CN109735064A - A kind of conductive agglomerate and preparation method thereof - Google Patents
A kind of conductive agglomerate and preparation method thereof Download PDFInfo
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- CN109735064A CN109735064A CN201811605857.0A CN201811605857A CN109735064A CN 109735064 A CN109735064 A CN 109735064A CN 201811605857 A CN201811605857 A CN 201811605857A CN 109735064 A CN109735064 A CN 109735064A
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Abstract
The present invention provides a kind of conductive agglomerate and preparation method thereof, and raw material includes graphite oxide, carbon nanotube, polymer powder, auxiliary agent.One of emphasis of the invention is to realize the uniform and stable dispersion of carbon nanotube.The present invention wraps up dispersing Nano carbon tubes using graphene oxide, it can effectively prevent carbon nanotube Second Aggregation, improve its dispersibility in high-viscosity polymer melt, simultaneously, the graphene oxide of addition restores under master batch processing temperature, the electric conductivity of conductive network of carbon nanotubes is further increased, the master batch with superior electrical conductivity is obtained in few additive.
Description
Technical field
The present invention relates to conductive plastics fields, more particularly to a kind of conductive agglomerate and preparation method thereof.
Background technique
Plastic products have many excellent performances, be therefore widely used in food, clothes, building, electronics, traffic,
The every field such as military affairs.But most polymers material is easy to produce accumulation of static electricity when in use, may cause product dust stratification, is stained with
Dirt, the problems such as causing electronic device electrostatic damage, accordingly, it sometimes is necessary to carry out antistatic treatment to polymer.Plastic products
Antistatic treatment is commonly divided into two methods of surface treatment type and internal addition type.Wherein, the modeling produced using conductive filler
Material products, antistatic property are typically derived from the electric conductivity of filler, antistatic durability and stability specific surface application type
It is good, and antistatic property influenced by ambient temperature and humidity it is small.
The conductive filler being widely adopted at present is carbon black, and carbon black generally forms conductive network in a manner of point contact, is led to
The conductive black for often needing to add high concentration (15~30wt%) in the polymer can just make material have antistatic or conductivity
Energy；Carbon black threshold value when using as conductive filler is higher and excessive section is narrow, and the fluctuation of carbon black concentration small range can be led
The variation for sending a telegraph 2~5 orders of magnitude of resistance is unfavorable for technology controlling and process, and there are problems that carbon black is migrated to product surface, makes product
Conductive stability decline.
Compared to carbon black, it is to prepare conductive plastics that carbon nanotube and graphene, which have excellent electric conductivity and mechanical property,
The ideal conducting filler of master batch.However, carbon nanotube and graphene all have high specific surface area, have between each other very strong
Van der Waals force, it is difficult to disperse.The prior art directly using carbon nanotube or graphene as conductive filler, passes through melt blending process
Polymer is added, the high viscosity of melt has been further exacerbated by the difficulty of carbon nanotube or graphene dispersion, has caused filler utilization rate
It is low, the problems such as resistivity is unevenly distributed, Mechanical Properties of Products decline.
In view of this, researcher proposes kinds of schemes to solve the dispersion of carbon nanotube or graphene.Wherein
Most common method is that the auxiliary agents such as surfactant are added in the medium, this improves carbon nanotube or graphite to a certain extent
The dispersibility of alkene, but dispersion effect is limited, and different medium may correspond to different dispersing agents, poor universality.Another method is
Carbon nanotube or graphene are subjected to chemical modification processing, this mode can change the surface chemistry form of packing material, destroy
Its physical property.And surfactant used in the above method and chemical modification medicament etc., it will increase the raw material of manufacturing process
Cost and environmentally friendly cost.
Therefore, the height of conductive filler how is realized on the basis of not destroying carbon nanotube and graphene excellent physicochemical property
Effect and stable dispersion, are the key that prepare conducting polymer materials.
Summary of the invention
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of conductive agglomerate and its preparation sides
Method promotes the electric conductivity of conductive agglomerate for reducing the surface resistivity of conductive agglomerate.
In order to achieve the above objects and other related objects, first aspect present invention provides a kind of conductive agglomerate, raw material packet
Include carbon nanotube, graphite oxide, polymer powder, auxiliary agent.
