CN106084404A - The polyethylene antistatic film that a kind of Activated Carbon Nanotubes is modified - Google Patents
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C08L2201/00—Properties
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- C08L2207/062—HDPE
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Abstract
The invention discloses the polyethylene antistatic film that a kind of Activated Carbon Nanotubes is modified, be made up of the component of following weight portion: PE polymeric matrix material 70～95 mass parts, Activated Carbon Nanotubes 0.01～10 mass parts, auxiliary agent 0.1～20 mass parts；Described auxiliary agent is one or more the mixing in dispersant B, coupling agent, antioxidant, lubricant, antifriction liniment；Described Activated Carbon Nanotubes is to be dissolved in solvent by dispersant A, obtains dispersant solution, is then sprayed into by dispersant solution in the CNT of high-speed stirred by high-pressure spraying method, after high-speed stirred mixing, prepares Activated Carbon Nanotubes.The polyethylene antistatic film electric conductivity that the present invention provides is good, and antistatic persistency is strong, and service life is long.
Description
One, technical field
The present invention relates to the polyethylene antistatic film that a kind of Activated Carbon Nanotubes is modified.
Two, background technology
Polyethylene (PE) enriches because of its raw material resources, moderate, and stable processing technique is reliable, and product combination property is excellent
More, its range of application day by day expands, particularly at packaging field, because its cost performance is better than other packaging material, and its consumption
Account for first of general-purpose plastics packaging material always.Along with the deep development of China's modernization construction, various plastics package materials
Material emerges in an endless stream, and its expense is the most increasing.Wherein PE packaging film accounts for more than the 30% of PE material total quantity consumed.Often
Year, PE material to be consumed was more than million tons.But owing to polythene material is non-polar molecular structure, be made up of its covalent bond divides
Subchain, can not ionize, and is also difficult to transmit free electron.Once after charged because friction makes electron exchange, be difficult to eliminate.PE
The electrostatic that material produces in the course of processing, to the many inconvenience being processed further bringing of packaging film material, have impact on system
Because being difficult to separately after being affected printing effect by static interference and making bag when the operating characteristics of product and thin film are used for packing
Or sealing, also can cause shock phenomenon time serious.
PE antistatic film mainly includes applying antistatic additive to prepare PE antistatic film, use conductivity type filler to produce PE
Antistatic plastic film, employing coating material production PE antistatic film etc..
Wherein, conductivity type filler is used to be possible not only to produce PE antistatic plastic thin film, and due to its antistatic behaviour base
In the electric conductivity of filler, persistency is good compared with surfactant type PE antistatic film, and antistatic behaviour is by the shadow of ambient humidity
Ring little.
In numerous conductivity type fillers, CNT has good electric conductivity, has again bigger draw ratio simultaneously, because of
And it is well suited for making conductive filler, relative to other metallic particles and graphite granule, its little consumption just can form conductive net,
And its density is more much smaller than metallic particles, it is difficult to the coagulation because of the effect of gravity.These characteristics utilizing CNT are made
Join in plastics for conducting medium, the electric conductivity of plastics can be produced strong impact.At present, CNT is at PE antistatic material
Applied research in material mainly by changing structure and the content of CNT, improves CNT dispersibility in PE,
And CNT is carried out surface process and equalize electric conductivity and other properties of PE anti-static material.
Three, summary of the invention
The invention provides the polyethylene antistatic film that a kind of Activated Carbon Nanotubes is modified, CNT is preprocessed to be changed
After property, add to PE material matrix as conductive filler, prepare polyethylene antistatic film.
The technical solution used in the present invention is:
The polyethylene antistatic film that a kind of Activated Carbon Nanotubes is modified, the polyethylene of described Activated Carbon Nanotubes modification resists
Electrostatic film is made up of the component of following weight portion:
PE polymeric matrix material 70～95 mass parts, Activated Carbon Nanotubes 0.01～10 mass parts, auxiliary agent 0.1～20 matter
Amount part；
Described auxiliary agent is the mixed of one or more in dispersant B, coupling agent, antioxidant, lubricant, antifriction liniment
Close；
Described Activated Carbon Nanotubes prepares by the following method:
Dispersant A is dissolved in solvent, obtains dispersant solution, then dispersant solution is sprayed into by high-pressure spraying method
In the CNT of high-speed stirred, after high-speed stirred mixing, prepare Activated Carbon Nanotubes.Described CNT, dispersant A, molten
The mass fraction ratio of agent is 85～95:0.1～5:5～10.
