CN106046708A - Preparation method of activated carbon nanotube modified PET antistatic thin film - Google Patents

Preparation method of activated carbon nanotube modified PET antistatic thin film Download PDF

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CN106046708A
CN106046708A CN201610528016.9A CN201610528016A CN106046708A CN 106046708 A CN106046708 A CN 106046708A CN 201610528016 A CN201610528016 A CN 201610528016A CN 106046708 A CN106046708 A CN 106046708A
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pet
dispersant
lubricant
activated carbon
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王鹏
甄万清
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Jiaxing Gaozhenggao Polymer Material Co Ltd
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Jiaxing Gaozhenggao Polymer Material Co Ltd
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    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
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    • C08J2439/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
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    • 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

Abstract

The invention discloses a preparation method of an activated carbon nanotube modified PET antistatic thin film. The preparation method includes: stirring a carbon nanotube at a high speed; at the same time, dissolving auxiliaries like a dispersant and a surfactant in a liquid; spraying the liquid into carbon nanotube powder being stirred to activate the surface of the carbon nanotube; adding the activated carbon nanotube obtained as a conductive filler into a PET material matrix to prepare PET/carbon nanotube conductive masterbatch good in conductive performance; utilizing the PET/carbon nanotube conductive masterbatch to prepare the PET antistatic thin film. The PET antistatic thin film prepared by the method is good in conductive performance, high in antistatic durability and long in service life.

Description

The preparation method of the PET antistatic film that a kind of Activated Carbon Nanotubes is modified
One, technical field
The present invention relates to the preparation method of the modified PET antistatic film of a kind of Activated Carbon Nanotubes.
Two, background technology
Polyethylene terephthalate (PET) has many excellent performances, thus PET film and thin slice are extensively applied In packaging material such as food, medicine, fiber, electronic components, be used as the most in large quantities tape, soft mould magnetic holder, photograph use Egative film etc..
But PET film is produced electrostatic phenomenon by friction, often can cause viscous carriage return, pollution, poor attachment, piebaldism, matter The lower degradation trouble of amount, accordingly, it would be desirable to carry out antistatic treatment to thin film.
PET film is carried out antistatic treatment and is commonly divided into surface processing-type and internal two kinds of methods of addition type.Surface Addition type is the purpose reaching to eliminate electrostatic at the film surface coating material such as antistatic additive or anti-static material.Internal addition type It is usually and in film manufacturing processes, anlistatig material is directly filled, thus reach anlistatig purpose.
Wherein, conductivity type filler is used to be possible not only to produce PET antistatic plastic thin film, and due to its antistatic behaviour base In the electric conductivity of filler, persistency is good compared with surface-coated type PET antistatic film, and antistatic behaviour is affected by ambient humidity 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 PET antistatic Applied research in material mainly by changing structure and the content of CNT, improves CNT dispersion in PET Property, and CNT is carried out surface process and equalize electric conductivity and other properties of PET anti-static material.
Three, summary of the invention
The invention provides the PET antistatic film that a kind of Activated Carbon Nanotubes is modified, the preprocessed modification of CNT After, add to PET material matrix as conductive filler, thus prepare the PET/ carbon nanotube conducting that electric conductivity is good Master batch, then utilizes PET/ carbon nanotube conducting master batch to prepare PET antistatic film.
The technical solution used in the present invention is:
The preparation method of the PET antistatic film that a kind of Activated Carbon Nanotubes is modified, 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；
(2) Activated Carbon Nanotubes and pet polymer matrix material stirring and evenly mixing, then mix with auxiliary agent, squeezes through twin screw Go out machine to melt extrude pelletize and prepare PET/ carbon nanotube conducting master batch；
Described pet polymer 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.
(3) PET/ carbon nanotube conducting master batch prepares activated carbon nanometer by blowing, curtain coating or stretch processes The PET antistatic film that pipe is modified.
Further, auxiliary agent described in preferred steps (2) is dispersant B, coupling agent, antioxidant, lubricant and antifriction liniment, The formula of described raw material is: pet polymer matrix material, Activated Carbon Nanotubes, 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 parts, wherein dispersant B, coupling agent, antioxidant, lubricant and antifriction Total mass fraction of liniment is 0.1～20 mass parts.
Further, in preferred steps (2), the formula of raw material is: pet polymer matrix material, Activated Carbon Nanotubes, point Powder B, coupling agent, antioxidant, lubricant, the mass fraction of antifriction liniment be 70～90 mass parts, 1～10 mass parts, 1～10 Mass parts, 0.01～3 mass parts, 0.01～2 mass parts, 0.01～3 mass parts, 0.01～5 mass parts, wherein dispersant B, idol Total mass fraction of connection agent, antioxidant, lubricant and antifriction liniment is 0.1～20 mass parts.
Further, in preferred steps (2), the formula of raw material is: pet polymer matrix material, Activated Carbon Nanotubes, point Powder B, coupling agent, antioxidant, lubricant, the mass fraction of antifriction liniment are 70～90 mass parts, 3～8 mass parts, 1～8 matter Amount 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.
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 pet polymer matrix material is particle or pulverulent material, pet polymer pulverulent material is preferably used, averagely Particle diameter be 0.5 μm be 2-100g/10min, preferably 10-30g/ to 5mm, the preferably melt index of pet polymer matrix material 10min, the beneficially CNT dispersion in PET 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 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, PP wax, montanin wax, One or more mixing in silicone powder, stearic acid, oleic acid, calcium stearate, ethylene bis stearic acid amide, erucyl amide Thing
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..
In described step (2), the processing technique of described double screw extruder is screw speed 100～1000r/min, extrusion Temperature is 250-280 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), using blowing, curtain coating or stretch processes to prepare thin film, the technique preparing thin film is this Known to skilled person.
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 PET material matrix as conductive filler In, prepare high efficiency dispersion PET/ carbon nanotube conducting master batch, then prepared not by blowing, curtain coating or stretch processes PET antistatic film with performance.Compared with traditional PET antistatic film, carbon nanometer during owing to reaching same electric conductivity The addition of pipe is well below the addition of other conductive fillers, hence in so that this antistatic film maintains to the full extent Original performance of PET matrix resin, improves antistatic persistency and the service life of thin film.
PET antistatic film prepared by the present invention, outward appearance: uniform color, without stain, corrugationless, surface is without projection, without broken Hole, without vestige；Excellent mechanical: hot strength: >=170MPA, elongation at break: >=120%, percent thermal shrinkage :≤5%, table 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 and pet polymer pulverulent material prepared by embodiment 1～16 (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, draws Stretch, cooling and dicing prepares PET/ carbon nanotube conducting master batch；The processing technique of double screw extruder is screw speed 200r/min, Extrusion temperature is 255 DEG C.
The content of carbon nanotubes of the PET/ carbon nanotube conducting master batch prepared is as shown in table 5.
The PET/ carbon nanotube conducting master batch of preparation is prepared antistatic film through biaxial tension, according to " GB/T1410- 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: >=170MPA, elongation at break: >=120%.

