CN109370217A - A kind of conductive polymer composites - Google Patents
A kind of conductive polymer composites Download PDFInfo
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- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2201/001—Conductive additives
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Abstract
The invention discloses a kind of composite high-molecular conductive materials, belong to technical field of polymer materials.The present invention is with 4- chloro-benzoic anhydride and 4,4,Diaminodiphenyl ether is raw material, prepares dichlorophthalein imide using toluene, water first, so that dichlorophthalein imide monomer and the double sylvite of bis-phenol is prepared base-material by nucleophilic substitution, adjusts the electric conductivity and mechanical property of this strong material system；The present invention enters graphene oxide ultrasonic disperse in acid solution, promotes system mechanical property further, TiO while improving system electric conductivity by situ aggregation method2After ingredient is fired effect, rutile-type can be converted into and greatly reinforced its electric conductivity, make system inner conductive increased activity, and toughness is promoted.The present invention solves the problems, such as to commonly use conductive material electric conductivity at present and mechanical property is bad.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of conductive polymer composites.
Background technique
High molecular material then is constituted equipped with other additive/auxiliary agent/reinforcing materials using high-molecular compound as matrix
Material.It combines the performance characteristics of original material, and can carry out design of material as needed.
With the rapid development of modern industry, high molecular material with more and more extensive, major colleges and universities, research institute all set
High molecular material research center is set.High molecular material is also referred to as polymer material, is furnished with using high molecular polymer as matrix
The material that other auxiliary agents are constituted, high molecular material are divided into rubber, fiber, plastics, polymer binder, macromolecule by characteristic and apply
Material and polymer-based composite etc..High molecular material is in electric and electronic industry, aerospace industry, construction industry, medical instrument, medical treatment packet
It suffers from and is widely applied in the every profession and trades such as dress, transportation, home electric, agricultural.
Conductive polymer material is with conducting function (including semiconduction, metallic conductivity and superconductivity), conductance
Polymer material of the rate in 10S/m or more.Macromolecule conducting material have density is small, easy processing, it is corrosion-resistant, can large area film forming
And conductivity the features such as being adjusted in the range of more than ten a orders of magnitude, it can be used as various metals material and inorganic
The substitute of conductive material, and have become the indispensable a kind of material of many advanced industrial departments and sophisticated technology field.
Conductive polymer material is due to good positive temperature coefficient effect (PTC effect), the resistance meeting of material at present
It increases with increasing temperature, electric heating component is made commonly used to substitute metal.When preparing conductive polymer material, usually
It adds conductive black in the substrate to realize, so will lead to conductive polymer since a large amount of conductive black is added
The mechanical property sharp fall of sub- material, and its electric conductivity is not very good, therefore a kind of mechanical property need to be developed and led
Electrically good conductive polymer composites.
Summary of the invention
The technical problems to be solved by the invention: for current common conductive material electric conductivity and mechanical property is bad asks
Topic, provides a kind of conductive polymer composites.
In order to solve the above technical problems, the present invention is using technical solution as described below:
A kind of conductive polymer composites, including following component: 6 ~ 10 parts of terephthalic acid (TPA)s, 3 ~ 7 parts of triethylene diamines, 10 ~
15 parts of epoxy resin, 1 ~ 4 part of plasticizer, 3 ~ 7 parts of surfactants, 2 ~ 5 parts of auxiliary agents, 20 ~ 45 parts of water, further includes: 25 ~ 50 parts multiple
Close base-material, 12 ~ 20 parts of conductive synergistic effect objects.
The preparation method of the composite base-material, includes the following steps:
(1) 4:1 ~ 2:30 ~ 50 take 4- chloro-benzoic anhydride, 4,4 in mass ratio,Diaminodiphenyl ether, reagent A mixing, lead to nitrogen and protect
Shield, stirring, obtains reactant, takes reactant 30 ~ 50:1:1 in mass ratio ~ 3 that toluene, water mixing is added, derived from monomer processed, takes
It makes monomer 12 ~ 18:1:1 in mass ratio ~ 3 by oneself and 4,4- dihydroxy diphenyl propane, potassium carbonate mixing is added, flow back in 150 ~ 170 DEG C
Reaction obtains the double sylvite of bisphenol-A, takes the double sylvite 1:6 in mass ratio ~ 10 of bisphenol-A that dehydrated alcohol mixing is added, stands, filter, take filter
Slag is washed with water, dry, obtains base-material；
(2) in 40 ~ 60 DEG C, 1:3 ~ 5:12 ~ 20 take silane coupling agent KH-560, white carbon black, sodium carbonate liquor mixing in mass ratio
Stirring is kept the temperature, and filtering takes filter cake to be washed with water, dry, obtains dried object, take dried object 1:5 ~ 8:0.1 in mass ratio be added base-material,
Auxiliary material mixing, ball milling obtain ball milling material, take ball milling material under an argon atmosphere, and low-temperature plasma processing discharges to get composite base-material.