Described PE polymeric matrix material, Activated Carbon Nanotubes, the mass fraction of auxiliary agent be 70～95 mass parts, 0.01～
10 mass parts, 0.1～20 mass parts, preferably 70～95 mass parts, 1～10 mass parts, 0.1～20 mass parts；
Described auxiliary agent is the mixed of one or more in dispersant B, coupling agent, antioxidant, lubricant, antifriction liniment
Close；The most described auxiliary agent is mixed with dispersant B of one or more in coupling agent, antioxidant, lubricant, antifriction liniment
Close, one or more during more preferably auxiliary agent is coupling agent, antioxidant, antifriction liniment with dispersant B, lubricant mixed
Close.
Further, the most described auxiliary agent is dispersant B, coupling agent, antioxidant, lubricant and antifriction liniment, described raw material
Formula be: PE polymeric matrix material, Activated Carbon Nanotubes, dispersant B, coupling agent, antioxidant, lubricant, antifriction liniment
Mass fraction be 70～90 mass parts, 1～10 mass parts, 0.1～10 mass parts, 0.01～5 mass parts, 0.01～2 mass
Part, 0.01～10 mass parts, 0.01～5 mass parts, wherein dispersant B, coupling agent, antioxidant, lubricant and antifriction liniment
Total mass fraction is 0.1～20 mass parts.
Further, in preferred steps (2), the formula of raw material is: PE polymeric matrix material, Activated Carbon Nanotubes, dispersion
Agent B, coupling agent, antioxidant, lubricant, the mass fraction of antifriction liniment are 70～90 mass parts, 1～10 mass parts, 1～10 matter
Amount part, 0.01～3 mass parts, 0.01～2 mass parts, 0.01～3 mass parts, 0.01～5 mass parts, wherein dispersant B, coupling
Total mass fraction of agent, antioxidant, lubricant and antifriction liniment is 0.1～20 mass parts.
Further, in preferred steps (2), the formula of raw material is: PE polymeric matrix material, Activated Carbon Nanotubes, dispersion
Agent B, coupling agent, antioxidant, lubricant, the mass fraction of antifriction liniment are 70～90 mass parts, 3～8 mass parts, 1～8 mass
Part, 0.5～3 mass parts, 0.5～2 mass parts, 0.5～3 mass parts, 0.5～3 mass parts.
In described method, dispersant A and dispersant B are for distinguishing the dispersant used in different step, and A, B do not have
Chemical sense.
Described dispersant A and dispersant B each stand alone as dodecylbenzene sodium sulfonate, polyvinylpyrrolidone, polyethylene
Alcohol, xanthan gum, sodium lauryl sulphate, Triton X-100, sodium carboxymethyl cellulose, Dihexadecylphosphate, Ah
Draw primary glue, cetyl trimethylammonium bromide, alkyl phenol ethylene oxide condensation substance emulsifying agent, cetyl trimethyl sodium bromide,
One or more mixture in Kynoar.
Described solvent be water, N,N-dimethylformamide, N-Methyl pyrrolidone, n-butyl alcohol, chloroform, dehydrated alcohol, third
One or more mixture in ketone, petroleum ether, ethyl acetate, butyl acetate；
Described CNT, dispersant A, the mass fraction ratio of solvent are 85～95:0.1～5:5～10.
Described CNT is one or both the mixture in multi-walled carbon nano-tubes, SWCN, the most
Wall carbon nano tube.
Described PE polymeric matrix material is particle or pulverulent material, and PE polymer pulverulent material, average particle are preferably used
Footpath be 0.5 μm can be LDPE, HDPE, LLDPE or MDPE to 5mm, PE polymeric matrix material, preferably PE polymeric matrix material
The melt index of material is 2-100g/10min, preferably 10-30g/10min, the beneficially CNT dispersion in PE matrix.
