is reduced, is dropped Low compound electromagnetic shielding action；If the dosage of graphene oxide is much smaller than the dosage of aniline monomer, composite wood is reduced The performance for expecting electromagnetic wave absorption, reduces the electromagnetic shielding action of composite 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 composite material have preferable conductivity, can electromagnetic wave be reflected and be played the work of electromagnetic shielding With.
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 the absorption electromagnetism of graphene oxide in the composite can be improved Wave 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 composite material；If the dosage of Bronsted acid is excessive, makes the conductivity of composite material excessive, drop instead The low effectiveness of composite 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；Institute It states in step (3), the mixture that the initiator is made of ammonium persulfate and potassium peroxydisulfate with weight ratio for 3-4:1.
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 the electromagnetic wave absorption stability of graphene oxide in the composite can be improved.
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 and draws into mixture B First controlling the temperature of initiator before hair agent 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 the suction of graphene oxide in the composite can be improved Receive electromagnetic wave stability；
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 system of such as above-mentioned shock resistance high heat resistance material Preparation Method includes the following steps:
Step A: in parts by weight, by polyvinyl chloride resin, TPE resin, PP resin, heat-resistant filler, coupling agent and compatilizer into Row is mixed for the first time, then adds remaining raw material, carries out second and is mixed, mixture is made；
Step B: the investment extrusion equipment of mixture made from step A is kneaded, squeezed out, is granulated, it is high that shock resistance is made Heat proof material.
Preferably, the speed of agitator that the first time is mixed is 800-1000r/min, second of mixing Speed of agitator be 1500-1800r/min；One area's temperature of the extrusion equipment is 285-290 DEG C, and two area's temperature are 290- 300 DEG C, three area's temperature are 305-310 DEG C, and four area's temperature are 310-315 DEG C, and five area's temperature are 290-305 DEG C.
The present invention by using batch mixed mode, using compatilizer and coupling agent first by polyvinyl chloride resin, TPE resin, PP Resin is sufficiently mixed, and forms stable resin complexes, while point of three kinds of resins is improved using the powder structure of heat-resistant filler Property is dissipated, disperses subsequent mix with other raw materials more evenly, composite material obtained has stable, uniform comprehensive performance；Again Remaining electromagnetic shielding material, anti-impact modifier and fire retardant is added, is fully mixed in above-mentioned mixture, improves compound The shock resistance and anti-flammability of material, and preparation method operating procedure is simple, easy to control, high production efficiency, production cost Low, composite material quality obtained is stablized, and is applicable to be mass produced.
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 shock resistance high heat resistance material is made, and the impact strength of the cable protection pipe is 19.81KJ/m2-23.75KJ/m2, Heat distortion temperature is 98-113 DEG C, electromagnet shield effect 19.78-38.16dB.
Preferably, the cable protection pipe is made by following steps: shock resistance high heat resistance material is heated to 295-305 DEG C It is melted, is then added and is formed into molding die, obtain cable protection pipe after cooling.
The present invention can make cable protection pipe obtained by molding, cooling after melting shock resistance high heat resistance material With the comprehensive performances such as excellent impact resistance, weatherability, electromagnetic shielding performance, anti-flammability, tensile strength, hardness, shock resistance Intensity is up to 19.81KJ/m2-23.75KJ/m2, heat distortion temperature up to 98-113 DEG C, and can by cable generate electromagnetic wave into Row reflection and absorption, play the role of electromagnetic shielding, electromagnet shield effect is up to 19.78-38.16dB.
The beneficial effects of the present invention are: shock resistance high heat resistance material of the invention has excellent high-fire resistance and anti-impact Performance is hit, and electromagnetic wave is reflected and absorbed by using polyaniline-graphene oxide composite material, utilizes polyaniline High conductivity reflects electromagnetic wave, absorbs in conjunction with the high microwave absorbing property of graphene oxide to electromagnetic wave, the two In conjunction with the graphene oxide of, the polyaniline-coated with reflection electromagnetic wave performance with performance of absorbing electromagnetic wave, make composite wood Material carries out reflection of electromagnetic wave first with the polyaniline of cladding, graphene oxide is recycled to inhale not fully reflective electromagnetic wave It receives, makes composite material obtained that there is excellent effectiveness, mechanical mechanics property is excellent.
