CN106117737A - A kind of polyethylene antistatic film of carbon nano-tube modification - Google Patents
A kind of polyethylene antistatic film of carbon nano-tube modification Download PDFInfo
- Publication number
- CN106117737A CN106117737A CN201610533075.5A CN201610533075A CN106117737A CN 106117737 A CN106117737 A CN 106117737A CN 201610533075 A CN201610533075 A CN 201610533075A CN 106117737 A CN106117737 A CN 106117737A
- Authority
- CN
- China
- Prior art keywords
- antistatic film
- carbon nano
- tube modification
- dispersant
- agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—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
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—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
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
Abstract
The invention discloses the polyethylene antistatic film of a kind of carbon nano-tube modification, the polyethylene antistatic film of described carbon nano-tube modification prepares by the following method: CNT is carried out high-speed stirred, dispersant is dissolved in liquid in the carbon nanotube dust being sprayed in stirring by the way of spraying simultaneously, carbon nano tube surface is activated, the Activated Carbon Nanotubes obtained adds to PE material matrix as conductive filler, thus prepare the PE/ carbon nanotube conducting master batch that electric conductivity is good, then by PE/ carbon nanotube conducting master batch and PE matrix resin and thermal oxidation stabilizer, flow ability modifying agent, the auxiliary agents such as antifriction liniment mix, by blowing, curtain coating or stretch processes prepare polyethylene antistatic film.Polyethylene antistatic film electric conductivity prepared by the present invention 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 of a kind of carbon nano-tube modification.
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 of a kind of carbon nano-tube modification, the preprocessed modification of CNT
After, add to PE material matrix as conductive filler, thus it is female to prepare the good PE/ carbon nanotube conducting of electric conductivity
Grain, then utilizes PE/ carbon nanotube conducting master batch to prepare polyethylene antistatic film.
The technical solution used in the present invention is:
A kind of polyethylene antistatic film of carbon nano-tube modification, the polyethylene antistatic film of described carbon nano-tube modification
Prepare by the following method:
(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；
(2) Activated Carbon Nanotubes and PE polymeric matrix material A stirring and evenly mixing, then mix with auxiliary agent A, squeezes through twin screw
Go out machine to melt extrude pelletize and prepare PE/ carbon nanotube conducting master batch；
Described PE polymeric matrix material A, Activated Carbon Nanotubes, the mass fraction of auxiliary agent A be 70～95 mass parts, 5～
30 mass parts, 0.1～20 mass parts；It is preferably 70～90 mass parts, 10～30 mass parts, 0.2～20 mass parts；
Described auxiliary agent A is one or more the mixing in dispersant B, coupling agent, antioxidant, lubricant；Preferably
Described auxiliary agent A is one or more mixing with dispersant B in coupling agent, antioxidant, lubricant, more preferably auxiliary agent A
For one or both in coupling agent, antioxidant and dispersant B, the mixing of lubricant.
Further, in preferred steps (2), the formula of raw material is: PE polymeric matrix material A, Activated Carbon Nanotubes, dispersion
Agent B, coupling agent, antioxidant, the mass fraction of lubricant be 70～90 mass parts, 10～30 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, lubricant
Total mass fraction is 0.2～20 mass parts.
Further, in preferred steps (2), the formula of raw material is: PE polymeric matrix material A, Activated Carbon Nanotubes, point
Powder B, coupling agent, antioxidant, the mass fraction of lubricant be 70～90 mass parts, 10～30 mass parts, 1～8 mass parts,
0.01～3 mass parts, 0.01～2 mass parts, 0.01～3 mass parts.
(3) PE/ carbon nanotube conducting master batch mixes with PE polymeric matrix material B, auxiliary agent B, by blowing, curtain coating or double
The polyethylene antistatic film of carbon nano-tube modification is prepared to drawing process
Based on described PE polymeric matrix material B, PE/ carbon nanotube conducting master batch and auxiliary agent B, PE/ CNT is led
The mass percent of the CNT contained in goddess of lightning's grain is 0.01～10%, and the mass percent of auxiliary agent B is 0.5～15%,
Surplus is PE matrix；Described PE matrix includes the PE contained in PE/ carbon nanotube conducting master batch and the PE polymerization being newly added
Thing matrix material B.
Further, based on described PE polymeric matrix material B, PE/ carbon nanotube conducting master batch and auxiliary agent B, PE/ carbon is received
The mass percent of the CNT contained in mitron conductive agglomerate is 1～10%, the mass percent of auxiliary agent B be 0.5～
15%, surplus is PE matrix；
Described auxiliary agent B is one or more the mixing in thermal oxidation stabilizer, flow ability modifying agent, antifriction liniment；Excellent
Selecting described auxiliary agent B is one or both mixing with flow ability modifying agent in thermal oxidation stabilizer, antifriction liniment.
