CN106046497A - Preparation method of PE (polyethylene) and carbon nanotube conductive masterbatch - Google Patents
Preparation method of PE (polyethylene) and carbon nanotube conductive masterbatch Download PDFInfo
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
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- 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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- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
Abstract
The invention discloses a preparation method of PE (polyethylene) and carbon nanotube conductive masterbatch, comprising: stirring carbon nanotubes at high speed, dissolving a dispersant in a liquid, spraying by means of mist spraying to stirred carbon nanotube powder so that the surface of the carbon nanotubes is activated, and adding obtained activated carbon nanotubes as a conductive filler to a PE material base so as to prepare the PE and carbon nanotube conductive masterbatch good in electrical conductivity. The PE and carbon nanotube conductive masterbatch prepared herein may be used to prepare antistatic products and is good in antistatic property.
Description
One, technical field
The present invention relates to the preparation method of a kind of PE/ carbon nanotube conducting master batch.
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, it is also difficult to transmission 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.Therefore, the conductive modified to PE material also becomes inevitable trend.
Traditional antistatic PE is material modified generally adds antistatic additive, metal dust or carbon system implant, thus makes
For going out antistatic PE goods, eliminate its surface electrostatic lotus produced during producing, using.
The advantage of antistatic additive filled-type product is that color articles is unrestricted, and wherein low molecule type antistatic additive is to product
Performance impact is little, and its surface resistivity is 1010-1013Ω.But the electrical property of low molecule antistatic additive filled-type product can be with
The passage of time and gradually lose.
Carbon system implant is mainly conductive black, graphite and carbon fiber, and the specific insulation of manufactured goods is 102-109Ω·
cm.The most carbon black filled is main flow, and why carbon black filled type conducting polymer is widely adopted, and the first is because of conductive black
Price is the cheapest；It two is because white carbon black and can have bigger choice according to different electric conductivity demands, its manufactured goods
Resistance value can be 102-109Change in broad range between Ω；Its three be electric conductivity persistently, stable；Therefore it is the most anti-
Electrostatic material.
Metal system conductive agglomerate is roughly divided into and forms the method for conductive layer at frosting and be mixed into by electroconductive stuffing
Plastics are made the method two kinds of conductive plastics.Different screen methods is respectively arranged with its pluses and minuses and the scope of application, and application in the past is relatively
Many is zinc spraying plating and electrically-conducting paint method.
But, use carbon system or metal based material the highest as consumption required during implant, as used conduction
White carbon black, its consumption to reach more than 20%, just can have preferable electric conductivity.This not only makes polymeric material spy inherently
Property is a greater impact, and makes mechanical property and the poor processability of composite.
CNT relies on the one-dimensional nano structure of its uniqueness and excellent electric property, and extremely low consumption can make polymerization
The electric conductivity of thing material obtains the biggest raising, and can be effectively improved the mechanical property of composite, becomes a kind of excellent
Conductive modified agent.
But, owing to CNT is a kind of high degree of polarization, ganoid inorganic macromolecule compound, surface defect
Less, lack active group, between CNT, there is stronger Van der Waals force and its huge specific surface area, the highest simultaneously
Draw ratio, causes in the ordinary course of things, and CNT is easily wound around reunion bunchy.CNT excellent in performance to be played makes it extensive
Application, the dispersion how solving CNT is critical problem.At present, the method for dispersing Nano carbon tubes have grinding with stirring,
The washing of high-energy ball milling, ultrasonic Treatment, strong acid and strong base, interpolation surfactant, growth in situ synthesis, multiple method integrated treatment
Deng.
Three, summary of the invention
The invention provides the preparation method of a kind of PE/ carbon nanotube conducting master batch, CNT is preprocessed modified,
Add to PE material matrix as conductive filler, thus prepare the PE/ carbon nanotube conducting master batch that electric conductivity is good.