The preparation method operating procedure of shock resistance high heat resistance material of the present invention is simple, easy to control, high production efficiency, production At low cost, composite material quality obtained is stablized, and is applicable to be mass produced.
The present invention has excellent high-fire resistance and anti-impact using cable protection pipe made from the shock resistance high heat resistance material Performance is hit, impact strength is up to 19.81KJ/m2-23.75KJ/m2, heat distortion temperature is up to 98-113 DEG C, and electromagnetic wave shielding Can be good, the electromagnetic wave that cable generates can be reflected and be absorbed, avoid electricity up to 19.78-38.16dB by electromagnet shield effect Magnetic wave interferes on electronic device or influences human health, has preferable anti-flammability, tensile strength and hardness etc. comprehensive Can, mechanical mechanics property is excellent.
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 shock resistance high heat resistance material, the raw material including following parts by weight:
The anti-impact modifier is what 1:3 was formed with weight ratio by silica filler and acrylic acid esters co-polymer Mixture；
The mixing that the heat-resistant filler is made of calcium carbonate, lignocellulosic and magnesium silicide with weight ratio for 3:2:1.5 Object.
The silica filler is SiO2The mixture of glass powder and glass flake.
The electromagnetic shielding material is polyaniline-graphene oxide composite material；The fire retardant is 2,4,6- tribromo-benzenes The mixture of base allyl ether and zinc borate.
The coupling agent is vinyltriethoxysilane；The compatilizer is that ethylene-acrylic acid-methyl esters is grafted methyl-prop Olefin(e) acid ethylene oxidic ester.
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 such as above-mentioned shock resistance high heat resistance material, includes the following steps:
Step A: in parts by weight, by polyvinyl chloride resin, TPE resin, PP resin, heat-resistant filler, coupling agent and compatilizer into Row is mixed for the first time, then adds remaining raw material, carries out second and is mixed, mixture is made；
Step B: the investment extrusion equipment of mixture made from step A is kneaded, squeezed out, is granulated, it is high that shock resistance is made Heat proof material.
The speed of agitator that the first time is mixed is 800r/min, and the speed of agitator of second of mixing is 1500r/min；One area's temperature of the extrusion equipment is 285 DEG C, and two area's temperature are 290 DEG C, and three area's temperature are 305 DEG C, 4th area Temperature is 310 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 shock resistance high heat resistance material.
Embodiment 2
The difference of the present embodiment and above-described embodiment 1 is:
A kind of shock resistance high heat resistance material, the raw material including following parts by weight:
The anti-impact modifier is with weight ratio by silica filler and acrylic acid esters co-polymer for 1.2:3.5 group At mixture；
The mixing that the heat-resistant filler is made of calcium carbonate, lignocellulosic and magnesium silicide with weight ratio for 4:3:1.6 Object.
The silica filler is the mixture of glass flake and glass fibre.
The electromagnetic shielding material is polyaniline-graphene oxide composite material；The fire retardant is decabrominated dipheny base second The mixture of alkane and zinc oxide.
The coupling agent is anilinomethyl triethoxysilane；The compatilizer is hydrogenated styrene-butadiene-styrene Copolymer grafted glycidyl methacrylate.
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 such as above-mentioned shock resistance high heat resistance material, includes the following steps:
Step A: in parts by weight, by polyvinyl chloride resin, TPE resin, PP resin, heat-resistant filler, coupling agent and compatilizer into Row is mixed for the first time, then adds remaining raw material, carries out second and is mixed, mixture is made；
Step B: the investment extrusion equipment of mixture made from step A is kneaded, squeezed out, is granulated, it is high that shock resistance is made Heat proof material.