Optionally, by mass, carbon nanotube: graphite oxide: polymer powder: auxiliary agent=(0.1~10): (0.5~
15): (75~98): (0.1~0.5).
Optionally, by mass, carbon nanotube: graphite oxide: polymer powder: auxiliary agent=8:(1~6): (85~90):
1。
Optionally, the specific surface area of the carbon nanotube is 200~280 ㎡/g.
Optionally, the polymer powder is selected from polyethylene terephthalate (PET), polybutylene terephthalate (PBT)
(PBT), polystyrene (PS), polycarbonate (PC), polyamide (PA), polypropylene (PP), polyformaldehyde (POM), acrylic nitrile-butadiene two
At least one of alkene-styrene copolymer (ABS), polyacrylonitrile (PAN), by the way that different polymer powders is added,
It is female that corresponding conducting PET master batch, conduction PBT master batch, conduction PS master batch, conduction PC master batch, conduction PA master batch, conduction PP is made
Grain, conduction POM master batch, conductive ABS masterbatch, conduction PAN master batch etc..
Optionally, the auxiliary agent is selected from least one of antioxidant, lubricant, coupling agent.
Optionally, the antioxidant is selected from antioxidant B215, antioxidant B561, antioxidant P-EPQ, anti-oxidant
At least one of agent B215, antioxidant B900, antioxidant S9228, antioxidant 1330.
Optionally, the lubricant is selected from ester lubricant, fatty acid lubricant, paraffin series lubricant agent and low-molecular-weight wax
At least one of lubricant.It is specifically as follows lubricant E wax etc..
Optionally, the coupling agent is selected from least one of titante coupling agent, silane coupling agent.
Optionally, the auxiliary agent includes antioxidant, lubricant, and the mass ratio of the two includes but is not limited to 1:1, anti-oxidant
Agent, lubricant mass ratio can according to need and be adjusted.
Second aspect of the present invention provides the preparation method of above-mentioned conductive agglomerate, comprising: is dissolved in graphite oxide, carbon nanotube
In water, graphene oxide-carbon nano tube dispersion liquid is made, graphene oxide-carbon nanotube mixed powder is dried to obtain, by the powder
Body is mixed with polymer powder, auxiliary agent, is granulated, is obtained conductive agglomerate.
Optionally, the wet concentration is from deionized water.
Optionally, first that graphite oxide is soluble in water, it is sanded, high-pressure homogeneous processing, obtains graphene oxide water solution,
Then carbon nanotube is added in the graphene oxide water solution, obtains the carbon nanotube dispersion dispersed by graphene oxide
Liquid.
Optionally, it is sanded, after high-pressure homogeneous processing, the D50 of obtained graphene oxide is 0.4~0.8 μm, average
The number of plies is 1~3.
Optionally, in graphene oxide water solution graphene oxide mass concentration be 0.1~1%, preferably 0.5~
1%.
Optionally, the concentration for first preparing graphite oxide is the aqueous solution of 3~5wt%, is sanded, high-pressure homogeneous processing obtains
Graphene oxide water solution and then the concentration for being diluted with water to graphene oxide are 0.1wt%~1wt%.It first prepares highly concentrated
The graphite oxide aqueous solution for spending (5%), can be improved sand milling and homogeneous efficiency.
Optionally, being sanded uses partial size for the zirconium pearl of 6~9mm, and revolving speed is set as 1200~2000 revs/min, grinding 3~5
Hour.
Optionally, homogeneous pressure is 20~200MPa, is recycled 2~5 times.
Homogeneous pressure is preferably 80~200MPa, more preferably 80~100MPa.
Optionally, after carbon nanotube being added into graphene oxide water solution, water is added to dilute mixed liquor, it is mixed after dilution
It closes in liquid, the gross mass content of graphene oxide and carbon nanotube is 1~2%.
Optionally, after the mixed liquor after being diluted, high speed shear, high-pressure homogeneous processing are carried out to mixed liquor.High speed is cut
Cutting speed degree is set as 3000~6000 revs/min.
Optionally, when high-pressure homogeneous processing, homogeneous pressure is 20~200MPa, is recycled 2~10 times.
Optionally, graphene oxide-carbon nano tube dispersion liquid drying mode selected from spray drying, freeze-drying in extremely
Few one kind.