Reagent A in the step (1): 30 ~ 50:1 in mass ratio takes n,N-dimethylacetamide, magnesium sulfate mixing to stir
It mixes, filters, collect filtrate decompression distillation, collect fraction and stand to get reagent A.
Auxiliary material in the step (2): 3:1 ~ 2 take glycerol, dimethyl silicone polymer mixing to get auxiliary material in mass ratio.
The preparation method of the conduction synergistic effect object, includes the following steps:
S1. it taking graphene oxide 1:20 in mass ratio ~ 30 that hydrochloric acid solution is added to be mixed, ultrasonic oscillation obtains dispersion liquid, in
0 ~ 5 DEG C, take dispersion liquid 15 ~ 25:1 in mass ratio that pyrroles is added, stirring obtains mixed liquor, in ice-water bath, in mass ratio 20 ~ 30:1:
4 take mixed liquor, ammonium persulfate, hydrochloric acid solution to be mixed, and ethanol solution is added and adjusts pH, is stored at room temperature, filters, and take filter residue dry
It is dry, obtain graphene oxide-polypyrrole；
S2. in 55 ~ 70 DEG C, petroleum coke powder, pre-treating fly ash, reagent B is taken to be mixed for 5:1 ~ 3:40 ~ 60 in mass ratio,
Mixture is obtained, takes mixture 8:1 in mass ratio ~ 3 that graphene oxide-polypyrrole mixing is added, ultrasonication obtains disperse materials,
Disperse materials are taken to be concentrated in vacuo to get conductive synergistic effect object.
Pre-treating fly ash in the step S2: it takes flyash 1:12 in mass ratio ~ 20 that hydrochloric acid solution mixing is added and stirs
It mixes, is stored at room temperature, filter, take filter residue 6 ~ 10:1:0.4 in mass ratio that iron powder, aluminium hydroxide mixing and ball milling is added, obtain ball milling material,
Take the roasting of ball milling material to get pre-treating fly ash.
Reagent B: 1:5 ~ 8:25 in mass ratio in the step S2 takes sodium citrate, ammonium persulfate, water mixing to get examination
Agent B.
The plasticizer: 1:3 ~ 6 take dibutyl phthalate, triethyl citrate mixing to get plasticising in mass ratio
Agent.
The auxiliary agent: 4:1 ~ 2 take carbamide, methyl-silicone oil mixing to get auxiliary agent in mass ratio.
The surfactant: 1:4 ~ 7 take neopelex, laureth sodium sulfovinate mixed in mass ratio
It closes to get surfactant.
The present invention is compared with other methods, and advantageous effects are:
(1) present invention is with 4- chloro-benzoic anhydride and 4,4,Diaminodiphenyl ether is raw material, to contain n,N-dimethylacetamide
Solvent A is solvent, prepares dichlorophthalein imide using toluene, water first, later in same reaction system, prepares the double potassium of bis-phenol
Salt finally makes dichlorophthalein imide monomer and the double sylvite of bis-phenol prepare base-material by nucleophilic substitution, wherein containing ehter bond, acyl
Imine group not only with the outstanding heat resistance and mechanical property of polyimides, but also has both good processing performance, cooperation activation
White carbon black, the compatibility of composite base-material system can be promoted well, be convenient for and conductive synergistic effect object coordinate enhance this material
The electric conductivity and mechanical property of system；
(2) present invention enters graphene oxide ultrasonic disperse in acid solution, passes through situ aggregation method, in low temperature whipping process, oxygen
Pyrrole monomer can be adsorbed in its surface by hydrogen bond or electrostatic attraction, in mistake by a large amount of oxygen-containing functional group in graphite alkene surface
Can further polypyrrole be attached to surface of graphene oxide again under the action of ammonium sulfate by non-covalent bond, form polyphenyl
Amine-graphene oxide network, and graphene oxide large specific surface area itself, density are low, can cooperate the composite base of high-compatibility
Material forms three-dimensional conductive network skeleton, system mechanical property can be made further to be mentioned while improving system electric conductivity
It rises, after pre-processing to flyash, can be used as functional stuffing, first acid is dissolved except behind active metal, mixed with iron powder, aluminium hydroxide
Ball milling is closed, to wherein main component SiO2A small amount of defect and hole are caused, it is micro conductive performance that it is non-conductive, which to change its, and therein
TiO2After ingredient is fired effect, rutile-type can be converted into and greatly reinforced its electric conductivity, be scattered in this material system, it can
Material internal is effectively filled, makes system inner conductive increased activity, and toughness is promoted.
Specific embodiment
Reagent A: 30 ~ 50:1 in mass ratio takes n,N-dimethylacetamide, magnesium sulfate mixing, with 400 ~ 600r/min magnetic force
Stirring 20 ~ for 24 hours, it filters, collects filtrate decompression distillation, collect fraction and be stored at room temperature to get reagent A.
Reagent B: 1:5 ~ 8:25 in mass ratio takes sodium citrate, ammonium persulfate, deionized water mixing to get reagent B.
Auxiliary agent: 4:1 ~ 2 take carbamide, methyl-silicone oil mixing to get auxiliary agent in mass ratio.