Further, described auxiliary agent is thermal oxidation stabilizer, flow ability modifying agent, antifriction liniment, the percent mass of described raw material
Than being respectively: the CNT 2～8% contained in PE/ carbon nanotube conducting master batch, thermal oxidation stabilizer 0.1～2%, flowing changes
Property agent 0.5～10%, antifriction liniment 0.5～3%, surplus is PE.
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.
PE polymeric matrix material A and B are for distinguishing the PE polymeric matrix material used in different step, and A, B are not
There is 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, 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 A or B each stand alone as particle or pulverulent material, and PE polymer powdery is preferably used
Material, mean diameter be 0.5 μm can be LDPE, HDPE, LLDPE or MDPE to 5mm, PE polymeric matrix material A or B, excellent
The melt index selecting PE polymeric matrix material A or B is 2-100g/10min, preferably 10-30g/10min, beneficially CNT
Dispersion in PE matrix.
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 preferably PE wax, montanin wax, silicone powder, stearic acid, oleic acid, calcium stearate, the double stearic acid of ethylene
One or more mixture in 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.
In described step (2), double screw extruder melt extrudes pelletize, and pelletize mode has multiple, and optional water cooling bracing is cut
Grain, air-cooled tie rod pelletizing, die face are earnestly, cut under water.The method being well known to those skilled in the art.
In described step (1), described high-pressure spraying method is that dispersant solution passes through the high-pressure spray device shape with spraying
Formula sprays into the CNT of high-speed stirred, and described high-pressure spray device can use high-pressure spraying machine, will dispersion by high-pressure hydraulic pump
Agent solution becomes spray form to spray in material through high-pressure nozzle.Described high-pressure spraying machine still belongs to the first time for CNT pretreatment.
Dispersant solution is atomized by high-pressure spraying method, obtains a large amount of fine droplet after atomization, significantly increases solution and CNT
Contact area, 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
In described step (1), 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.
In described step (3), thermal oxidation stabilizer is preferably 1098,168,1010,1076, DLTP, in MB, 164,264
One or more mixture.
It is described that to prepare flow ability modifying agent used during thin film be fatty acid, aliphatic amide type and ester lubricant, stone
One or more mixing in wax series lubricant agent, metallic soap salt lubricant, low-molecular-weight wax, further, described flowing changes
In property agent preferred PE wax, montanin wax, silicone powder, stearic acid, oleic acid, calcium stearate, ethylene bis stearic acid amide, erucyl amide
One or more mixture.
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 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 CNT of this project innovation, after pretreatment modification, adds to PE material matrix as conductive filler
In, prepare high efficiency dispersion PE/ carbon nanotube conducting master batch, then according to product properties requirement, by its according to different ratio with
The auxiliary agents such as PE matrix resin and thermal oxidation stabilizer, flow ability modifying agent, antifriction liniment mix, by blowing, curtain coating or two-way
Drawing process prepares the PE antistatic film of different performance.Compared with traditional PE antistatic film, owing to reaching to lead equally
During electrical property, the addition of CNT is well below the addition of other conductive fillers, hence in so that this antistatic film is
Maintain original performance of PE matrix resin in big degree, improve antistatic persistency and the service life of thin film.
Polyethylene antistatic film prepared by the present invention, 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, 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 PE/ carbon nanotube conducting master batch of preparation is mixed with PE base material and each analog assistant according to the formula of table 5, through blowing
Machine blowing prepares antistatic film, according to " GB/T1410-2006 solid insulating material specific insulation and surface resistivity test
Method " surface resistivity of testing film, and detect its physical property, result is as shown in table 6.
Table 3
Table 4
Table 5
Table 6
Embodiment data show, the surface resistivity of antistatic film prepared by conductive agglomerate prepared by the present invention is preferable,
In the case of about content of carbon nanotubes 3wt.%, surface resistivity is 106～109About Ω, antistatic property is good.And
And excellent mechanical, hot strength: >=20MPA, elongation at break: >=100%.