The speed of agitator that the first time is mixed is 850r/min, and the speed of agitator of second of mixing is 1600r/min；One area's temperature of the extrusion equipment is 286 DEG C, and two area's temperature are 292 DEG C, and three area's temperature are 306 DEG C, 4th area Temperature is 311 DEG C, and five area's temperature are 294 DEG C.
A kind of cable protection pipe, the cable protection pipe are made by above-mentioned shock resistance high heat resistance material.
Embodiment 3
The difference of the present embodiment and above-described embodiment 1 is:
A kind of shock resistance high heat resistance material, the raw material including following parts by weight:
The anti-impact modifier is made of silica filler and acrylic acid esters co-polymer with weight ratio for 1.5:4 Mixture；
The mixing that the heat-resistant filler is made of calcium carbonate, lignocellulosic and magnesium silicide with weight ratio for 5:4:1.7 Object.
The silica filler is SiO2The mixture of glass powder and glass flake.
The electromagnetic shielding material is polyaniline-graphene oxide composite material；The fire retardant be deca-BDE and The mixture of antimony oxide.
The coupling agent is methyltriethoxysilane；The compatilizer is that ethylene-acrylic acid-methyl esters is grafted metering system Acid glycidyl ester.
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 such as above-mentioned shock resistance high heat resistance material, includes the following steps:
Step A: in parts by weight, by polyvinyl chloride resin, TPE resin, PP resin, heat-resistant filler, coupling agent and compatilizer into Row is mixed for the first time, then adds remaining raw material, carries out second and is mixed, mixture is made；
Step B: the investment extrusion equipment of mixture made from step A is kneaded, squeezed out, is granulated, it is high that shock resistance is made Heat proof material.
The speed of agitator that the first time is mixed is 900r/min, and the speed of agitator of second of mixing is 1700r/min；One area's temperature of the extrusion equipment is 287 DEG C, and two area's temperature are 295 DEG C, and three area's temperature are 307 DEG C, 4th area Temperature is 312 DEG C, and five area's temperature are 298 DEG C.
A kind of cable protection pipe, the cable protection pipe are made by above-mentioned shock resistance high heat resistance material.
Embodiment 4
The difference of the present embodiment and above-described embodiment 1 is:
A kind of shock resistance high heat resistance material, the raw material including following parts by weight:
The anti-impact modifier is with weight ratio by silica filler and acrylic acid esters co-polymer for 1.8:4.5 group At mixture；
The mixing that the heat-resistant filler is made of calcium carbonate, lignocellulosic and magnesium silicide with weight ratio for 6:5:1.8 Object.
The silica filler is SiO2The mixture of glass powder and glass fibre.
The electromagnetic shielding material is polyaniline-graphene oxide composite material；The fire retardant is 2,4,6- tribromo-benzenes The mixture of base allyl ether and zinc borate.
The coupling agent is γ-methacryloxypropyl trimethoxy silane；The compatilizer is hydrogenated styrene- Butadiene-styrene copolymer graft glycidyl methacrylate.
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 such as above-mentioned shock resistance high heat resistance material, includes the following steps:
Step A: in parts by weight, by polyvinyl chloride resin, TPE resin, PP resin, heat-resistant filler, coupling agent and compatilizer into Row is mixed for the first time, then adds remaining raw material, carries out second and is mixed, mixture is made；
Step B: the investment extrusion equipment of mixture made from step A is kneaded, squeezed out, is granulated, it is high that shock resistance is made Heat proof material.
The speed of agitator that the first time is mixed is 950r/min, and the speed of agitator of second of mixing is 1700r/min；One area's temperature of the extrusion equipment is 288 DEG C, and two area's temperature are 298 DEG C, and three area's temperature are 308 DEG C, 4th area Temperature is 313 DEG C, and five area's temperature are 302 DEG C.
A kind of cable protection pipe, the cable protection pipe are made by above-mentioned shock resistance high heat resistance material.