Plasticizer: 1:3 ~ 6 take dibutyl phthalate, triethyl citrate mixing to get plasticizer in mass ratio.
Pre-treating fly ash: taking flyash 1:12 in mass ratio ~ 20 that the hydrochloric acid solution that mass fraction is 10% is added and mix,
With 350 ~ 600r/min, 25 ~ 50min of magnetic agitation, it is stored at room temperature 1 ~ 3h, is filtered, filter residue 6 ~ 10:1:0.4 in mass ratio is taken to be added
Iron powder, aluminium hydroxide are mixed in ball grinder, with 350 ~ 550r/min, 1 ~ 3h of ball milling, are obtained ball milling material, are taken ball milling material in 500 ~ 700 DEG C
Muffle furnace roasts 1 ~ 3h to get pre-treating fly ash.
Auxiliary material: 3:1 ~ 2 take glycerol, dimethyl silicone polymer mixing to get auxiliary material in mass ratio.
Surfactant: 1:4 ~ 7 take neopelex, the mixing of laureth sodium sulfovinate in mass ratio, i.e.,
Obtain surfactant.
The preparation method of composite base-material, includes the following steps:
(1) 4:1 ~ 2:30 ~ 50 take 4- chloro-benzoic anhydride, 4,4 in mass ratio,Diaminodiphenyl ether, reagent A are mixed in reaction kettle, are led to
Nitrogen protection stirs 1 ~ 3h with 300 ~ 500r/min, obtains reactant, reactant 30 ~ 50:1:1 ~ 3 in mass ratio is taken to add at room temperature
Enter toluene, deionized water mixing, 20 ~ 45min is stirred with 400 ~ 600r/min and is derived from monomer processed in mass ratio derived from monomer processed
4,4- dihydroxy diphenyl propane, potassium carbonate mixing is added in 12 ~ 18:1:1 ~ 3, in 150 ~ 170 DEG C of 2 ~ 4h of back flow reaction, obtains bisphenol-A
Double sylvite take the double sylvite 1:6 in mass ratio ~ 10 of bisphenol-A that dehydrated alcohols mixing is added, stand 3 ~ 5h, filter, take filter residue spend from
After sub- water cleans 3 ~ 5 times, in 100 ~ 110 DEG C of 8 ~ 12h of oven drying, base-material is obtained；
(2) in 40 ~ 60 DEG C, 1:3 ~ 5:12 ~ 20 carbon that takes silane coupling agent KH-560, white carbon black, mass fraction 10% in mass ratio
Acid sodium solution mixing keeps the temperature 3 ~ 6h with 400 ~ 600r/min, 1 ~ 3h of magnetic agitation, and filtering takes filter cake to be washed with deionized 3 ~ 5
It is dry to constant weight in 70 ~ 90 DEG C of vacuum ovens after secondary, obtain dried object, take dried object 1:5 ~ 8:0.1 in mass ratio add base-material,
Auxiliary material mixing, with 300 ~ 450r/min, 1 ~ 3h of ball milling, obtains ball milling material, takes ball milling material in low-temperature plasma processor, in argon gas
Under atmosphere, 10 ~ 15min 5 ~ 8MPa, is handled under the conditions of 12 ~ 20 DEG C, is discharged to get composite base-material.
The preparation method of conductive synergistic effect object, includes the following steps:
S1. the hydrochloric acid solution for taking graphene oxide 1:20 in mass ratio ~ 30 that concentration 1mol/L is added is mixed in container, with 300 ~
After 30 ~ 50min of 500r/min magnetic agitation, ultrasonic oscillation instrument is moved to, 30 ~ 50min is shaken with 55 ~ 65kHz frequency ultrasonic wave,
Dispersion liquid, in 0 ~ 5 DEG C, take dispersion liquid 15 ~ 25:1 in mass ratio be added pyrroles, with 400 ~ 700r/min magnetic agitation 40 ~
60min obtains mixed liquor, and in ice-water bath, 20 ~ 30:1:4 in mass ratio takes mixed liquor, ammonium persulfate, the hydrochloric acid of concentration 1mol/L molten
Liquid mixing after stirring 25 ~ 45min with 350 ~ 550r/min, is added the ethanol solution that volume fraction is 70% and adjusts pH to neutrality,
It is stored at room temperature 1 ~ 3h, is filtered, takes filter residue in 65 ~ 80 DEG C of oven dryings 20 ~ for 24 hours, obtains graphene oxide-polypyrrole；
S2. in 55 ~ 70 DEG C, take petroleum coke powder, pre-treating fly ash, reagent B mixed in reaction kettle for 5:1 ~ 3:40 ~ 60 in mass ratio
It closes, 2 ~ 5h is stirred with 500 ~ 800r/min, obtains mixture, takes mixture 8:1 in mass ratio ~ 3 that graphene oxide-polypyrrole is added
Mixing moves to supersonic oscillations instrument with 45 ~ 55kHz frequency ultrasonic wave and handles 12 ~ 25min, obtains disperse materials, take disperse materials in 60 ~
80 DEG C are concentrated in vacuo to the 40 ~ 55% of original volume to get conductive synergistic effect object.
A kind of conductive polymer composites, according to the mass fraction, including following component: 6 ~ 10 parts of terephthalic acid (TPA)s, 3 ~ 7
Part triethylene diamine, 10 ~ 15 parts of epoxy resin, 1 ~ 4 part of plasticizer, 3 ~ 7 parts of surfactants, 2 ~ 5 parts of auxiliary agents, 20 ~ 45 parts of water,
25 ~ 50 parts of composite base-materials, 12 ~ 20 parts of conductive synergistic effect objects.