Optionally, using high speed mixer by the graphene oxide-carbon nanotube mixed powder and polymer powder, help
Agent mixing.
Optionally, high speed mixer revolving speed is 500~1500r/min.
Optionally, stop stirring when temperature of charge is raised to 80~100 DEG C in equipment, when material reaches the temperature, wherein
Moisture be also sufficiently removed.
Optionally, it is granulated by double screw extruder.
Optionally, Granulation Equipments is selected from parallel dual-screw extruding machine.
Optionally, the parallel dual-screw extruding machine is divided into the control of 9 sections of warm areas, and the temperature of each section of warm area is set in 150~
300℃。
Conductive agglomerate obtained by the above method can be used separately as PP Pipe Compound, can also be by it with corresponding polymer
It is used after dilution.
Third aspect present invention provides the conductive plastics obtained using above-mentioned conductive agglomerate.
As described above, conductive agglomerate and preparation method thereof of the invention, have the advantages that emphasis of the invention it
One is to realize the uniform and stable dispersion of carbon nanotube.The present invention wraps up dispersing Nano carbon tubes using graphene oxide, can be effective
Carbon nanotube Second Aggregation is prevented, its dispersibility in high-viscosity polymer melt is improved, meanwhile, the graphene oxide of addition
It is restored under master batch processing temperature, further increases the electric conductivity of conductive network of carbon nanotubes, obtained in few additive
Master batch with superior electrical conductivity.
Detailed description of the invention
Fig. 1 is shown as the preparation flow figure of conducting polymer master batch in embodiment.
Fig. 2 is shown as the carbon nanotube concentration and surface resistivity relationship of conductive agglomerate obtained by this patent method.
Fig. 3 is shown as graphene oxide in embodiment-carbon nano tube dispersion liquid photo.
Fig. 4 is shown as the resulting conducting polymer master batch scanning electron microscope microphoto of embodiment 1.
Fig. 5 is shown as the resulting conducting polymer master batch scanning electron microscope microphoto of embodiment 2.
Fig. 6 is shown as the resulting conducting polymer master batch scanning electron microscope microphoto of embodiment 3.
Fig. 7 is shown as the resulting conducting polymer master batch scanning electron microscope microphoto of comparative example 1.
Specific embodiment
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
The present invention provides a kind of preparation method of conductive agglomerate, Fig. 1 is shown as the preparation flow of conducting polymer master batch
Figure, one of emphasis are to realize that the efficient stable of carbon nanotube disperses, and method includes:
Graphite oxide is obtained into graphene oxide water solution with high-pressure homogeneous through being sanded；Graphite oxide is added in carbon nanotube
It is clipped and high-pressure homogeneous in aqueous solution, obtain graphene oxide-carbon nano tube dispersion liquid.Because graphene oxide is with more
Polar group, not needing complicated technology can be evenly dispersed in water；Under high shear condition, carbon nanotube is opened, oxygen
Graphite alkene wraps up carbon nanotube, and stable dispersion is in water, without adding chemical assistant, preparation process environmental protection.
High-pressure homogeneous treated mixed solution is subjected to spray drying treatment, it is mixed to obtain graphene oxide-carbon nanotube
Close powder.
Graphene oxide-carbon nanotube dust, polymer powder and auxiliary agent are stirred evenly through high speed mixer, using double
Screw extruder is granulated, and mutually overlap joint forms conductive network to carbon nanotube in the melt；Simultaneous oxidation graphene is being granulated
At a temperature of be reduced to graphene, further increase the electric conductivity of conductive network of carbon nanotubes, graphene and polymer are steady
It is fixed to combine, it migrate carbon nanotube can not, enhance conductive stability.
Specifically, comprising:
S1: graphite oxide is sanded and high-pressure homogeneous dispersion obtains graphene oxide water solution；
It is sanded and uses 6~9mm zirconium pearl, revolving speed is set as 1200~2000 revs/min, grinds 3~5 hours；Homogeneous pressure is
20-200MPa is recycled 2~5 times.This step makes oxidized graphite into oxidation stone using the shearing force being sanded and homogenizing process generates
Black aqueous solution, and reduce the number of plies and piece diameter of graphene oxide, so that the D50 of graphene oxide is reached 0.4~0.8 μm, it is average
The number of plies is 1~3 layer.