Embodiment 5
The difference of the present embodiment and above-described embodiment 1 is:
A kind of shock resistance high heat resistance material, the raw material including following parts by weight:
The anti-impact modifier is what 2:5 was formed with weight ratio by silica filler and acrylic acid esters co-polymer Mixture；
The mixture that the heat-resistant filler is made of calcium carbonate, lignocellulosic and magnesium silicide with weight ratio for 8:6:2.
The silica filler is the mixture of glass flake and glass fibre.
The electromagnetic shielding material is polyaniline-graphene oxide composite material；The fire retardant is decabrominated dipheny base second The mixture of alkane and zinc oxide.
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 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 such as above-mentioned shock resistance high heat resistance material, includes the following steps:
Step A: in parts by weight, by polyvinyl chloride resin, TPE resin, PP resin, heat-resistant filler, coupling agent and compatilizer into Row is mixed for the first time, then adds remaining raw material, carries out second and is mixed, mixture is made；
Step B: the investment extrusion equipment of mixture made from step A is kneaded, squeezed out, is granulated, it is high that shock resistance is made Heat proof material.
The speed of agitator that the first time is mixed is 1000r/min, second of speed of agitator being mixed For 1800r/min；One area's temperature of the extrusion equipment be 290 DEG C, two area's temperature be 300 DEG C, three area's temperature be 310 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 shock resistance high heat resistance material.
Embodiment 6
The difference of the present embodiment and above-described embodiment 1 is:
The fire retardant is by deca-BDE, 2, and 4,6- tribromo phenyl allyl ethers and zinc borate are with weight ratio for 2: 1.2:1 the mixture of composition.
The coupling agent be by methyltriethoxysilane, pyrophosphate titanate esters and anilinomethyl triethoxysilane with Weight ratio is the mixture of 1:1:2 composition.
The compatilizer is by hydrogenated styrene-butadiene-styrene copolymer grafted glycidyl methacrylate The mixture formed with ethylene-acrylic acid-methyl esters graft glycidyl methacrylate with weight ratio for 2.4:1.
Embodiment 7
The difference of the present embodiment and above-described embodiment 2 is:
The fire retardant is by deca-BDE, 2, and 4,6- tribromo phenyl allyl ethers and zinc borate are with weight ratio for 2.2: 1.4:1 the mixture of composition.
The coupling agent be by methyltriethoxysilane, pyrophosphate titanate esters and anilinomethyl triethoxysilane with Weight ratio is the mixture of 1.2:1:2.2 composition.
The compatilizer is by hydrogenated styrene-butadiene-styrene copolymer grafted glycidyl methacrylate The mixture formed with ethylene-acrylic acid-methyl esters graft glycidyl methacrylate with weight ratio for 2.6:1.
Embodiment 8
The difference of the present embodiment and above-described embodiment 3 is:
The fire retardant is by deca-BDE, 2, and 4,6- tribromo phenyl allyl ethers and zinc borate are with weight ratio for 2.5: 1.5:1 the mixture of composition.
The coupling agent be by methyltriethoxysilane, pyrophosphate titanate esters and anilinomethyl triethoxysilane with Weight ratio is the mixture of 1.5:1:2.5 composition.
The compatilizer is by hydrogenated styrene-butadiene-styrene copolymer grafted glycidyl methacrylate The mixture formed with ethylene-acrylic acid-methyl esters graft glycidyl methacrylate with weight ratio for 2.8:1.
Embodiment 9
The difference of the present embodiment and above-described embodiment 4 is:
The fire retardant is by deca-BDE, 2, and 4,6- tribromo phenyl allyl ethers and zinc borate are with weight ratio for 2.8: 1.6:1 the mixture of composition.
The coupling agent be by methyltriethoxysilane, pyrophosphate titanate esters and anilinomethyl triethoxysilane with Weight ratio is the mixture of 1.8:1:2.8 composition.