Claims (10)

1. the preparation method of the PET antistatic film that an Activated Carbon Nanotubes is modified, it is characterised in that described method include with Lower step:
(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 pet polymer matrix material stirring and evenly mixing, then mix with auxiliary agent, through double screw extruder Melt extrude pelletize and prepare PET/ carbon nanotube conducting master batch；
Described pet polymer 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；
Described auxiliary agent is one or more the mixing in dispersant B, coupling agent, antioxidant, lubricant, antifriction liniment；
(3) PET/ carbon nanotube conducting master batch is prepared Activated Carbon Nanotubes changed by blowing, curtain coating or stretch processes The PET antistatic film of property.
2. 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.
3. the method for claim 1, it is characterised in that in described step (2), described auxiliary agent be dispersant B, coupling agent, Antioxidant, lubricant and antifriction liniment, the formula of described raw material is: pet polymer matrix material, Activated Carbon Nanotubes, dispersion Agent 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 parts, wherein dispersant B, Total mass fraction of coupling agent, antioxidant, lubricant and antifriction liniment is 0.1～20 mass parts.
4. method as claimed in claim 3, it is characterised in that in described step (2), the formula of described raw material is: PET is polymerized Thing matrix material, Activated Carbon Nanotubes, dispersant B, coupling agent, antioxidant, lubricant, the mass fraction of antifriction liniment be 70～ 90 mass parts, 1～10 mass parts, 1～10 mass parts, 0.01～3 mass parts, 0.01～2 mass parts, 0.01～3 mass parts, 0.01～5 mass parts, wherein total mass fraction of dispersant B, coupling agent, antioxidant, lubricant and antifriction liniment be 0.1～ 20 mass parts.
5. 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.
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 or 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 in described step (2), described lubricant is PE wax, PP wax, illiteracy One or more in denier wax, silicone powder, stearic acid, oleic acid, calcium stearate, ethylene bis stearic acid amide, erucyl amide Mixture.
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.
CN201610528016.9A 2016-06-30 2016-06-30 Preparation method of activated carbon nanotube modified PET antistatic thin film Pending CN106046708A (en)

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CN112127005A (en) * 2020-10-10 2020-12-25 杭州成江纺织有限公司 Polyester filament yarn and preparation process thereof
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* Cited by examiner, † Cited by third party
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CN112127005A (en) * 2020-10-10 2020-12-25 杭州成江纺织有限公司 Polyester filament yarn and preparation process thereof
CN112852121A (en) * 2020-12-31 2021-05-28 东莞市基烁实业有限公司 Conductive master batch for PET (polyethylene terephthalate) sheet as well as preparation method and application thereof

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