A kind of preparation method of conductive polymer composites, includes the following steps:
(1) according to the mass fraction, 6 ~ 10 parts of terephthalic acid (TPA)s, 3 ~ 7 parts of triethylene diamines, 10 ~ 15 parts of epoxy resin, 1 ~ 4 part are taken
Plasticizer, 3 ~ 7 parts of surfactants, 2 ~ 5 parts of auxiliary agents, 20 ~ 45 parts of water, 25 ~ 50 parts of composite base-materials, 12 ~ 20 parts of conductive synergy are made
Use object；
(2) prior to 35 ~ 50 DEG C, terephthalic acid (TPA), water, surfactant, plasticizer is taken to mix in high-speed mixer, with 1000
~ 2000r/min stirs 30 ~ 50min, then is warming up to 80 ~ 100 DEG C, and triethylene diamine, auxiliary agent, composite base-material, conductive synergy is added
Agent, epoxy resin mixing are sent into double screw extruder, melt and make at 170 ~ 190 DEG C after moving to 1 ~ 3h of kneader kneading
Grain, discharging, natural cooling is to get conductive polymer composites.
Embodiment 1
Reagent A: 30:1 in mass ratio takes n,N-dimethylacetamide, magnesium sulfate mixing to take out with 400r/min magnetic agitation 20h
Filtrate decompression distillation is collected in filter, is collected fraction and is stored at room temperature to get reagent A.
Reagent B: 1:5:25 in mass ratio takes sodium citrate, ammonium persulfate, deionized water mixing to get reagent B.
Auxiliary agent: 4:1 in mass ratio takes carbamide, methyl-silicone oil mixing to get auxiliary agent.
Plasticizer: 1:3 in mass ratio takes dibutyl phthalate, triethyl citrate mixing to get plasticizer.
Pre-treating fly ash: taking flyash 1:12 in mass ratio that the hydrochloric acid solution that mass fraction is 10% is added and mix, with
350r/min magnetic agitation 25min, is stored at room temperature 1h, and filtering takes filter residue 6:1:0.4 in mass ratio that iron powder, aluminium hydroxide is added
It is mixed in ball grinder, with 350r/min ball milling 1h, obtains ball milling material, take ball milling material in 500 DEG C of Muffle furnace roasting 1h to get pretreatment
Flyash.
Auxiliary material: 3:1 in mass ratio takes glycerol, dimethyl silicone polymer mixing to get auxiliary material.
Surfactant: 1:4 in mass ratio take neopelex, laureth sodium sulfovinate mixing to get
Surfactant.
The preparation method of composite base-material, includes the following steps:
(1) 4:1:30 in mass ratio takes 4- chloro-benzoic anhydride, 4,4,Diaminodiphenyl ether, reagent A are mixed in reaction kettle, lead to nitrogen
Protection stirs 2h with 300r/min, obtains reactant, take reactant 30:1:1 in mass ratio that toluene, deionized water is added at room temperature
Mixing stirs 20min with 400r/min, derived from monomer processed, is derived from monomer processed 12:1:1 in mass ratio and 4,4- dihydroxy two is added
Phenylpropyl alcohol alkane, potassium carbonate mixing obtain the double sylvite of bisphenol-A in 150 DEG C of back flow reaction 2h, and the double sylvite 1:6 in mass ratio of bisphenol-A is taken to add
Enter dehydrated alcohol mixing, stand 3h, filters, after taking filter residue to clean 3 times with deionized water, in 100 DEG C of oven drying 10h, obtain base
Material；
(2) in 40 DEG C, 1:3:12 in mass ratio takes the sodium carbonate liquor of silane coupling agent KH-560, white carbon black, mass fraction 10%
Mixing keeps the temperature 3h with 400r/min magnetic agitation 1h, and filtering is dry in 70 DEG C of vacuum after taking filter cake to be washed with deionized 3 times
Dry case is dry to constant weight, obtains dried object, takes dried object 1:5:0.1 in mass ratio to add base-material, auxiliary material mixing, with 300r/min ball milling
1h obtains ball milling material, takes ball milling material in low-temperature plasma processor, under an argon atmosphere, 5MPa, handles under the conditions of 12 DEG C
10min discharges to get composite base-material.