S2: carbon nanotube is added in graphene oxide water solution through high speed shear and high-pressure homogeneous, graphite oxide is obtained
Alkene-carbon nano tube dispersion liquid, Fig. 3 are shown as graphene oxide-carbon nano tube dispersion liquid photo.
This step weakens the model moral between carbon nanotube using the high shear force that high-speed mixer and high pressure homogenizer generate
Hua Li, after carbon nanotube is opened, graphene oxide is wrapped in carbon nano tube surface, prevents the Second Aggregation of carbon nanotube, obtains
To graphene oxide-carbon nano tube dispersion liquid；Homogeneous 20~200Mpa of pressure, solution recycle 2~10 times in homogenizer, homogeneous
The high shear force of machine is evenly dispersed in aqueous solution by carbon nanotube and graphene oxide, obtains graphene oxide and carbon nanotube
Mixed dispersion liquid.
S2: treated that dispersion liquid is spray-dried to high-pressure homogeneous, obtains graphene oxide-carbon nanotube mixed powder
Body；
Mixed dispersion liquid is dried to obtain uniformly mixed graphene oxide-carbon in the way of spray drying by this step
Nanotube mixed powder.
S3: by graphene oxide-carbon nanotube dust, polymer powder and auxiliary agent through high speed mixer uniform stirring, most
It is granulated afterwards using double screw extruder, obtains conductive agglomerate.
In this step, high speed mixer can effectively be mixed graphene oxide-carbon nanotube dust with polymer powder
Uniformly, polymer powder used removes moisture through 120 DEG C of bakings in advance, and when mixing, generated temperature reached 80-100 DEG C, also may be used
Moisture remaining in mixture is removed；Double screw extruder is arranged using parallel equidirectional two-screw, and graphene oxide is in master batch
It is restored under processing temperature, and forms stable conductive network in a polymer matrix together with carbon nanotube.
In order to become apparent from the preparation method for introducing a kind of conductive agglomerate provided by the present invention in detail, below with reference to tool
Body embodiment is illustrated.
In following embodiment, polymer P ET slice is purchased from Co., Ltd, Fujian petrochemical industry group, antioxidant
B215 and lubricant E wax are purchased from BASF China.
Embodiment 1
In the present embodiment, by mass, the raw material proportioning used is carbon nanotube: graphite oxide: polymer P ET powder:
Antioxidant B215: lubricant E wax=8:1:90:0.5:0.5.
The conductive agglomerate preparation method of the present embodiment includes the following steps:
(1) 50g graphite oxide is sanded together with 950g deionized water, sand mill revolving speed is set as 1800 revs/min, is sanded
Time is 3 hours；Add deionization, gained slurry water is diluted to the 1wt% (matter i.e. according to graphite oxide in entire aqueous solution
Amount accounting carries out adding water for 1%), it is then added into high pressure homogenizer, homogenization pressure is set as 80Mpa, and homogeneous 5 are followed
Ring obtains the graphene oxide water solution that mass ratio is 1%；
It (2) is 250m by 400g specific surface area2The carbon nanotube of/g is added in graphene oxide water solution, and deionization is added
Water, by mixed liquor be diluted to 1wt% (i.e. according to graphite oxide and the gross mass accounting of carbon nanotube in aqueous solution be 1% into
Row plus water), and stir evenly；By the homogenization under 80Mpa pressure of above-mentioned mixed solution, graphene oxide-carbon nanotube is obtained
Dispersion liquid；
(3) mixed dispersion liquid is spray-dried, obtain graphene oxide-carbon nanotube mixed powder, drier air inlet
Temperature is controlled at 240 DEG C；
(4) by graphene oxide-carbon nanotube mixed powder, polymer P ET powder, antioxidant B215 and lubricant E
Wax is added high speed mixer and is uniformly mixed, and stops stirring when equipment inner powder temperature is raised to 100 DEG C, powder is passed through twin-screw
Extruder is granulated to obtain conductive agglomerate, and extruder is divided into 9 sections of warm area controls, and specifically, the temperature of 1~warm area of warm area 9 is set respectively
Be set to: 220 DEG C, 265 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 260 DEG C, screw speed is set as 320
Rev/min.