The compatilizer is by hydrogenated styrene-butadiene-styrene copolymer grafted glycidyl methacrylate The mixture formed with ethylene-acrylic acid-methyl esters graft glycidyl methacrylate with weight ratio for 4:1.
Embodiment 10
The difference of the present embodiment and above-described embodiment 5 is:
The fire retardant is by deca-BDE, 2, and 4,6- tribromo phenyl allyl ethers and zinc borate are with weight ratio for 3: 1.8:1 the mixture of composition.
The coupling agent be by methyltriethoxysilane, pyrophosphate titanate esters and anilinomethyl triethoxysilane with Weight ratio is the mixture of 2:1:3 composition.
The compatilizer is by hydrogenated styrene-butadiene-styrene copolymer grafted glycidyl methacrylate The mixture formed with ethylene-acrylic acid-methyl esters graft glycidyl methacrylate with weight ratio for 3.2:1.
Comparative example 1
A kind of shock resistance high heat resistance material, the raw material including following parts by weight:
The anti-impact modifier is made of silica filler and acrylic acid esters co-polymer with weight ratio for 1.5:4 Mixture；
The mixing that the heat-resistant filler is made of calcium carbonate, lignocellulosic and magnesium silicide with weight ratio for 5:4:1.7 Object.
The silica filler is SiO2The mixture of glass powder and glass flake.
The fire retardant is the mixture of deca-BDE and antimony oxide.
The coupling agent is methyltriethoxysilane；The compatilizer is that ethylene-acrylic acid-methyl esters is grafted metering system Acid glycidyl ester.
A kind of preparation method of such as above-mentioned shock resistance high heat resistance material, includes the following steps:
Step A: in parts by weight, by polyvinyl chloride resin, TPE resin, PP resin, heat-resistant filler, coupling agent and compatilizer into Row is mixed for the first time, then adds remaining raw material, carries out second and is mixed, mixture is made；
Step B: the investment extrusion equipment of mixture made from step A is kneaded, squeezed out, is granulated, it is high that shock resistance is made Heat proof material.
The speed of agitator that the first time is mixed is 900r/min, and the speed of agitator of second of mixing is 1700r/min；One area's temperature of the extrusion equipment is 287 DEG C, and two area's temperature are 295 DEG C, and three area's temperature are 307 DEG C, 4th area Temperature is 312 DEG C, and five area's temperature are 298 DEG C.
A kind of cable protection pipe, the cable protection pipe are made by above-mentioned shock resistance high heat resistance material.
Comparative example 2
A kind of high heat resistance material, the raw material including following parts by weight:
The mixing that the heat-resistant filler is made of calcium carbonate, lignocellulosic and magnesium silicide with weight ratio for 5:4:1.7 Object.
The silica filler is SiO2The mixture of glass powder and glass flake.
The electromagnetic shielding material is polyaniline-graphene oxide composite material；The fire retardant be deca-BDE and The mixture of antimony oxide.
The coupling agent is methyltriethoxysilane；The compatilizer is that ethylene-acrylic acid-methyl esters is grafted metering system Acid glycidyl ester.
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 such as above-mentioned high heat resistance material, includes the following steps:
Step A: in parts by weight, by polyvinyl chloride resin, TPE resin, PP resin, heat-resistant filler, coupling agent and compatilizer into Row is mixed for the first time, then adds remaining raw material, carries out second and is mixed, mixture is made；
Step B: the investment extrusion equipment of mixture made from step A is kneaded, squeezed out, is granulated, high heat resistance material is made Material.
The speed of agitator that the first time is mixed is 900r/min, and the speed of agitator of second of mixing is 1700r/min；One area's temperature of the extrusion equipment is 287 DEG C, and two area's temperature are 295 DEG C, and three area's temperature are 307 DEG C, 4th area Temperature is 312 DEG C, and five area's temperature are 298 DEG C.
A kind of cable protection pipe, the cable protection pipe are made by above-mentioned high heat resistance material.