The preparation method of conductive synergistic effect object, includes the following steps:
S1. the hydrochloric acid solution for taking graphene oxide 1:20 in mass ratio that concentration 1mol/L is added is mixed in container, with 300r/min
After magnetic agitation 30min, ultrasonic oscillation instrument is moved to, 30min is shaken with 55kHz frequency ultrasonic wave, dispersion liquid is obtained, in 0 DEG C, takes
Dispersion liquid 15:1 in mass ratio is added pyrroles and obtains mixed liquor with 400r/min magnetic agitation 40min, in ice-water bath, in mass ratio
20:1:4 takes the hydrochloric acid solution mixing of mixed liquor, ammonium persulfate, concentration 1mol/L, and after stirring 25min with 350r/min, body is added
The ethanol solution that fraction is 70% adjusts pH to neutrality, is stored at room temperature 1h, filters, take filter residue in 65 DEG C of oven drying 20h, obtain
Graphene oxide-polypyrrole；
S2. in 55 DEG C, petroleum coke powder, pre-treating fly ash, reagent B is taken to mix in reaction kettle for 5:1:40 in mass ratio, with
500r/min stirs 2h, obtains mixture, takes mixture 8:1 in mass ratio that graphene oxide-polypyrrole mixing is added, moves to ultrasound
Wave shaker handles 12min with 45kHz frequency ultrasonic wave, obtains disperse materials, disperse materials is taken to be concentrated in vacuo to original volume in 60 DEG C
40% to get conductive synergistic effect object.
A kind of conductive polymer composites, according to the mass fraction, including following component: 6 parts of terephthalic acid (TPA)s, 3 part three
Ethylene diamine, 10 parts of epoxy resin, 1 part of plasticizer, 3 parts of surfactants, 2 parts of auxiliary agents, 20 parts of water, 25 parts of composite base-materials, 12
The conductive synergistic effect object of part.
A kind of preparation method of conductive polymer composites, includes the following steps:
(1) according to the mass fraction, 6 parts of terephthalic acid (TPA)s, 3 parts of triethylene diamines, 10 parts of epoxy resin, 1 part of plasticizer, 3 parts are taken
Surfactant, 2 parts of auxiliary agents, 20 parts of water, 25 parts of composite base-materials, 12 parts of conductive synergistic effect objects；
(2) prior to 35 DEG C, terephthalic acid (TPA), water, surfactant, plasticizer is taken to mix in high-speed mixer, with 1000r/
Min stirs 30min, then is warming up to 80 DEG C, and triethylene diamine, auxiliary agent, composite base-material, conductive synergistic effect object, asphalt mixtures modified by epoxy resin is added
Rouge mixing is sent into double screw extruder after moving to kneader kneading 1h, and the melt pelletization at 170 DEG C discharges, natural cooling, i.e.,
Obtain conductive polymer composites.
Embodiment 2
Reagent A: 40:1 in mass ratio takes n,N-dimethylacetamide, magnesium sulfate mixing to take out with 500r/min magnetic agitation 22h
Filtrate decompression distillation is collected in filter, is collected fraction and is stored at room temperature to get reagent A.
Reagent B: 1:6:25 in mass ratio takes sodium citrate, ammonium persulfate, deionized water mixing to get reagent B.
Auxiliary agent: 4:1.5 in mass ratio takes carbamide, methyl-silicone oil mixing to get auxiliary agent.
Plasticizer: 1:5 in mass ratio takes dibutyl phthalate, triethyl citrate mixing to get plasticizer.
Pre-treating fly ash: taking flyash 1:18 in mass ratio that the hydrochloric acid solution that mass fraction is 10% is added and mix, with
400r/min magnetic agitation 40min, is stored at room temperature 2h, and filtering takes filter residue 8:1:0.4 in mass ratio that iron powder, aluminium hydroxide is added
It is mixed in ball grinder, with 450r/min ball milling 2h, obtains ball milling material, take ball milling material in 600 DEG C of Muffle furnace roasting 2h to get pretreatment
Flyash.
Auxiliary material: 3:1.5 in mass ratio takes glycerol, dimethyl silicone polymer mixing to get auxiliary material.
Surfactant: 1:5 in mass ratio take neopelex, laureth sodium sulfovinate mixing to get
Surfactant.
The preparation method of composite base-material, includes the following steps:
(1) 4:1.5:40 in mass ratio takes 4- chloro-benzoic anhydride, 4,4,Diaminodiphenyl ether, reagent A are mixed in reaction kettle, lead to nitrogen
Gas shielded stirs 2h with 400r/min, obtains reactant, take reactant 40:1:2 in mass ratio that toluene, deionization is added at room temperature
Water mixing stirs 35min with 500r/min, derived from monomer processed, is derived from monomer processed 16:1:2 in mass ratio and 4,4- dihydroxy is added
Diphenyl propane, potassium carbonate mixing obtain the double sylvite of bisphenol-A in 160 DEG C of back flow reaction 3h, take the double sylvite of bisphenol-A 1:8 in mass ratio
Dehydrated alcohol mixing is added, stands 4h, filters, after taking filter residue to clean 4 times with deionized water, in 105 DEG C of oven drying 10h, obtains
Base-material；
(2) in 50 DEG C, 1:4:18 in mass ratio takes the sodium carbonate liquor of silane coupling agent KH-560, white carbon black, mass fraction 10%
Mixing keeps the temperature 5h with 500r/min magnetic agitation 2h, and filtering is dry in 80 DEG C of vacuum after taking filter cake to be washed with deionized 4 times
Dry case is dry to constant weight, obtains dried object, takes dried object 1:6:0.1 in mass ratio to add base-material, auxiliary material mixing, with 350r/min ball milling
2h obtains ball milling material, takes ball milling material in low-temperature plasma processor, under an argon atmosphere, 6MPa, handles under the conditions of 18 DEG C
13min discharges to get composite base-material.