Fig. 4 show the resulting conducting polymer master batch scanning electron microscope microphoto of the present embodiment.
Embodiment 2
In the present embodiment, by mass, the raw material proportioning used is carbon nanotube: graphite oxide: polymer P ET powder:
Antioxidant B215: lubricant E wax=8:2:89:0.5:0.5.
The conductive agglomerate preparation method of the present embodiment includes the following steps:
(1) 100g graphite oxide is sanded together with 1900g deionized water, sand mill revolving speed is set as 1800 revs/min, sand
Time consuming is 3 hours；Deionized water is added to be diluted to 1wt% (i.e. according to graphite oxide in entire aqueous solution in gained slurry
Quality accounting carries out adding water for 1%), it is then added into high pressure homogenizer, homogenization pressure is set as 80Mpa, and homogeneous 5 are followed
Ring obtains the graphene oxide water solution that mass ratio is 1%；
It (2) is 250m by 400g specific surface area2Graphene oxide water solution is added in the carbon nanotube of/g, and deionization is added
Mixed liquor is diluted to 1wt% by water, and is stirred evenly (i.e. according to graphite oxide and the gross mass of carbon nanotube in aqueous solution
Accounting carries out adding water for 1%)；By the homogenization under 80Mpa pressure of above-mentioned mixed solution, graphene oxide-carbon nanotube is obtained
Dispersion liquid；
(3) mixed dispersion liquid is spray-dried, obtain graphene oxide-carbon nanotube mixed powder, drier air inlet
Temperature is controlled at 240 DEG C；
(4) by graphene oxide-carbon nanotube mixed powder, polymer P ET powder, antioxidant B215 and lubricant E
Wax is added high speed mixer and is uniformly mixed, and stops stirring when equipment inner powder temperature is raised to 100 DEG C, powder is passed through twin-screw
Extruder is granulated to obtain conductive agglomerate, and extruder is divided into 9 sections of warm area controls, and specifically, the temperature of 1~warm area of warm area 9 is set respectively
Be set to: 220 DEG C, 265 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 260 DEG C, screw speed is set as 320
Rev/min.
Fig. 5 show the resulting conducting polymer master batch scanning electron microscope microphoto of the present embodiment.
Embodiment 3
In the present embodiment, by mass, the raw material proportioning used is carbon nanotube: graphite oxide: polymer P ET powder:
Antioxidant B215: lubricant E wax=8:6:85:0.5:0.5.
The conductive agglomerate preparation method of the present embodiment includes the following steps:
(1) 300g graphite oxide is sanded together with 5700g deionized water, sand mill revolving speed is set as 1800 revs/min, sand
Time consuming is 3 hours；Deionized water is added to be diluted to 1wt% (i.e. according to graphite oxide in entire aqueous solution in gained slurry
Quality accounting carries out adding water for 1%), it is then added into high pressure homogenizer, homogenization pressure is set as 80Mpa, and homogeneous 5 are followed
Ring obtains the graphene oxide water solution that mass ratio is 1%；Each embodiment
It (2) is 250m by 400g specific surface area2The carbon nanotube of/g is added in graphene oxide water solution, and deionization is added
Water, by mixed liquor be diluted to 1wt% (i.e. according to graphite oxide and the gross mass accounting of carbon nanotube in aqueous solution be 1% into
Row plus water), and stir evenly；By the homogenization under 80Mpa pressure of above-mentioned mixed solution, graphene oxide-carbon nanotube is obtained
Dispersion liquid；
(3) mixed dispersion liquid is spray-dried, obtain graphene oxide-carbon nanotube mixed powder, drier air inlet
Temperature is controlled at 240 DEG C；
(4) by graphene oxide-carbon nanotube mixed powder, polymer P ET powder, antioxidant B215 and lubricant E
Wax is added high speed mixer and is uniformly mixed, and stops stirring when equipment inner powder temperature is raised to 100 DEG C, powder is passed through twin-screw
Extruder is granulated to obtain conductive agglomerate, and the temperature of 1~warm area of warm area 9 of extruder is set separately are as follows: 220 DEG C, 265 DEG C, 270
DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 260 DEG C, screw speed is set as 320 revs/min.
Fig. 6 show the resulting conducting polymer master batch scanning electron microscope microphoto of the present embodiment.