Comparative example 3
A kind of anti-ballistic materials, the raw material including following parts by weight:
The anti-impact modifier is made of silica filler and acrylic acid esters co-polymer with weight ratio for 1.5:4 Mixture.
The silica filler is SiO2The mixture of glass powder and glass flake.
The electromagnetic shielding material is polyaniline-graphene oxide composite material；The fire retardant be deca-BDE and The mixture of antimony oxide.
The coupling agent is methyltriethoxysilane；The compatilizer is that ethylene-acrylic acid-methyl esters is grafted metering system Acid glycidyl ester.
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 such as above-mentioned anti-ballistic materials, includes the following steps:
Step A: in parts by weight, by polyvinyl chloride resin, TPE resin, PP resin, anti-impact modifier, coupling agent and compatible Agent carries out first time mixing, then adds remaining raw material, carries out second and is mixed, mixture is made；
Step B: the investment extrusion equipment of mixture made from step A is kneaded, squeezed out, is granulated, shock resistance material is made Material.
The speed of agitator that the first time is mixed is 900r/min, and the speed of agitator of second of mixing is 1700r/min；One area's temperature of the extrusion equipment is 287 DEG C, and two area's temperature are 295 DEG C, and three area's temperature are 307 DEG C, 4th area Temperature is 312 DEG C, and five area's temperature are 298 DEG C.
A kind of cable protection pipe, the cable protection pipe are made by above-mentioned anti-ballistic materials.
Comparative example 4
A kind of shock resistance high heat resistance material, the raw material including following parts by weight:
The anti-impact modifier is made of silica filler and acrylic acid esters co-polymer with weight ratio for 1.5:4 Mixture；
The mixing that the heat-resistant filler is made of calcium carbonate, lignocellulosic and magnesium silicide with weight ratio for 5:4:1.7 Object.
The silica filler is SiO2The mixture of glass powder and glass flake.
The electromagnetic shielding material is polyaniline-graphene oxide composite material；The fire retardant be deca-BDE and The mixture of antimony oxide.
The coupling agent is methyltriethoxysilane；The compatilizer is that ethylene-acrylic acid-methyl esters is grafted metering system Acid glycidyl ester.
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, is carried out Mixture A is made after ultrasonic agitation；
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 (2), the Bronsted acid is to be with weight ratio by sulfosalicylic acid, p-methyl benzenesulfonic acid and perchloric acid 3.5:2.5:1.2 the mixture of composition；In the step (3), the initiator is by ammonium persulfate and potassium peroxydisulfate with weight Than the mixture formed 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.
A kind of preparation method of such as above-mentioned shock resistance high heat resistance material, includes the following steps:
Step A: in parts by weight, by polyvinyl chloride resin, TPE resin, PP resin, heat-resistant filler, coupling agent and compatilizer into Row is mixed for the first time, then adds remaining raw material, carries out second and is mixed, mixture is made；
Step B: the investment extrusion equipment of mixture made from step A is kneaded, squeezed out, is granulated, it is high that shock resistance is made Heat proof material.
The speed of agitator that the first time is mixed is 900r/min, and the speed of agitator of second of mixing is 1700r/min；One area's temperature of the extrusion equipment is 287 DEG C, and two area's temperature are 295 DEG C, and three area's temperature are 307 DEG C, 4th area Temperature is 312 DEG C, and five area's temperature are 298 DEG C.
A kind of cable protection pipe, the cable protection pipe are made by above-mentioned shock resistance high heat resistance material.
Comparative example 5
A kind of shock resistance high heat resistance material, the raw material including following parts by weight:
The anti-impact modifier is made of silica filler and acrylic acid esters co-polymer with weight ratio for 1.5:4 Mixture；
The mixing that the heat-resistant filler is made of calcium carbonate, lignocellulosic and magnesium silicide with weight ratio for 5:4:1.7 Object.
The silica filler is SiO2The mixture of glass powder and glass flake.
The electromagnetic shielding material is polyaniline-graphene oxide composite material；The fire retardant be deca-BDE and The mixture of antimony oxide.