The technical solution used in the present invention is:
The preparation method of a kind of PE/ carbon nanotube conducting master batch, said method comprising the steps of:
(1) dispersant A is dissolved in solvent, obtains dispersant solution, then by dispersant solution by high-pressure spraying method
Spray in the CNT of high-speed stirred, after high-speed stirred mixing, prepare Activated Carbon Nanotubes；
Described CNT, dispersant A, the mass fraction ratio of solvent are 85～95:0.1～5:5～10；
(2) Activated Carbon Nanotubes and PE polymeric matrix material stirring and evenly mixing, then mix with auxiliary agent, through twin-screw extrusion
Machine melt extrudes pelletize and prepares PE/ carbon nanotube conducting master batch；
Described PE polymeric matrix material, Activated Carbon Nanotubes, the mass fraction of auxiliary agent be 70～95 mass parts, 0.01～
30 mass parts, 0.1～20 mass parts；
Described auxiliary agent is one or more the mixing in dispersant B, coupling agent, antioxidant, lubricant；Preferably institute
State auxiliary agent be one or more mixing with dispersant B, more preferably auxiliary agent in coupling agent, antioxidant, lubricant be idol
One or both in connection agent, antioxidant are with dispersant B, the mixing of lubricant.
Further, in preferred steps (2), the formula of raw material is: PE polymeric matrix material, Activated Carbon Nanotubes, dispersant
The mass fraction of B is 70～95 mass parts, 0.01～30 mass parts, 0.1～10 mass parts.
Further, in preferred steps (2), the formula of raw material is: PE polymeric matrix material, Activated Carbon Nanotubes, dispersant
B, the mass fraction of coupling agent are 70～95 mass parts, 0.01～30 mass parts, 0.1～10 mass parts, 0.01～5 mass parts.
Further, in preferred steps (2), the formula of raw material is: PE polymeric matrix material, Activated Carbon Nanotubes, dispersant
B, the mass fraction of antioxidant are 70～95 mass parts, 0.01～30 mass parts, 0.1～10 mass parts, 0.01～2 mass parts.
Further, in preferred steps (2), the formula of raw material is: PE polymeric matrix material, Activated Carbon Nanotubes, dispersant
B, the mass fraction of lubricant are 70～95 mass parts, 0.01～30 mass parts, 0.1～10 mass parts, 0.01～10 mass parts.
Further, in preferred steps (2), the formula of raw material is: PE polymeric matrix material, Activated Carbon Nanotubes, dispersant
B, coupling agent, the mass fraction of antioxidant be 70～95 mass parts, 0.01～30 mass parts, 0.1～10 mass parts, 0.01～5
Mass parts, 0.01～2 mass parts.
Further, in preferred steps (2), the formula of raw material is: PE polymeric matrix material, Activated Carbon Nanotubes, dispersant
B, coupling agent, the mass fraction of lubricant be 70～95 mass parts, 0.01～30 mass parts, 0.1～10 mass parts, 0.01～5
Mass parts, 0.01～10 mass parts, wherein dispersant B, coupling agent, total mass fraction of lubricant are 0.2～20 mass parts.
Further, in preferred steps (2), the formula of raw material is: PE polymeric matrix material, Activated Carbon Nanotubes, dispersant
B, antioxidant, the mass fraction of lubricant be 70～95 mass parts, 0.01～30 mass parts, 0.1～10 mass parts, 0.01～2
Mass parts, 0.01～10 mass parts, wherein dispersant B, antioxidant, total mass fraction of lubricant are 0.2～20 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, the mass fraction of lubricant are 70～95 mass parts, 0.01～30 mass parts, 0.1～10 mass
Part, 0.01～5 mass parts, 0.01～2 mass parts, 0.01～10 mass parts, wherein dispersant B, coupling agent, antioxidant, lubrication
Total mass fraction of agent is 0.2～20 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, the mass fraction of lubricant be 70～95 mass parts, 0.1～30 mass parts, 1～10 mass parts,
0.01～3 mass parts, 0.01～2 mass parts, 0.01～3 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, the mass fraction of lubricant be 70～95 mass parts, 1～30 mass parts, 1～10 mass parts, 0.01
～3 mass parts, 0.01～2 mass parts, 0.01～3 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.