Comparative example 1
Comparative example 1 is not add the conductive agglomerate of graphene oxide, and by mass, raw material proportioning is carbon nanotube: oxidation
Graphite: polymer P ET powder: antioxidant B215: lubricant E wax=8:0:91:0.5:0.5.
Preparation process is as follows:
It (1) is 250m by 400g specific surface area2The carbon nanotube of/g is mixed with deionized water, obtains quality through high speed shear
Than for 1wt% aqueous solution (quality accounting i.e. according to graphite oxide in entire aqueous solution be 1% carry out plus water), by its
Homogenization under 80Mpa pressure, obtains carbon nano tube dispersion liquid；
(2) carbon nano tube dispersion liquid is spray-dried, obtain carbon nanotube dust；
(3) high speed mixer is added in carbon nanotube dust, polymer P ET powder, antioxidant B215 and lubricant E wax
It is uniformly mixed, stops stirring when equipment inner powder temperature is raised to 100 DEG C, powder will be granulated to obtain by double screw extruder
Conductive agglomerate, extruder are divided into 9 sections of warm area controls, and specifically, the temperature of 1~warm area of warm area 9 is set separately are as follows: 220 DEG C, 265
DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 260 DEG C, screw speed is set as 320 revs/min.
Fig. 7 show the resulting conducting polymer master batch scanning electron microscope microphoto of this comparative example.
Resistance test and scanning electron microscope analysis are as follows:
Conductive agglomerate obtained by above-mentioned all embodiment and comparative examples is quickly cooled down through hot pressing, is made with a thickness of the thin of 1mm
Piece, and sheet resistance test and sem test are carried out, sheet resistance test reference " GB/T1410-2006 solid insulation material
Expect volume resistivity and surface resistivity test method ", in conjunction with the stereoscan photograph of Fig. 4-7, obtain following result:
Table 1
Above-described embodiment statistics indicate that, when graphene oxide content is lower in master batch, carbon nanotube is preferably dispersed；Oxygen
When graphite alkene adding too much, the electric conductivity of master batch declines instead, and graphene oxide excessive at this time will inhibit carbon nanometer
Overlap joint, hinders the formation of conductive network.
Embodiment statistics indicate that, using the method for the present invention prepare conducting polymer master batch, carbon nanotube and oxidation stone
For black alkene when mass ratio is 8:2 in master batch, the surface resistivity of agglomerate material is 1.35 ± 0.03*103Ohm/sq, electric conductivity
Well, it is better than embodiment 1 and 3.
Embodiment 4-9
The formula and sheet resistance of embodiment 4-9 is as shown in table 2, and preparation method is referring to embodiment 1.
Table 2
From table 2 it can be seen that the conduction that different surfaces resistivity can also be made is female according to the different demands to electric conductivity
Grain, obtained conductive agglomerate reunion is less, and well dispersed, conductive network is uniform.
Fig. 2 is the carbon nanotube additive amount and surface resistivity relational graph of the conductive agglomerate of the method for the invention preparation,
Wherein, the percentages of total raw material quality are accounted for by each raw material component quality, carbon nanotube additive amount as shown in the abscissa of Fig. 2,
Graphite oxide additive amount is 2wt%, and antioxidant B215 and lubricant E wax respectively add 0.5wt%, and surplus is polymer P ET powder
Body, figure it is seen that since carbon nanotube is in the polymer by the dispersion of efficient stable, so with the increasing of carbon pipe content
Add, material surface resistivity variation tendency is more gentle.
In conclusion one of emphasis of the invention is to realize the uniform and stable dispersion of carbon nanotube.The present invention uses oxygen
Graphite alkene wraps up dispersing Nano carbon tubes, can effectively prevent carbon nanotube Second Aggregation, improve it in high-viscosity polymer melt
In dispersibility, meanwhile, the graphene oxide of addition restores under master batch processing temperature, further increases carbon nanotube conducting
The electric conductivity of network obtains the master batch with superior electrical conductivity in few additive.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (10)
1. a kind of conductive agglomerate, it is characterised in that: its raw material includes carbon nanotube, graphite oxide, polymer powder, auxiliary agent.