The preparation method of conductive synergistic effect object, includes the following steps:
S1. the hydrochloric acid solution for taking graphene oxide 1:25 in mass ratio that concentration 1mol/L is added is mixed in container, with 400r/min
After magnetic agitation 40min, ultrasonic oscillation instrument is moved to, 40min is shaken with 60kHz frequency ultrasonic wave, dispersion liquid is obtained, in 3 DEG C, takes
Dispersion liquid 20:1 in mass ratio is added pyrroles and obtains mixed liquor with 500r/min magnetic agitation 50min, in ice-water bath, in mass ratio
25:1:4 takes the hydrochloric acid solution mixing of mixed liquor, ammonium persulfate, concentration 1mol/L, and after stirring 30min with 450r/min, body is added
The ethanol solution that fraction is 70% adjusts pH to neutrality, is stored at room temperature 2h, filters, take filter residue in 70 DEG C of oven drying 22h, obtain
Graphene oxide-polypyrrole；
S2. in 60 DEG C, petroleum coke powder, pre-treating fly ash, reagent B is taken to mix in reaction kettle for 5:2:50 in mass ratio, with
600r/min stirs 4h, obtains mixture, takes mixture 8:2 in mass ratio that graphene oxide-polypyrrole mixing is added, moves to ultrasound
Wave shaker handles 20min with 50kHz frequency ultrasonic wave, obtains disperse materials, disperse materials is taken to be concentrated in vacuo to original volume in 70 DEG C
45% to get conductive synergistic effect object.
A kind of conductive polymer composites, according to the mass fraction, including following component: 8 parts of terephthalic acid (TPA)s, 5 part three
Ethylene diamine, 13 parts of epoxy resin, 3 parts of plasticizer, 5 parts of surfactants, 3 parts of auxiliary agents, 35 parts of water, 40 parts of composite base-materials, 18
The conductive synergistic effect object of part.
A kind of preparation method of conductive polymer composites, includes the following steps:
(1) according to the mass fraction, 8 parts of terephthalic acid (TPA)s, 5 parts of triethylene diamines, 13 parts of epoxy resin, 3 parts of plasticizer, 5 parts are taken
Surfactant, 3 parts of auxiliary agents, 30 parts of water, 35 parts of composite base-materials, 18 parts of conductive synergistic effect objects；
(2) prior to 40 DEG C, terephthalic acid (TPA), water, surfactant, plasticizer is taken to mix in high-speed mixer, with 1500r/
Min stirs 40min, then is warming up to 90 DEG C, and triethylene diamine, auxiliary agent, composite base-material, conductive synergistic effect object, asphalt mixtures modified by epoxy resin is added
Rouge mixing is sent into double screw extruder after moving to kneader kneading 2h, and the melt pelletization at 180 DEG C discharges, natural cooling, i.e.,
Obtain conductive polymer composites.
Embodiment 3
Reagent A: 50:1 in mass ratio takes n,N-dimethylacetamide, magnesium sulfate mixing for 24 hours with 600r/min magnetic agitation to take out
Filtrate decompression distillation is collected in filter, is collected fraction and is stored at room temperature to get reagent A.
Reagent B: 1:8:25 in mass ratio takes sodium citrate, ammonium persulfate, deionized water mixing to get reagent B.
Auxiliary agent: 4:2 in mass ratio takes carbamide, methyl-silicone oil mixing to get auxiliary agent.
Plasticizer: 1:6 in mass ratio takes dibutyl phthalate, triethyl citrate mixing to get plasticizer.
Pre-treating fly ash: taking flyash 1:20 in mass ratio that the hydrochloric acid solution that mass fraction is 10% is added and mix, with
600r/min magnetic agitation 50min, is stored at room temperature 3h, and filtering takes filter residue 10:1:0.4 in mass ratio that iron powder, aluminium hydroxide is added
It is mixed in ball grinder, with 550r/min ball milling 3h, obtains ball milling material, take ball milling material in 700 DEG C of Muffle furnace roasting 3h to get pretreatment
Flyash.
Auxiliary material: 3:2 in mass ratio takes glycerol, dimethyl silicone polymer mixing to get auxiliary material.
Surfactant: 1:7 in mass ratio take neopelex, laureth sodium sulfovinate mixing to get
Surfactant.