Described coupling agent is one or more the mixture in titante coupling agent, silane coupling agent；Institute
Stating titante coupling agent can be isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, isopropyl three (dioctyl phosphoric acid
Acyloxy) titanate esters, isopropyl two oleic acid acyloxy (dioctyl phosphoric acid acyloxy) titanate esters, monoalkoxy unsaturated fatty acid
One or more mixture in titanate esters or Di(dioctylpyrophosphato) ethylene titanate；Described silane is even
Connection agent can use KH550, one or more the mixture in KH560, KH570, KH792, DL602, DL171；
Described antioxidant is preferably 1098,168,1010,1076, DLTP, one or more in MB, 164,264
Mixture.
Described lubricant is fatty acid, aliphatic amide type or ester lubricant, paraffin class lubricant, metallic soap salt profit
One or more mixing in lubrication prescription, low-molecular-weight wax, further, described lubricant preferred PE wax, montanin wax, silicone
One or more mixture in powder, stearic acid, oleic acid, calcium stearate, ethylene bis stearic acid amide, erucyl amide
Described antifriction liniment is preferably nano inorganic implant or nano plastic micropowder, and described nano inorganic implant is usual
For nano-calcium carbonate, nanometer calcium silicates, nano silicon, nanoclay etc..
The polyethylene antistatic film of the Activated Carbon Nanotubes modification that the present invention provides can prepare by the following method: by activity
CNT and PE polymeric matrix material stirring and evenly mixing, then mix with auxiliary agent, melt extrude pelletize through double screw extruder
Prepare PE/ carbon nanotube conducting master batch；PE/ carbon nanotube conducting master batch is prepared into by blowing, curtain coating or stretch processes
To the polyethylene antistatic film that Activated Carbon Nanotubes is modified.Prepare what the technique of thin film was known to the skilled person.
The processing technique of described double screw extruder is screw speed 100～1000r/min, and extrusion temperature is 180-250
℃。
Double screw extruder melt extrudes pelletize, and pelletize mode has multiple, and optional water cooling bracing pelletizing, air-cooled tie rod are cut
Grain, die face are earnestly, cut under water.The method being well known to those skilled in the art.
Present invention high-pressure spraying method used when preparing Activated Carbon Nanotubes is to be filled by high-pressure spraying by dispersant solution
Putting the CNT spraying into high-speed stirred with the form of spraying, described high-pressure spray device can use high-pressure spraying machine, by height
Dispersant solution is become spray form to spray in material through high-pressure nozzle by water pump.Described high-pressure spraying machine is located in advance for CNT
Reason still belongs to the first time.High-pressure spraying method by dispersant solution be atomized, obtain a large amount of fine droplet after atomization, significantly increase solution with
The contact area of CNT, beneficially carbon nanotube particulate are coated with by auxiliary agent, strengthen its dispersibility.
In described high-pressure spraying method, spray rate is generally 10～100ml/min；
Atomized particle size is 0.1～1um.
The rotating speed of described high-speed stirred is 300～1500 turns/min.
The time of described high-speed stirred mixing is generally 1 minute～1 hour, preferably 5～40 minutes.
The present invention carries out high-speed stirred to CNT, to its surface pretreatment, simultaneously by dispersant, surface activity
The auxiliary agents such as agent are dissolved in liquid in the carbon nanotube dust being sprayed in stirring by the way of spraying so that CNT table
Face activates, and simultaneously by the material uniform wet such as dispersant, surfactant, causes to be formed between CNT and repels, significantly carry
The high dispersibility of CNT, and the bulk density of CNT can be improved, to obtain optimal dispersion effect with good simultaneously
Good processability.
The present invention innovation by CNT after pretreatment modification, as conductive filler add to PE material matrix
In, prepare high efficiency dispersion PE/ carbon nanotube conducting master batch, then prepared not by blowing, curtain coating or stretch processes
PE antistatic film with performance.Compared with traditional PE antistatic film, CNT during owing to reaching same electric conductivity
Addition well below the addition of other conductive fillers, hence in so that this antistatic film maintains PE to the full extent
Original performance of matrix resin, improves antistatic persistency and the service life of thin film.
The polyethylene antistatic film that the present invention provides, outward appearance: uniform color, without stain, corrugationless, surface without projection,
Without broken hole, without vestige；Excellent mechanical: hot strength: >=20MPA, elongation at break: >=100%, surface resistivity
(Ω): 106～109(content of carbon nanotubes=3wt.%).
