CN104844822B - A kind of graphene conductive master batch and its preparation method and application - Google Patents
A kind of graphene conductive master batch and its preparation method and application Download PDFInfo
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- CN104844822B CN104844822B CN201510200391.6A CN201510200391A CN104844822B CN 104844822 B CN104844822 B CN 104844822B CN 201510200391 A CN201510200391 A CN 201510200391A CN 104844822 B CN104844822 B CN 104844822B
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Abstract
The present invention relates to plastic master batch preparing technical fields, specifically disclose a kind of graphene conductive master batch and its preparation method and application.The preparation method of the graphene conductive master batch, comprises the following steps：S1. antistatic agent dissolving is obtained into solution A in organic solvent；S2. graphene is put into organic solvent for ultrasonic dispersion, solution A is added under ultrasound and mechanical agitation, concentration removes organic solvent and obtains paste；S3. paste is heated and melted, then the paste of melting through freely falling body is dripped, is cooled down up to the graphene conductive master batch.The graphene conductive master batch has excellent volume resistivity, can form the high-effective conductive network of rotation section phase separation structure in the application.
Description
Technical field
The present invention relates to plastic master batch preparing technical fields, and in particular to a kind of graphene conductive master batch and preparation method thereof
And application.
Background technology
High molecular material obtains large-scale application in various fields such as national defence, military project, electronic products at present.It is but most of high
Molecular material has higher volume resistivity, and due to high molecular material self-resistance rate height, electrostatic is not easy to remove and cause to accumulate
Tired voltage is very big, production to plastic products and very big negative effect is caused using process.For example electrostatic can make in air
Dust be adsorbed on product and influence its appearance, reduce its commercial value, for another example product static electricity during printing can make ink or fuel
Attachment unevenness easily comes off, and electrostatic can generate electric discharge phenomena for another example, and then click is caused to be caught fire, the accidents such as smashed district.Electrostatic
It is also possible to the performance of damage product, such as the envelope assembly and disassembly behavior of electronic chip.It is most effective that this kind of electrostatic is reduced at present
Method be that conductive agglomerate is added in high molecular material.
The antistatic agents such as the carbon materials such as graphene and polyethylene is are squeezed by the existing method for preparing conductive agglomerate through twin-screw
Go out machine or mixer melt blending is prepared.Graphene can not effectively be divided in the preparation method of existing this conductive agglomerate
It dissipates, graphene is in mutual aggregating state（As shown in Figure 1）, it is necessary to lead each aggregate conductive network close to each other that could be formed
Electricity.Cause final application to reach certain volume resistivity as a result, must increase graphene dosage.Due to graphene
Material is somewhat expensive, increases graphene dosage so as to which the cost of material can be caused to increase.On the other hand increasing graphene dosage can lead
Its material property applied is caused to decline.Therefore, develop it is a kind of have excellent volume resistivity, in practical applications being capable of shape
Conductive agglomerate into high-effective conductive network has good market prospects.
Invention content
The technical problems to be solved by the invention are, in order to overcome in the prior art conductive agglomerate cannot form high-effective conductive
The technical issues of network, bad electric conductivity, provides a kind of graphene conductive master batch.
Above-mentioned technical problem to be solved by this invention is achieved by the following technical programs：
A kind of preparation method of graphene conductive master batch, which is characterized in that comprise the following steps：
S1. antistatic agent dissolving is obtained into solution A in organic solvent；
S2. graphene is put into organic solvent for ultrasonic dispersion, adds in solution A under ultrasound and mechanical agitation, concentration removes
Organic solvent is gone to obtain paste；
S3. paste is heated and melted, then the paste of melting through freely falling body is dripped, is cooled down up to described
Graphene conductive master batch；
Antistatic agent described in S1 is in oleamide, erucyl amide, stearmide and pentaerythrite stearate
One or more.
The selected oleamide of the present invention, erucyl amide, stearmide and pentaerythrite stearate etc. are amorphous, have
The organic material of dispersion, lubrication and certain antistatic property, is mixed with conductive agglomerate, this side with graphene under solution state
Method can effectively open graphene dispersion, and the high-effective conductive network of rotation section phase separation structure is formed in practical application（Such as
Shown in Fig. 2）.It effectively prevents graphene dispersion in the prior art not open, forms happening for aggregating state.It can save significantly
About graphene usage amount, is greatly lowered industrial production cost.
Preferably, the weight consumption ratio of the graphene in the antistatic agent and S2 described in S1 is 1 ~ 2：1~2.
Most preferably, the weight consumption ratio of the graphene in the antistatic agent and S2 described in S1 is 1:1.
Preferably, the organic solvent described in S1 and S2 is ethyl alcohol.
Preferably, the ultrasonic disperse described in S2, jitter time are 1 ~ 3h.