In described step (1), described solvent is water, DMF, N-Methyl pyrrolidone, n-butyl alcohol, chlorine
One or more mixture in imitative, dehydrated alcohol, acetone, petroleum ether, ethyl acetate, butyl acetate；
In described step (1), described CNT is one or both in multi-walled carbon nano-tubes, SWCN
Mixture, preferably multi-walled carbon nano-tubes.
In described step (2), described PE polymeric matrix material is particle or pulverulent material, and PE polymer powder is preferably used
Shape material, mean diameter be 0.5 μm can be LDPE, HDPE, LLDPE or MDPE to 5mm, PE polymeric matrix material, preferably
The melt index of PE polymeric matrix material is that 2-100g/10min, preferably 10-30g/10min, beneficially CNT are at PE base
Dispersion in body.
In described step (2), described coupling agent be in titante coupling agent, silane coupling agent one or both with
On mixture；Described 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, single alcoxyl
One or more mixed in base unsaturated fatty acid titanate esters or Di(dioctylpyrophosphato) ethylene titanate
Compound；Described silane coupler can use KH550, one or both in KH560, KH570, KH792, DL602, DL171
Above mixture；
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 and ester lubricant, paraffin class lubricant, metallic soap salt profit
One or more mixing in lubrication prescription, low-molecular-weight wax, further, described lubricant is preferably PE wax, montanin wax, silicone
One or more mixture in powder, stearic acid, oleic acid, calcium stearate, ethylene bis stearic acid amide, erucyl amide.
In described step (2), the processing technique of described double screw extruder is screw speed 100～1000r/min, extrusion
Temperature is 180-250 DEG C.
Described double screw extruder melt extrudes pelletize, and pelletize mode has multiple, optional water cooling bracing pelletizing, air-cooled tie rod
Pelletizing, die face are earnestly, cut under water.The method being well known to those skilled in the art.
High-pressure spraying method used when preparing Activated Carbon Nanotubes is that dispersant solution is passed through high-pressure spray device with spray
The form of mist sprays into the CNT of high-speed stirred, and described high-pressure spray device can use high-pressure spraying machine, pass through high-pressure hydraulic pump
Spray form is become to spray in material through high-pressure nozzle dispersant solution.Described high-pressure spraying machine still belongs to for CNT pretreatment
First.Dispersant solution is atomized by high-pressure spraying method, obtains a large amount of fine droplet after atomization, significantly increases solution and carbon nanometer
The contact area of pipe, 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.
When preparing Activated Carbon Nanotubes, the rotating speed of described high-speed stirred is 300～1500 turns/min.
The time of described high-speed stirred mixing is generally 0～1 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 activation, simultaneously by the material uniform wet such as dispersant, surfactant, causes to be formed between CNT and repels, and can be same
The bulk density of Shi Tigao CNT, to obtain optimal dispersion effect and good processability.
The present invention, by preprocessed for CNT modified, adds to PE material matrix as conductive filler, thus
Prepare PE/ carbon nanotube conducting master batch.Compared with traditional antistatic modified material of PE, reaching same electric conductivity condition
Under, the Activated Carbon Nanotubes implant consumption that the present invention uses can reduce by more than 5 times, therefore can make PE characteristic inherently
Hardly suffer from impact, and the mechanical property and processing characteristics impact on composite is relatively low, also assures that antistatic simultaneously
The persistency of performance.Therefore, the PE conductive agglomerate that the present invention provides can expand the range of PE antistatic article, improves system
The service life of product.