Claims (10)
1. the polyethylene antistatic film of a carbon nano-tube modification, it is characterised in that the polyethylene of described carbon nano-tube modification resists
Electrostatic film prepares by the following method:
(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；
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 A stirring and evenly mixing, then mix with auxiliary agent A, through double screw extruder
Melt extrude pelletize and prepare PE/ carbon nanotube conducting master batch；
Described PE polymeric matrix material A, Activated Carbon Nanotubes, the mass fraction of auxiliary agent A are 70～95 mass parts, 5～30 matter
Amount part, 0.1～20 mass parts；
Described auxiliary agent A is one or more the mixing in dispersant B, coupling agent, antioxidant, lubricant；
(3) PE/ carbon nanotube conducting master batch mixes with PE polymeric matrix material B, auxiliary agent B, by blowing, curtain coating or two-way draw
Stretching process prepares the polyethylene antistatic film of carbon nano-tube modification
Based on described PE polymeric matrix material B, PE/ carbon nanotube conducting master batch and auxiliary agent B, PE/ carbon nanotube conducting is female
The mass percent of the CNT contained in Li is 0.01～10%, and the mass percent of auxiliary agent B is 0.5～15%, surplus
It is PE matrix；Described PE matrix includes the PE contained in PE/ carbon nanotube conducting master batch and the PE polymer base being newly added
Body material B；
Described auxiliary agent B is one or more the mixing in thermal oxidation stabilizer, flow ability modifying agent, antifriction liniment.
2. the polyethylene antistatic film of carbon nano-tube modification as claimed in claim 1, it is characterised in that described dispersant A and
Dispersant B each stands alone as dodecylbenzene sodium sulfonate, polyvinylpyrrolidone, polyvinyl alcohol, xanthan gum, lauryl sulphate acid
Sodium, Triton X-100, sodium carboxymethyl cellulose, Dihexadecylphosphate, arabic gum, cetyl trimethyl bromine
Change in ammonium, alkyl phenol ethylene oxide condensation substance emulsifying agent, cetyl trimethyl sodium bromide, Kynoar one or both
Above mixture.
3. the polyethylene antistatic film of carbon nano-tube modification as claimed in claim 1, it is characterised in that in described step (2)
The formula of raw material is: PE polymeric matrix material A, Activated Carbon Nanotubes, dispersant B, coupling agent, antioxidant, the matter of lubricant
Amount number be 70～90 mass parts, 10～30 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.
4. the polyethylene antistatic film of carbon nano-tube modification as claimed in claim 1, it is characterised in that described step (3)
In, described auxiliary agent is thermal oxidation stabilizer, flow ability modifying agent, antifriction liniment, and the mass percent of described raw material is respectively: PE/ carbon
The CNT 2～8% contained in nanotube conductive master batch, thermal oxidation stabilizer 0.1～2%, flow ability modifying agent 0.5～10%,
Antifriction liniment 0.5～3%, surplus is PE.
5. the polyethylene antistatic film of carbon nano-tube modification as claimed in claim 1, it is characterised in that described step (1)
In, described solvent is water, DMF, N-Methyl pyrrolidone, n-butyl alcohol, chloroform, dehydrated alcohol, acetone, stone
One or more mixture in oil ether, ethyl acetate, butyl acetate.
6. the polyethylene antistatic film of carbon nano-tube modification as claimed in claim 1, it is characterised in that described step (2)
In, described coupling agent is one or more the mixture in titante coupling agent, silane coupling agent；Described antioxygen
Agent is 1098,168,1010,1076, DLTP, one or more mixture in MB, 164,264；Described lubricant is
One in PE wax, montanin wax, silicone powder, stearic acid, oleic acid, calcium stearate, ethylene bis stearic acid amide, erucyl amide or two
Plant above mixture.
7. the polyethylene antistatic film of carbon nano-tube modification as claimed in claim 1, it is characterised in that described step (3)
In, described thermal oxidation stabilizer is 1098,168,1010,1076, DLTP, one or more mixing in MB, 164,264
Thing.
8. the polyethylene antistatic film of carbon nano-tube modification as claimed in claim 1, it is characterised in that described step (3)
In, described flow ability modifying agent 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.
9. the polyethylene antistatic film of carbon nano-tube modification as claimed in claim 8, it is characterised in that described step (3)
In, described flow ability modifying agent be PE wax, montanin wax, silicone powder, stearic acid, oleic acid, calcium stearate, ethylene bis stearic acid amide,
One or more mixture in erucyl amide.