2. conductive agglomerate according to claim 1, which is characterized in that by mass, carbon nanotube: graphite oxide: polymerization
Powder: auxiliary agent=(0.1~10): (0.5~15): (75~98): (0.1~0.5), it is preferable that carbon nanotube: oxidation stone
Ink: polymer powder: auxiliary agent=8:(1~6): (85~90): 1.
3. conductive agglomerate according to claim 1 or 2, it is characterised in that: the polymer powder is selected from poly- terephthaldehyde
Sour second diester (PET), polybutylene terephthalate (PBT) (PBT), polystyrene (PS), polycarbonate (PC), polyamide (PA),
Polypropylene (PP), POM (polyformaldehyde), acrylonitrile-butadiene-styrene terpolymer (ABS), in polyacrylonitrile (PAN)
It is at least one.
4. conductive agglomerate according to claim 1, it is characterised in that: the auxiliary agent is selected from antioxidant, lubricant, coupling
At least one of agent.
5. conductive agglomerate according to claim 4, it is characterised in that: the antioxidant is selected from antioxidant B215, resists
Oxidant B561, antioxidant P-EPQ, antioxidant B215, antioxidant B900, antioxidant S9228, antioxidant 1330
At least one of；
And/or the lubricant is selected from ester lubricant, fatty acid lubricant, paraffin series lubricant agent, low-molecular-weight wax lubricant
At least one of；
And/or the coupling agent is selected from least one of titante coupling agent, silane coupling agent.
6. conductive agglomerate according to claim 4, it is characterised in that: the auxiliary agent includes antioxidant, lubricant, the two
Mass ratio be 1:1.
7. the preparation method of conductive agglomerate described in -6 any one according to claim 1 characterized by comprising stone will be aoxidized
Ink, carbon nanotube are soluble in water, and graphene oxide-carbon nano tube dispersion liquid is made, is dried to obtain graphene oxide-carbon nanotube
Mixed powder mixes the powder with polymer powder, auxiliary agent, is granulated, obtains conductive agglomerate.
8. preparation method according to claim 7, it is characterised in that: be first dispersed in water graphite oxide, aoxidized
Then graphene aqueous solution carbon nanotube is added in the graphene oxide water solution, obtain by graphene oxide dispersion
Carbon nano tube dispersion liquid.
9. preparation method according to claim 7, which is characterized in that further include one or more in following technical characteristic
It is a:
1) graphene oxide water solution concentration is 0.1~1wt%, preferably 0.5~1wt%；
2) wet concentration is from deionized water；
3) first that graphite oxide is soluble in water, it is sanded, high-pressure homogeneous processing, graphene oxide water solution is obtained, then by carbon
Nanotube is added in the graphene oxide water solution, obtains the carbon nano tube dispersion liquid dispersed by graphene oxide；
4) through being sanded, after high-pressure homogeneous processing, the D50 of obtained graphene oxide is 0.4~0.8 μm, the average number of plies is 1~
3 layers；
5) it is first sanded, the graphene oxide water solution that high-pressure homogeneous processing obtains concentration as 3~5wt%, adds water and be diluted to
The concentration of graphite oxide is 0.1wt%~1wt%；
6) when being sanded, revolving speed is set as 1200~2000 revs/min, grinds 3~5h；
7) when preparing graphene oxide water solution, homogeneous pressure is 20~200MPa, is recycled 2~5 times；
8) after carbon nanotube being added into graphene aqueous solution, water is added to dilute mixed liquor, in the mixed liquor after dilution, aoxidizes stone
The gross mass content of ink and carbon nanotube is 1~2%；
9) after the mixed liquor after being diluted, high speed shear, high-pressure homogeneous processing are carried out to mixed liquor；
10) after the mixed liquor after being diluted, when carrying out high-pressure homogeneous processing to mixed liquor, homogeneous pressure is 20~200MPa,
Circulation 2~10 times；
11) graphene oxide-carbon nano tube dispersion liquid drying mode is selected from least one of spray drying, freeze-drying；
12) graphene oxide-carbon nanotube mixed powder is mixed with polymer powder, auxiliary agent using high speed mixer；
13) high speed mixer revolving speed is 500~1500r/min；
14) stop stirring when temperature of charge is raised to 80~100 DEG C in equipment, into subsequent granulation process；
15) it is granulated by double screw extruder；
16) Granulation Equipments is selected from parallel dual-screw extruding machine；
17) parallel dual-screw extruding machine is divided into 9 sections of warm area controls, in addition to feed end, the temperature setting of remaining every section warm area
At 150~300 DEG C.