The preparation method of composite base-material, includes the following steps:
(1) 4:2:50 in mass ratio takes 4- chloro-benzoic anhydride, 4,4,Diaminodiphenyl ether, reagent A are mixed in reaction kettle, lead to nitrogen
Protection stirs 1 ~ 3h with 500r/min, obtains reactant, take reactant 50:1:3 in mass ratio that toluene, deionization is added at room temperature
Water mixing stirs 45min with 600r/min, derived from monomer processed, is derived from monomer processed 18:1:3 in mass ratio and 4,4- dihydroxy is added
Diphenyl propane, potassium carbonate mixing obtain the double sylvite of bisphenol-A in 170 DEG C of back flow reaction 4h, take the double sylvite of bisphenol-A 1:10 in mass ratio
Dehydrated alcohol mixing is added, stands 5h, filters, after taking filter residue to clean 5 times with deionized water, in 110 DEG C of oven drying 12h, obtains
Base-material；
(2) in 60 DEG C, 1:5:20 in mass ratio takes the sodium carbonate liquor of silane coupling agent KH-560, white carbon black, mass fraction 10%
Mixing keeps the temperature 6h with 600r/min magnetic agitation 3h, and filtering is dry in 90 DEG C of vacuum after taking filter cake to be washed with deionized 5 times
Dry case is dry to constant weight, obtains dried object, takes dried object 1:8:0.1 in mass ratio to add base-material, auxiliary material mixing, with 450r/min ball milling
3h obtains ball milling material, takes ball milling material in low-temperature plasma processor, under an argon atmosphere, 8MPa, handles under the conditions of 20 DEG C
15min discharges to get composite base-material.
The preparation method of conductive synergistic effect object, includes the following steps:
S1. the hydrochloric acid solution for taking graphene oxide 1:30 in mass ratio that concentration 1mol/L is added is mixed in container, with 500r/min
After magnetic agitation 50min, ultrasonic oscillation instrument is moved to, 50min is shaken with 65kHz frequency ultrasonic wave, dispersion liquid is obtained, in 5 DEG C, takes
Dispersion liquid 25:1 in mass ratio is added pyrroles and obtains mixed liquor with 700r/min magnetic agitation 60min, in ice-water bath, in mass ratio
30:1:4 takes the hydrochloric acid solution mixing of mixed liquor, ammonium persulfate, concentration 1mol/L, and after stirring 45min with 550r/min, body is added
The ethanol solution that fraction is 70% adjusts pH to neutrality, is stored at room temperature 3h, filters, filter residue is taken for 24 hours, to obtain in 80 DEG C of oven dryings
Graphene oxide-polypyrrole；
S2. in 70 DEG C, petroleum coke powder, pre-treating fly ash, reagent B is taken to mix in reaction kettle for 5:3:60 in mass ratio, with
800r/min stirs 5h, obtains mixture, takes mixture 8:3 in mass ratio that graphene oxide-polypyrrole mixing is added, moves to ultrasound
Wave shaker handles 25min with 55kHz frequency ultrasonic wave, obtains disperse materials, disperse materials is taken to be concentrated in vacuo to original volume in 80 DEG C
55% to get conductive synergistic effect object.
A kind of conductive polymer composites, according to the mass fraction, including following component: 10 parts of terephthalic acid (TPA)s, 7 part three
Ethylene diamine, 15 parts of epoxy resin, 4 parts of plasticizer, 7 parts of surfactants, 5 parts of auxiliary agents, 45 parts of water, 50 parts of composite base-materials, 20
The conductive synergistic effect object of part.
A kind of preparation method of conductive polymer composites, includes the following steps:
(1) according to the mass fraction, 10 parts of terephthalic acid (TPA)s, 7 parts of triethylene diamines, 15 parts of epoxy resin, 4 parts of plasticizer, 7 parts are taken
Surfactant, 5 parts of auxiliary agents, 45 parts of water, 50 parts of composite base-materials, 20 parts of conductive synergistic effect objects；
(2) prior to 50 DEG C, terephthalic acid (TPA), water, surfactant, plasticizer is taken to mix in high-speed mixer, with 2000r/
Min stirs 50min, then is warming up to 100 DEG C, and triethylene diamine, auxiliary agent, composite base-material, conductive synergistic effect object, asphalt mixtures modified by epoxy resin is added
Rouge mixing is sent into double screw extruder after moving to kneader kneading 3h, and the melt pelletization at 190 DEG C discharges, natural cooling, i.e.,
Obtain conductive polymer composites.
Comparative example 1: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that lacking composite base-material.
Comparative example 2: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that lacking conductive synergistic effect object.
Comparative example 3: the conductive polymer composites of Wuxi City company production.
Embodiment and comparative example are tested according to GB/T 15738-1995 standard, test result is as shown in table 1.
Table 1:
In summary, conductive polymer composites of the invention have preferable mechanical property electric conductivity, are worth promoting.