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
Dispersibility experiment detection by the following method: the Activated Carbon Nanotubes 10mg that embodiment 1～16 prepares is separately added into
10mL prepares in the solvent (seeing table 1) used by this Activated Carbon Nanotubes, and ultrasonic disperse 30 minutes obtains suspension, stands, goes out
When being the most substantially layered, the record time is the holding time, and acquired results refers to table 2.Holding time is the longest, shows that its dispersibility is more
Good.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, consumption is shown in Table 3, and then the auxiliary agent with table 4 mixes, and melt extrudes through double screw extruder, stretches, cooling and dicing system
Obtain PE/ carbon nanotube conducting master batch；The processing technique of double screw extruder is screw speed 200r/min, and extrusion temperature is 180
℃。
The content of carbon nanotubes of the PE/ carbon nanotube conducting master batch prepared is as shown in table 5.
The content of carbon nanotubes of conductive agglomerate of embodiment 17,21,24 preparation more than 10%, the conduction of these high-loads
Master batch is conducive to production and sales.When subsequent production is applied can by the conductive agglomerate of high content of carbon nanotubes again with PE matrix material
Material and the mixing of other auxiliary agent, prepare antistatic article.
Concrete, PE/ carbon nanotube conducting master batch prepared by embodiment 17～32 is mixed with PE base material according to the formula of table 5
Close, and add the auxiliary agents such as flow ability modifying agent, thermal oxidation stabilizer, antifriction liniment, prepare antistatic film through blow moulding machine blowing, according to
The sheet resistance of " GB/T1410-2006 solid insulating material specific insulation and surface resistivity test method " testing film
Rate, result is as shown in table 5.
Table 3
Table 4
Table 5
In table 5, thermal oxidation stabilizer is 1098, and flow ability modifying agent is erucyl amide, and antifriction liniment is nano-calcium carbonate.
Embodiment data show, the surface resistivity of antistatic article prepared by conductive agglomerate prepared by the present invention is preferable,
In the case of content of carbon nanotubes 2～4wt.%, surface resistivity is 103～106About Ω, antistatic property is good.
Claims (10)
1. the preparation method of a PE/ carbon nanotube conducting master batch, it is characterised in that said method comprising the steps of:
(1) 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；
(2) Activated Carbon Nanotubes and PE polymeric matrix material stirring and evenly mixing, then mix with auxiliary agent, melts through double screw extruder
Melt extruding pelletization and prepare PE/ carbon nanotube conducting master batch
Described PE polymeric matrix material, Activated Carbon Nanotubes, the mass fraction of auxiliary agent are 70～95 mass parts, 0.01～30 matter
Amount part, 0.1～20 mass parts；
Described auxiliary agent is one or more the mixing in dispersant B, coupling agent, antioxidant, lubricant.
2. the method for claim 1, it is characterised in that in described step (1), described CNT, dispersant A, solvent
Mass fraction ratio be 85～95:0.1～5:5～10.
3. the method for claim 1, it is characterised in that described dispersant A and dispersant B each stand alone as dodecyl
Benzene sulfonic acid sodium salt, polyvinylpyrrolidone, polyvinyl alcohol, xanthan gum, sodium lauryl sulphate, Triton X-100, carboxylic
Sodium carboxymethylcellulose pyce, Dihexadecylphosphate, arabic gum, cetyl trimethylammonium bromide, alkyl phenol ethylene oxide are condensed
One or more mixture in thing emulsifying agent, cetyl trimethyl sodium bromide, Kynoar.
4. the method for claim 1, it is characterised in that in described step (1), described solvent is water, N, N-dimethyl methyl
In amide, N-Methyl pyrrolidone, n-butyl alcohol, chloroform, dehydrated alcohol, acetone, petroleum ether, ethyl acetate, butyl acetate one
Kind or two or more mixture.