The coupling agent is methyltriethoxysilane；The compatilizer is that ethylene-acrylic acid-methyl esters is grafted metering system Acid glycidyl ester.
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 perchloric acid 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 (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.
A kind of preparation method of such as above-mentioned shock resistance high heat resistance material, includes the following steps:
Step A: in parts by weight, by polyvinyl chloride resin, TPE resin, PP resin, heat-resistant filler, coupling agent and compatilizer into Row is mixed for the first time, then adds remaining raw material, carries out second and is mixed, mixture is made；
Step B: the investment extrusion equipment of mixture made from step A is kneaded, squeezed out, is granulated, it is high that shock resistance is made Heat proof material.
The speed of agitator that the first time is mixed is 900r/min, and the speed of agitator of second of mixing is 1700r/min；One area's temperature of the extrusion equipment is 287 DEG C, and two area's temperature are 295 DEG C, and three area's temperature are 307 DEG C, 4th area Temperature is 312 DEG C, and five area's temperature are 298 DEG C.
A kind of cable protection pipe, the cable protection pipe are made by above-mentioned shock resistance high heat resistance material.
Cable protection pipe made from above-described embodiment 1-10 and comparative example 1-5 is subjected to impact strength respectively, is stretched The performance tests such as intensity, weatherability, electromagnet shield effect, fire protecting performance, it is shown that test result is as follows:
By upper table data it is found that cable protection pipe produced by the present invention passes through with excellent shock resistance and heat-resisting Property, impact strength reaches 19.81KJ/m2-23.75KJ/m2, heat distortion temperature reaches 98-113 DEG C；And by using electromagnetic screen It covers material electromagnetic wave is reflected and absorbed, electromagnetic wave be reflected using the high conductivity of polyaniline, in conjunction with oxygen The high microwave absorbing property of graphite alkene absorbs electromagnetic wave, and the two combines, the polyaniline-coated with reflection electromagnetic wave performance The graphene oxide with performance of absorbing electromagnetic wave, make composite material first with cladding polyaniline carry out reflection of electromagnetic wave, It recycles graphene oxide to absorb not fully reflective electromagnetic wave, reaches preferable effectiveness, be electromagnetically shielded Efficiency reaches 19.78-38.16dB, and mechanical mechanics property is excellent.
Compared with comparative example 1, comparative example 1 does not use electromagnetic shielding material, and composite material obtained does not obviously have electricity Magnetic screening action, the electromagnetic wave that can not be generated to cable inside shield, and electromagnetic wave is easy to other electronic devices or human body Health impacts；
Compared with comparative example 2, comparative example 2 does not use anti-impact modifier, the shock resistance of composite material obtained Significant lower, the performance for resisting foreign impacts is weaker, illustrates that anti-impact modifier of the invention can effectively improve composite material Shock resistance；
Compared with comparative example 3, comparative example 3 does not use heat-resistant filler, and the heat distortion temperature of composite material obtained is obvious Lower, so that composite material can just deform at a lower temperature, stability is low, illustrates that heat-resistant filler of the invention can be effective The heat resistance and thermal stability of ground raising composite material；
Compared with comparative example 4, without using stabilizer to graphite oxide in the electromagnetic shielding material preparation method of comparative example 4 Alkene carries out spatial stability, and the electromagnet shield effect of composite material obtained is significant lower, illustrates that the present invention is prepared using stabilizer Graphene oxide-polyaniline composite material can effectively improve the spatial stability of graphene oxide, and then it is multiple to improve subsequent preparation The electromagnetic wave shielding performance of condensation material；
Compared with comparative example 5, do not have in the electromagnetic shielding material preparation method of comparative example 5 using Bronsted acid of the invention into The electromagnet shield effect of row doping treatment, composite material obtained is also significant lower, illustrates (to utilize using Bronsted acid of the invention The high conductivity and surface activation of the high conductivity of perchloric acid and sulfosalicylic acid, p-methyl benzenesulfonic acid, effectively enhancing are made Polyaniline solubility, improve shield effectiveness and processing performance) electromagnetic wave shielding of composite material of the present invention can be effectively improved Performance.