Preferably, the graphene of 30 ~ 70% weight is contained in the paste described in S2.
Most preferably, the graphene containing 50% weight in the paste described in S2.
Preferably, the grain size that graphene conductive master batch is prepared in S3 is 2 ~ 4mm.
Most preferably, the grain size that graphene conductive master batch is prepared in S3 is 3mm.
The present invention provides a kind of graphene conductive master batch being prepared by above-mentioned preparation method.
The graphene conductive master batch is forming the application in revolving section Phase Separating Morphology high-effective conductive network.
Preferably, the application is that graphene conductive master batch and melt polymer material are blended, is formed after cooling
Rotation section Phase Separating Morphology high-effective conductive network.
Preferably, the high molecular material is polypropylene material（PP）, polythene material（PE）, polystyrene material
（PS）, ABS polymer（ABS）, impact resistant polystyrene material（HIPS）, polyamide 6 material
Material（PA6）Or polybutylene terephthalate (PBT) material（PBT）.
Relative to the prior art, the present invention has the advantages that：
（1）The present invention prepares graphene conductive master batch by the way of solution blending, has overturned existing melt blended side
Formula prepares graphene conductive master batch so that under the dosage for using identical grapheme material, volume resistivity is than prior art system
Small 5 ~ 6 orders of magnitude of volume resistivity of standby conductive agglomerate；
（2）Graphene is first disperseed in organic solvent, antistatic agent is then added in, stone can be effectively prevent after removing solvent
The reunion again of black alkene by tear drop after melting, is made with particle similar in plastic pellet size, appearance during convenient for then applying
Uneven situation is mixed, is used after facilitating mixing；
（3）With sour amide, erucyl amide, stearmide or pentaerythrite stearate, these are amorphous, have dispersion,
The organic material of lubrication and certain antistatic property can make graphene form rotation section phase separation structure in subsequent application
High-effective conductive network；Rather than as traditional master batch, it is necessary to which conducting particles forms leading for overlap joint close to each other in entire matrix
It is just conductive after electric network（Generally to reach 106, need more than 8% graphene）, in this way can be less with expensive graphene（Only need
4% or so graphene can reach 102Conductive effect）, reach identical conductive effect, greatly reduce cost.
Description of the drawings
Fig. 1 is the aggregate conductive schematic diagram close to each other that traditional graphene conductive master batch is formed.
Fig. 2 is the fully dispersed high-effective conductive network conduction schematic diagram for forming rotation section phase separation structure of graphene of the present invention.
Fig. 3 is the carbon nanomaterial scatter diagram in anti-static material PP described in embodiment 5.
Specific embodiment
The present invention is explained further, but embodiment does not do any type of limit to the present invention below in conjunction with specific embodiment
It is fixed.
Embodiment 1
S1. 200g oleamides are dissolved in 1L ethyl alcohol and obtain solution A；
S2. 200g graphenes are put into ultrasonic disperse 1h in 4L ethyl alcohol, add in solution A under ultrasound and mechanical agitation, subtract
Pressure concentration removes ethyl alcohol and obtains the paste containing 50% weight graphene；
S3. paste is heated and melted, then the paste of melting through freely falling body is dripped, is dropped in cold metal plate
Cool down grain size about 3mm graphene conductive master batch.
Embodiment 2
S1. 200g erucyl amides are dissolved in 1L ethyl alcohol and obtain solution A；
S2. 200g graphenes are put into ultrasonic disperse 1h in 4L ethyl alcohol, add in solution A under ultrasound and mechanical agitation, subtract
Pressure concentration removes ethyl alcohol and obtains the paste containing 50% weight graphene；
S3. paste is heated and melted, then the paste of melting through freely falling body is dripped, is dropped in cold metal plate
Cool down grain size about 3mm graphene conductive master batch.
Embodiment 3
S1. 200g stearmides are dissolved in 1L ethyl alcohol and obtain solution A；
S2. 200g graphenes are put into ultrasonic disperse 1h in 4L ethyl alcohol, add in solution A under ultrasound and mechanical agitation, subtract
Pressure concentration removes ethyl alcohol and obtains the paste containing 50% weight graphene；
S3. paste is heated and melted, then the paste of melting through freely falling body is dripped, is dropped in cold metal plate
Cool down grain size about 3mm graphene conductive master batch.
Embodiment 4
S1. 200g pentaerythrite stearates are dissolved in 1L ethyl alcohol and obtain solution A；
S2. 200g graphenes are put into ultrasonic disperse 1h in 4L ethyl alcohol, add in solution A under ultrasound and mechanical agitation, subtract
Pressure concentration removes ethyl alcohol and obtains the paste containing 50% weight graphene；
S3. paste is heated and melted, then the paste of melting through freely falling body is dripped, is dropped in cold metal plate
Cool down grain size about 3mm graphene conductive master batch.