10. the polyethylene antistatic film of carbon nano-tube modification as claimed in claim 1, it is characterised in that described step (3)
In, described antifriction liniment is nano inorganic implant or nano plastic micropowder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610533075.5A CN106117737A (en) | 2016-06-30 | 2016-06-30 | A kind of polyethylene antistatic film of carbon nano-tube modification |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610533075.5A CN106117737A (en) | 2016-06-30 | 2016-06-30 | A kind of polyethylene antistatic film of carbon nano-tube modification |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106117737A true CN106117737A (en) | 2016-11-16 |
Family
ID=57282320
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610533075.5A Pending CN106117737A (en) | 2016-06-30 | 2016-06-30 | A kind of polyethylene antistatic film of carbon nano-tube modification |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106117737A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111647219A (en) * | 2020-07-28 | 2020-09-11 | 吉林省塑料研究院 | Antistatic agent master batch special for polyethylene plastic film |
| CN111825915A (en) * | 2020-08-06 | 2020-10-27 | 浙江乔正新材料科技有限公司 | Environment-friendly antistatic cast film and preparation method thereof |
| CN112194837A (en) * | 2020-10-22 | 2021-01-08 | 长治市昌路矿山机械设备制造有限公司 | Semiconductor medicine delivery rubber tube |
| CN114292476A (en) * | 2021-12-31 | 2022-04-08 | 山东日科化学股份有限公司 | Multifunctional compound polarity modified inorganic micro-nano filler and preparation method thereof |
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 |
-
2016
- 2016-06-30 CN CN201610533075.5A patent/CN106117737A/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 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111647219A (en) * | 2020-07-28 | 2020-09-11 | 吉林省塑料研究院 | Antistatic agent master batch special for polyethylene plastic film |
| CN111825915A (en) * | 2020-08-06 | 2020-10-27 | 浙江乔正新材料科技有限公司 | Environment-friendly antistatic cast film and preparation method thereof |
| CN112194837A (en) * | 2020-10-22 | 2021-01-08 | 长治市昌路矿山机械设备制造有限公司 | Semiconductor medicine delivery rubber tube |
| CN114292476A (en) * | 2021-12-31 | 2022-04-08 | 山东日科化学股份有限公司 | Multifunctional compound polarity modified inorganic micro-nano filler and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106046709A (en) | Carbon nanotube modified PET antistatic thin film | |
| CN106084404A (en) | The polyethylene antistatic film that a kind of Activated Carbon Nanotubes is modified | |
| CN106117737A (en) | A kind of polyethylene antistatic film of carbon nano-tube modification | |
| CN106084738A (en) | A kind of TPU antistatic film of carbon nano-tube modification | |
| CN103992548B (en) | Modified low density polyethylene nanocomposite material used for 3D printing, and preparation method thereof | |
| CN106046496A (en) | Preparation method of activated carbon nanotube modified polyethylene antistatic thin film | |
| CN106832547A (en) | Opening slipping agent master batch and preparation method thereof | |
| CN105504713B (en) | A kind of 3D printing is material modified and preparation method thereof with polylactic acid microsphere | |
| CN106189178A (en) | The preparation method of the TPU antistatic film that a kind of Activated Carbon Nanotubes is modified | |
| CN106167554A (en) | A kind of PA/ carbon nanotube conducting master batch | |
| CN106046707A (en) | PET (polyethylene glycol terephthalate) and carbon nanotube conductive masterbatch | |
| CN110229495A (en) | A kind of preparation method of nanocomposite | |
| CN106146977A (en) | A kind of PE/ carbon nanotube conducting master batch | |
| CN111286108B (en) | Anti-sagging master batch for plastic pipes and preparation method and application thereof | |
| CN106188828A (en) | The preparation method of the polypropylene antistatic thin film that a kind of Activated Carbon Nanotubes is modified | |
| CN109810448A (en) | Conductive resin composition and preparation method thereof | |
| CN106432899A (en) | Activated carbon nanotube modified polypropylene (PP) antistatic film | |
| CN106147200A (en) | The modified TPU antistatic film of a kind of Activated Carbon Nanotubes | |
| CN106046708A (en) | Preparation method of activated carbon nanotube modified PET antistatic thin film | |
| CN106243637A (en) | The PET antistatic film that a kind of Activated Carbon Nanotubes is modified | |
| CN107446231A (en) | A kind of composite polyethylene material being modified jointly by graphene, CNT and fullerene and preparation method thereof | |
| CN106188827A (en) | A kind of PP/ carbon nanotube conducting master batch | |
| CN106046752A (en) | TPU (thermoplastic polyurethane) and carbon nanotube conductive masterbatch | |
| CN110229473A (en) | A kind of PET nanocomposite and preparation method thereof | |
| CN106084680A (en) | A kind of preparation method of PET/ carbon nanotube conducting master batch |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20161116 |
|
| RJ01 | Rejection of invention patent application after publication |