10. utilizing conductive plastics made from conductive agglomerate described in claim 1-6 any one.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110305437A (en) * | 2019-06-14 | 2019-10-08 | 新奥石墨烯技术有限公司 | Graphene/carbon nano-tube compound, conducting function macromolecule, preparation method |
| CN110437579A (en) * | 2019-08-02 | 2019-11-12 | 宁波墨西科技有限公司 | A kind of antistatic PEEK composite material and preparation method of graphene |
| CN111293311A (en) * | 2020-02-20 | 2020-06-16 | 北京辉腾格勒石墨烯科技有限公司 | Conductive agent slurry, preparation method of conductive agent slurry and battery positive electrode slurry |
| CN112266548A (en) * | 2020-09-28 | 2021-01-26 | 山东鲁泰化学有限公司 | Long-acting antistatic foamed polyvinyl chloride |
| CN113929932A (en) * | 2021-08-30 | 2022-01-14 | 镇江新纳材料科技有限公司 | Preparation method and preparation equipment applied to carbon nanotube master batch |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090227162A1 (en) * | 2006-03-10 | 2009-09-10 | Goodrich Corporation | Low density lightning strike protection for use in airplanes |
| CN103333368A (en) * | 2013-07-19 | 2013-10-02 | 中物院成都科学技术发展中心 | Compound dispersing agent of carbon nanomaterial and method for preparing electric conduction polymeric composite thereof |
| CN104292488A (en) * | 2014-08-25 | 2015-01-21 | 哈尔滨工业大学 | Preparation method of polyimides composite film with high conductive surface |
| CN105131359A (en) * | 2015-09-19 | 2015-12-09 | 四川大学 | Graphene/carbon nano tube hybridized filler network enhanced rubber material and preparation method thereof |
| CN106189088A (en) * | 2016-07-19 | 2016-12-07 | 沈阳航空航天大学 | A kind of preparation method of CNT graphene oxide hybrid buildup composite |
-
2018
- 2018-12-27 CN CN201811605857.0A patent/CN109735064A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090227162A1 (en) * | 2006-03-10 | 2009-09-10 | Goodrich Corporation | Low density lightning strike protection for use in airplanes |
| CN103333368A (en) * | 2013-07-19 | 2013-10-02 | 中物院成都科学技术发展中心 | Compound dispersing agent of carbon nanomaterial and method for preparing electric conduction polymeric composite thereof |
| CN104292488A (en) * | 2014-08-25 | 2015-01-21 | 哈尔滨工业大学 | Preparation method of polyimides composite film with high conductive surface |
| CN105131359A (en) * | 2015-09-19 | 2015-12-09 | 四川大学 | Graphene/carbon nano tube hybridized filler network enhanced rubber material and preparation method thereof |
| CN106189088A (en) * | 2016-07-19 | 2016-12-07 | 沈阳航空航天大学 | A kind of preparation method of CNT graphene oxide hybrid buildup composite |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110305437A (en) * | 2019-06-14 | 2019-10-08 | 新奥石墨烯技术有限公司 | Graphene/carbon nano-tube compound, conducting function macromolecule, preparation method |
| CN110437579A (en) * | 2019-08-02 | 2019-11-12 | 宁波墨西科技有限公司 | A kind of antistatic PEEK composite material and preparation method of graphene |
| CN111293311A (en) * | 2020-02-20 | 2020-06-16 | 北京辉腾格勒石墨烯科技有限公司 | Conductive agent slurry, preparation method of conductive agent slurry and battery positive electrode slurry |
| CN112266548A (en) * | 2020-09-28 | 2021-01-26 | 山东鲁泰化学有限公司 | Long-acting antistatic foamed polyvinyl chloride |
| CN113929932A (en) * | 2021-08-30 | 2022-01-14 | 镇江新纳材料科技有限公司 | Preparation method and preparation equipment applied to carbon nanotube master batch |
| CN113929932B (en) * | 2021-08-30 | 2023-09-05 | 镇江新纳材料科技有限公司 | Preparation method and preparation equipment applied to carbon nano tube master batch |
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