Claims (10)
1. a kind of conductive polymer composites, according to the mass fraction, including following component: 6 ~ 10 parts of terephthalic acid (TPA)s, 3 ~ 7 parts
Triethylene diamine, 10 ~ 15 parts of epoxy resin, 1 ~ 4 part of plasticizer, 3 ~ 7 parts of surfactants, 2 ~ 5 parts of auxiliary agents, 20 ~ 45 parts of water,
It is characterized in that, further includes: 25 ~ 50 parts of composite base-materials, 12 ~ 20 parts of conductive synergistic effect objects.
2. a kind of conductive polymer composites according to claim 1, which is characterized in that the preparation side of the composite base-material
Method includes the following steps:
(1) 4:1 ~ 2:30 ~ 50 take 4- chloro-benzoic anhydride, 4,4 in mass ratio,Diaminodiphenyl ether, reagent A mixing, lead to nitrogen protection,
Stirring, obtains reactant, takes reactant 30 ~ 50:1:1 in mass ratio ~ 3 that toluene, water mixing is added, derived from monomer processed, is derived from
4,4- dihydroxy diphenyl propane, potassium carbonate mixing is added in monomer processed 12 ~ 18:1:1 in mass ratio ~ 3, anti-in 150 ~ 170 DEG C of reflux
It answers, obtains the double sylvite of bisphenol-A, take the double sylvite 1:6 in mass ratio ~ 10 of bisphenol-A that dehydrated alcohol mixing is added, stand, filter, take filter residue
It is washed with water, it is dry, obtain base-material；
(2) in 40 ~ 60 DEG C, 1:3 ~ 5:12 ~ 20 take silane coupling agent KH-560, white carbon black, sodium carbonate liquor mixing in mass ratio
Stirring is kept the temperature, and filtering takes filter cake to be washed with water, dry, obtains dried object, take dried object 1:5 ~ 8:0.1 in mass ratio be added base-material,
Auxiliary material mixing, ball milling obtain ball milling material, take ball milling material under an argon atmosphere, and low-temperature plasma processing discharges to get composite base-material.
3. a kind of conductive polymer composites according to claim 2, which is characterized in that the reagent in the step (1)
A: 30 ~ 50:1 in mass ratio takes n,N-dimethylacetamide, magnesium sulfate to be mixed, and filters, and collects filtrate decompression distillation, collects
Fraction stands to get reagent A.
4. a kind of conductive polymer composites according to claim 2, which is characterized in that the auxiliary material in the step (2):
3:1 ~ 2 take glycerol, dimethyl silicone polymer mixing to get auxiliary material in mass ratio.
5. a kind of conductive polymer composites according to claim 1, which is characterized in that the conduction synergistic effect object
Preparation method includes the following steps:
S1. it taking graphene oxide 1:20 in mass ratio ~ 30 that hydrochloric acid solution is added to be mixed, ultrasonic oscillation obtains dispersion liquid, in
0 ~ 5 DEG C, take dispersion liquid 15 ~ 25:1 in mass ratio that pyrroles is added, stirring obtains mixed liquor, in ice-water bath, in mass ratio 20 ~ 30:1:
4 take mixed liquor, ammonium persulfate, hydrochloric acid solution to be mixed, and ethanol solution is added and adjusts pH, is stored at room temperature, filters, and take filter residue dry
It is dry, obtain graphene oxide-polypyrrole；
S2. in 55 ~ 70 DEG C, petroleum coke powder, pre-treating fly ash, reagent B is taken to be mixed for 5:1 ~ 3:40 ~ 60 in mass ratio,
Mixture is obtained, takes mixture 8:1 in mass ratio ~ 3 that graphene oxide-polypyrrole mixing is added, ultrasonication obtains disperse materials,
Disperse materials are taken to be concentrated in vacuo to get conductive synergistic effect object.
6. a kind of conductive polymer composites according to claim 5, which is characterized in that the pretreatment in the step S2
Flyash: it takes flyash 1:12 in mass ratio ~ 20 that hydrochloric acid solution is added and is mixed, be stored at room temperature, filter, take filter residue by quality
Iron powder, aluminium hydroxide mixing and ball milling is added than 6 ~ 10:1:0.4, obtains ball milling material, takes the roasting of ball milling material to get pre-treating fly ash.
7. a kind of conductive polymer composites according to claim 5, which is characterized in that the reagent B in the step S2:
1:5 ~ 8:25 in mass ratio takes sodium citrate, ammonium persulfate, water mixing to get reagent B.
8. a kind of conductive polymer composites according to claim 1, which is characterized in that the plasticizer: in mass ratio
1:3 ~ 6 take dibutyl phthalate, triethyl citrate mixing to get plasticizer.
9. a kind of conductive polymer composites according to claim 1, which is characterized in that the auxiliary agent: 4:1 in mass ratio
~ 2 take carbamide, methyl-silicone oil mixing to get auxiliary agent.
10. a kind of conductive polymer composites according to claim 1, which is characterized in that the surfactant: pressing matter
Amount takes neopelex, the mixing of laureth sodium sulfovinate to get surfactant than 1:4 ~ 7.
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