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 shock resistance high heat resistance material, it is characterised in that: the raw material including following parts by weight:
The anti-impact modifier is what 1-2:3-5 was formed with weight ratio by silica filler and acrylic acid esters co-polymer Mixture；
The heat-resistant filler is made of calcium carbonate, lignocellulosic and magnesium silicide with weight ratio for 3-8:2-6:1.5-2 mixed Close object.
2. a kind of shock resistance high heat resistance material according to claim 1, it is characterised in that: the silica filler is SiO2At least two in glass powder, glass flake and glass fibre.
3. a kind of shock resistance high heat resistance material according to claim 1, it is characterised in that: the electromagnetic shielding material is poly- Aniline-graphene oxide composite material；The fire retardant is deca-BDE, decabromodiphenylethane, 2,4,6- tribromo phenyl At least one of allyl ether, antimony oxide, zinc oxide and zinc borate.
4. a kind of shock resistance high heat resistance material according to claim 1, it is characterised in that: the coupling agent is three second of methyl Oxysilane, pyrophosphate titanate esters, three (β-of vinyltriethoxysilane, anilinomethyl triethoxysilane and vinyl At least one of methoxy ethoxy) silane；The compatilizer is hydrogenated styrene-butadiene-styrene copolymer grafted One acrylonitrile of glycidyl methacrylate, ethylene-acrylic acid-methyl esters graft glycidyl methacrylate and styrene At least one of copolymer grafted glycidyl methacrylate.
5. a kind of shock resistance high heat resistance material according to claim 3, it is characterised in that: the polyaniline-graphite oxide Alkene 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 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 shock resistance high heat resistance material according to claim 5, it is characterised in that: described steady in the step (1) Determining agent is polyvinylpyrrolidone；In the step (2), the Bronsted acid is by sulfosalicylic acid, p-methyl benzenesulfonic acid and height Chloric acid is with the mixture that weight ratio is that 3-4:2-3:1-1.5 is formed；In the step (3), the initiator is by ammonium persulfate The mixture formed with potassium peroxydisulfate with weight ratio for 3-4:1.
7. a kind of shock resistance high heat resistance material according to claim 5, it is characterised in that: in the step (1), ultrasound is stirred The power mixed 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), being added before initiator into mixture B first is -5 DEG C~4 DEG C by the temperature control of initiator, The temperature of mixing is -5 DEG C~4 DEG C.
8. a kind of preparation method of such as described in any item shock resistance high heat resistance materials of claim 1-7, it is characterised in that: including Following steps:
Step A: in parts by weight, polyvinyl chloride resin, TPE resin, PP resin, heat-resistant filler, coupling agent and compatilizer are carried out the Mixed once stirring, then adds remaining raw material, carries out second and is mixed, mixture is made；
Step B: the investment extrusion equipment of mixture made from step A is kneaded, squeezed out, is granulated, shock resistance high heat resistance is made Material.
9. a kind of preparation method of shock resistance high heat resistance material according to claim 7, it is characterised in that: the first time The speed of agitator of mixing is 800-1000r/min, and described second speed of agitator being mixed is 1500-1800r/ min；One area's temperature of the extrusion equipment is 285-290 DEG C, and two area's temperature are 290-300 DEG C, and three area's temperature are 305-310 DEG C, four area's temperature are 310-315 DEG C, and 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 any one of claim 8-9 preparation method system Standby shock resistance high heat resistance material is made, and the impact strength of the cable protection pipe is 19.81KJ/m2-23.75KJ/m2, heat Deformation temperature is 98-113 DEG C, electromagnet shield effect 19.78-38.16dB.
CN201810806126.6A 2018-07-20 2018-07-20 A kind of shock resistance high heat resistance material and preparation method thereof and cable protection pipe obtained Pending CN109021450A (en)

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