Four, detailed description of the invention
With specific embodiment, technical scheme is described further below, but the protection content of the present invention is not
It is limited to this.
Embodiment 1～16
According to the form below 1 takes each raw material, is dissolved in solvent by dispersant, obtains dispersant solution, is then led to by dispersant solution
Cross high pressure spray process and spray into the CNT (diameter 1～30nm, length 1～100 μm, bulk density 0.02g/mL) of high-speed stirred
In, technological parameter is as shown in table 1, after high-speed stirred mixing, prepares Activated Carbon Nanotubes；
Table 1
The performance test results such as table 2 below of the Activated Carbon Nanotubes prepared
Table 2
Described dispersibility experiment detection by the following method: Activated Carbon Nanotubes 10mg embodiment 1～16 prepared is respectively
Add 10mL and prepare in the solvent (seeing table 1) used by this Activated Carbon Nanotubes, ultrasonic disperse 30 minutes, obtain suspension, quiet
Putting, when occurring substantially being layered, the record time is the holding time, and acquired results refers to table 2.Holding time is the longest, shows that it disperses
Property is the best.The most pretreated CNT cannot form stable suspension.
Above-mentioned test result indicate that, after pretreatment, the bulk density of CNT improve about 10 times (untreated
The bulk density of CNT is about 0.02g/mL), dispersibility is all significantly increased.
Embodiment 17～32
Activated Carbon Nanotubes prepared by embodiment 1～16 and PE polymer pulverulent material (mean diameter 100 μm～2mm)
Stirring and evenly mixing, then mixes with auxiliary agent, and each raw material dosage refers to table 3 and table 4, melt extrudes through double screw extruder, stretches, cold
But pelletizing prepares PE/ carbon nanotube conducting master batch；The processing technique of double screw extruder is screw speed 200r/min, extrusion temperature
Degree is 180 DEG C.
The content of carbon nanotubes of the PE/ carbon nanotube conducting master batch prepared is as shown in table 5.
The PE/ carbon nanotube conducting master batch of preparation is prepared antistatic film, according to " GB/T1410-through blow moulding machine blowing
2006 solid insulating material specific insulations and surface resistivity test method " surface resistivity of testing film, and detect it
Physical property, result is as shown in table 5.
Table 3
Table 4
Table 5
Embodiment data show, the surface resistivity of antistatic film prepared by the present invention is preferable, in content of carbon nanotubes
In the case of about 3wt.%, surface resistivity is 106～109About Ω, antistatic property is good.And excellent mechanical,
Hot strength: >=20MPA, elongation at break: >=100%.
Claims (10)
1. the polyethylene antistatic film that an Activated Carbon Nanotubes is modified, it is characterised in that the modification of described Activated Carbon Nanotubes
Polyethylene antistatic film is made up of the component of following weight portion:
PE polymeric matrix material 70～95 mass parts, Activated Carbon Nanotubes 0.01～10 mass parts, auxiliary agent 0.1～20 mass
Part；
Described auxiliary agent is one or more the mixing in dispersant B, coupling agent, antioxidant, lubricant, antifriction liniment；
Described Activated Carbon Nanotubes prepares by the following method:
Dispersant A is dissolved in solvent, obtains dispersant solution, then dispersant solution is sprayed at a high speed by high-pressure spraying method
In the CNT of stirring, after high-speed stirred mixing, prepare Activated Carbon Nanotubes.
2. the polyethylene antistatic film that Activated Carbon Nanotubes as claimed in claim 1 is modified, it is characterised in that described carbon is received
Mitron, dispersant A, the mass fraction ratio of solvent are 85～95:0.1～5:5～10.
3. the polyethylene antistatic film that Activated Carbon Nanotubes as claimed in claim 1 is modified, it is characterised in that described dispersion
Agent A and dispersant B each stand alone as dodecylbenzene sodium sulfonate, polyvinylpyrrolidone, polyvinyl alcohol, xanthan gum, dodecane
Base sodium sulfate, Triton X-100, sodium carboxymethyl cellulose, Dihexadecylphosphate, arabic gum, cetyl three
One in methyl bromide ammonium, alkyl phenol ethylene oxide condensation substance emulsifying agent, cetyl trimethyl sodium bromide, Kynoar
Or two or more mixture.