5. the method for claim 1, it is characterised in that in described step (2), the formula of described raw material is one of following:
Formula (one) PE polymeric matrix material, Activated Carbon Nanotubes, the mass fraction of dispersant B be 70～95 mass parts,
0.01～30 mass parts, 0.1～10 mass parts；
Formula (two) PE polymeric matrix material, Activated Carbon Nanotubes, dispersant B, the mass fraction of coupling agent are 70～95 matter
Amount part, 0.01～30 mass parts, 0.1～10 mass parts, 0.01～5 mass parts；
Formula (three) PE polymeric matrix material, Activated Carbon Nanotubes, dispersant B, the mass fraction of antioxidant are 70～95 matter
Amount part, 0.01～30 mass parts, 0.1～10 mass parts, 0.01～2 mass parts；
Formula (four) PE polymeric matrix material, Activated Carbon Nanotubes, dispersant B, the mass fraction of lubricant are 70～95 matter
Amount part, 0.01～30 mass parts, 0.1～10 mass parts, 0.01～10 mass parts；
Formula (five) PE polymeric matrix material, Activated Carbon Nanotubes, dispersant B, coupling agent, the mass fraction of antioxidant are 70
～95 mass parts, 0.01～30 mass parts, 0.1～10 mass parts, 0.01～5 mass parts, 0.01～2 mass parts；
Formula (six) PE polymeric matrix material, Activated Carbon Nanotubes, dispersant B, coupling agent, the mass fraction of lubricant are 70
～95 mass parts, 0.01～30 mass parts, 0.1～10 mass parts, 0.01～5 mass parts, 0.01～10 mass parts, wherein disperse
Agent B, coupling agent, total mass fraction of lubricant are 0.2～20 mass parts；
Formula (seven) PE polymeric matrix material, Activated Carbon Nanotubes, dispersant B, antioxidant, the mass fraction of lubricant are 70
～95 mass parts, 0.01～30 mass parts, 0.1～10 mass parts, 0.01～2 mass parts, 0.01～10 mass parts, wherein disperse
Agent B, antioxidant, total mass fraction of lubricant are 0.2～20 mass parts；
Formula (eight) PE polymeric matrix material, Activated Carbon Nanotubes, dispersant B, coupling agent, antioxidant, the quality of lubricant
Number be 70～95 mass parts, 0.01～30 mass parts, 0.1～10 mass parts, 0.01～5 mass parts, 0.01～2 mass parts,
0.01～10 mass parts, wherein dispersant B, coupling agent, antioxidant, total mass fraction of lubricant are 0.2～20 mass parts.
6. the method for claim 1, it is characterised in that in described step (2), described coupling agent is titanate ester coupling
One or more mixture in agent, silane coupling agent.
7. the method for claim 1, it is characterised in that in described step (2), described antioxidant is 1098,168,
1010,1076, one or more the mixture in DLTP, MB, 164,264.
8. the method for claim 1, it is characterised in that in described step (2), described lubricant is fatty acid, fat
In race's amide-type and ester lubricant, paraffin class lubricant, metallic soap salt lubricant, low-molecular-weight wax one or more
Mixing.
9. method as claimed in claim 8, it is characterised in that described lubricant be PE wax, montanin wax, silicone powder, stearic acid,
One or more mixture in oleic acid, calcium stearate, ethylene bis stearic acid amide, erucyl amide.
10. the method for claim 1, it is characterised in that in described step (2), the formula of raw material is: PE polymer base
Body material, Activated Carbon Nanotubes, dispersant B, coupling agent, antioxidant, the mass fraction of lubricant be 70～95 mass parts, 1～
30 mass parts, 1～10 mass parts, 0.01～3 mass parts, 0.01～2 mass parts, 0.01～3 mass parts.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101230145A (en) * | 2003-02-13 | 2008-07-30 | 斯蒂茨丁荷兰聚合物学会 | Reinforced polymer |
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2016
- 2016-06-30 CN CN201610530096.1A patent/CN106046497A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101230145A (en) * | 2003-02-13 | 2008-07-30 | 斯蒂茨丁荷兰聚合物学会 | Reinforced polymer |
Non-Patent Citations (1)
| Title |
|---|
| 王琛 主编: "《高分子材料改性技术》", 30 April 2007, 中国纺织出版社 * |
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