The preparation of 5 anti-static material PP of embodiment
The graphene conductive master batch 800g and polypropylene material that embodiment 1 is prepared（PP）Material 9200g meltings are altogether
It is mixed, the anti-static material PP with rotation section Phase Separating Morphology high-effective conductive network is formed after double screw extruder squeezes out cooling
（The content of graphene is 4%）.
Embodiment 6
With reference to the preparation method of embodiment 5, the content for preparing graphene respectively is 4% anti-static material PE, antistatic material
Expect PS, anti-static material ABS, anti-static material HIPS, anti-static material PA6, anti-static material PBT.
The preparation of 1 conventional graphite alkene conductive agglomerate of comparative example
With traditional melting, by 200g polyethylene and 200g graphenes through mixer melt blending, then through single screw rod
Extruder extruding pelletization obtains conventional graphite alkene conductive agglomerate containing 50% weight graphene of the grain size for 3mm or so.
Comparative example 2
The conventional graphite alkene conductive agglomerate being prepared with comparative example 1 is blended with molten polymer material, is squeezed through twin-screw
Go out machine and squeeze out anti-static material PP that the content of graphene is 4%, anti-static material PE, antistatic is prepared after cooling respectively
Material PS, anti-static material ABS, anti-static material HIPS, anti-static material PA6, anti-static material PBT.
7 volume resistivity of embodiment and material properties test
The test method of volume resistivity：Using EST121 type numbers ultra-high resistance, micro current instrument, according to GB/
T1410-2006 is tested, and sample diameter 82mm, thick 2mm, each sample survey five groups, takes its average value.
As can be seen from Table 1, the graphene conductive master batch that the present invention is prepared has good volume resistivity.From table
2 and table 3 in data can be seen that the anti-static material that the graphene conductive master batch that is prepared of the present invention is prepared,
Graphene conductive master batch can form the high-effective conductive network of rotation section phase separation structure wherein so that its volume resistivity ratio uses
The resistivity of graphene conductive master batch that conventional method is prepared low 5 ~ 6 orders of magnitude, performance greatly improve.
Claims (9)
1. a kind of preparation method of graphene conductive master batch, which is characterized in that comprise the following steps：
S1. antistatic agent dissolving is obtained into solution A in organic solvent；
S2. graphene is put into organic solvent for ultrasonic dispersion, solution A is added under ultrasound and mechanical agitation, concentration, which removes, to be had
Solvent obtains paste；Contain the graphene of 30 ~ 70% weight in the paste；
S3. paste is heated and melted, then the paste of melting through freely falling body is dripped, is cooled down up to the graphite
Alkene conductive agglomerate；
Wherein, the antistatic agent described in S1 is in oleamide, erucyl amide, stearmide and pentaerythritol stearate
One or more；
The weight consumption ratio of the graphene in antistatic agent and S2 described in S1 is 1 ~ 2：1~2.
2. preparation method according to claim 1, which is characterized in that the graphene in antistatic agent and S2 described in S1
Weight consumption ratio be 1:1.
3. preparation method according to claim 1, which is characterized in that the organic solvent described in S1 and S2 is ethyl alcohol.
4. preparation method according to claim 1, which is characterized in that the ultrasonic disperse described in S2, jitter time 1
~3h。
5. the graphene conductive master batch being prepared by any one of claim 1 ~ 4 preparation method.
6. graphene conductive master batch described in claim 5 is forming the application in revolving section Phase Separating Morphology high-effective conductive network.
7. application according to claim 6, which is characterized in that be total to graphene conductive master batch with melt polymer material
It is mixed, rotation section Phase Separating Morphology high-effective conductive network is formed after cooling.
8. application according to claim 7, which is characterized in that the high molecular material is polypropylene material, polyethylene
Material, polystyrene material, ABS polymer, polyamide 6 material or poly terephthalic acid fourth
Naphthalate material.
9. application according to claim 8, which is characterized in that the polystyrene material is impact resistant polystyrene material
Material.
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| CN106128562B (en) | 2016-05-31 | 2017-07-28 | 京东方科技集团股份有限公司 | Conducting particles and its manufacture method and conducting resinl and its manufacture method |
| CN106977914A (en) * | 2017-04-17 | 2017-07-25 | 杭州高烯科技有限公司 | A kind of 6/ polypropylene of nylon/graphene nanocomposite material and preparation method thereof |
| CN110105785A (en) * | 2019-05-23 | 2019-08-09 | 浙江金彩新材料有限公司 | A kind of modified graphene master batch and preparation method thereof |
| CN113372648A (en) * | 2021-05-21 | 2021-09-10 | 大河宝利材料科技(苏州)有限公司 | Polypropylene and graphene conductive composite material |
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