4. the polyethylene antistatic film that Activated Carbon Nanotubes as claimed in claim 1 is modified, it is characterised in that described auxiliary agent
For one or more in coupling agent, antioxidant, antifriction liniment and dispersant B, the mixing of lubricant.
5. the polyethylene antistatic film that Activated Carbon Nanotubes as claimed in claim 1 is modified, it is characterised in that described auxiliary agent
For dispersant B, coupling agent, antioxidant, lubricant and antifriction liniment, the formula of described raw material is: PE polymeric matrix material, work
Property CNT, dispersant B, coupling agent, antioxidant, lubricant, the mass fraction of antifriction liniment be 70～90 mass parts, 1～
10 mass parts, 0.1～10 mass parts, 0.01～5 mass parts, 0.01～2 mass parts, 0.01～10 mass parts, 0.01～5 mass
Part, wherein total mass fraction of dispersant B, coupling agent, antioxidant, lubricant and antifriction liniment is 0.1～20 mass parts.
6. the polyethylene antistatic film that Activated Carbon Nanotubes as claimed in claim 1 is modified, it is characterised in that described solvent
For water, N,N-dimethylformamide, N-Methyl pyrrolidone, n-butyl alcohol, chloroform, dehydrated alcohol, acetone, petroleum ether, acetic acid second
One or more mixture in ester, butyl acetate.
7. the polyethylene antistatic film that Activated Carbon Nanotubes as claimed in claim 1 is modified, it is characterised in that described coupling
Agent is one or more the mixture in titante coupling agent, silane coupling agent.
8. the polyethylene antistatic film that Activated Carbon Nanotubes as claimed in claim 1 is modified, it is characterised in that described antioxygen
Agent is 1098,168,1010,1076, DLTP, one or more mixture in MB, 164,264.
9. the polyethylene antistatic film that Activated Carbon Nanotubes as claimed in claim 1 is modified, it is characterised in that described lubrication
Agent is in fatty acid, aliphatic amide type or ester lubricant, paraffin class lubricant, metallic soap salt lubricant, low-molecular-weight wax
One or more mixing.
10. the method for claim 1, it is characterised in that in described step (2), described antifriction liniment is that nano inorganic is filled out
Fill thing or nano plastic micropowder.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107262179A (en) * | 2017-07-31 | 2017-10-20 | 苏州坤阳机械科技有限公司 | A kind of resistant pipet stand with cleaning device |
| CN110387079A (en) * | 2019-07-25 | 2019-10-29 | 宁波睿诺包装材料有限公司 | A kind of halogen-free high flame-retardant polyethylene foam-material |
| CN111253656A (en) * | 2019-12-24 | 2020-06-09 | 浙江瑞堂塑料科技股份有限公司 | Carbon nano tube/antistatic agent composite modified polyethylene material and preparation method thereof |
| CN112341660A (en) * | 2020-11-04 | 2021-02-09 | 科伦塑业集团股份有限公司 | Antistatic polymer film and preparation method thereof |
| CN113912920A (en) * | 2021-09-02 | 2022-01-11 | 深圳烯湾科技有限公司 | Polyvinyl conductive composite material and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107262179A (en) * | 2017-07-31 | 2017-10-20 | 苏州坤阳机械科技有限公司 | A kind of resistant pipet stand with cleaning device |
| CN110387079A (en) * | 2019-07-25 | 2019-10-29 | 宁波睿诺包装材料有限公司 | A kind of halogen-free high flame-retardant polyethylene foam-material |
| CN111253656A (en) * | 2019-12-24 | 2020-06-09 | 浙江瑞堂塑料科技股份有限公司 | Carbon nano tube/antistatic agent composite modified polyethylene material and preparation method thereof |
| CN112341660A (en) * | 2020-11-04 | 2021-02-09 | 科伦塑业集团股份有限公司 | Antistatic polymer film and preparation method thereof |
| CN112341660B (en) * | 2020-11-04 | 2021-06-22 | 科伦塑业集团股份有限公司 | Antistatic polymer film and preparation method thereof |
| CN113912920A (en) * | 2021-09-02 | 2022-01-11 | 深圳烯湾科技有限公司 | Polyvinyl conductive composite material and preparation method and application thereof |
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