CN110183764A - Antistatic, self-cleaning carbon nanotube composition and preparation method and application - Google Patents

Antistatic, self-cleaning carbon nanotube composition and preparation method and application Download PDF

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CN110183764A
CN110183764A CN201910580746.7A CN201910580746A CN110183764A CN 110183764 A CN110183764 A CN 110183764A CN 201910580746 A CN201910580746 A CN 201910580746A CN 110183764 A CN110183764 A CN 110183764A
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carbon nanotube
self
cleaning
antistatic
composition
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CN110183764B (en
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倪奉尧
伍金奎
倪奉龙
孔智勇
李冰晶
孔涛
孔伟川
孙之状
刘树
孔德彬
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Shandong Donghong Pipe Industry Co Ltd
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Shandong Donghong Pipe Industry Co Ltd
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    • 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
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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
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions 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; Compositions of derivatives of such polymers
    • C08L27/02—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
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    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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    • 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
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    • C08K2201/001—Conductive additives
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    • C08L2203/18—Applications used for pipes
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    • 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

Abstract

The invention discloses antistatic, self-cleaning carbon nanotube composition and preparation method and application, it is characterised in that the carbon nanotube composition includes 65-98.5 parts of polymeric matrix；0.5-6 parts of carbon nanotube；Self-cleaning dose 0.5-4 parts；0.5-25 parts of function additive, and it is prepared by ball milling dispersion, the beneficial effects of the present invention are: surface treatment, solid-phase ball milling two kinds of technological means of dispersion in conjunction with self-cleaning dose, by the carbon nanotube of surface treatment, polymer using ball milling shearing, roll, pulverization realizes carbon nanotube in the polymer evenly dispersed, solve the problems, such as carbon nanotube be easy to reunite in polymer, difficulties in dispersion；Introduce the carbon nanotube of inertia, nonpolarity, good conductivity；Self-cleaning dose of carbon nanotube introducing and the interaction of carbon nanotube are handled, so that the surface of the plastic pipe of preparation has hydrophobic, oleophobic property, greasy dirt, silt etc. are not easy to adhere to tube surfaces, thus tubing has self-cleaning function.

Description

Antistatic, self-cleaning carbon nanotube composition and preparation method and application
Technical field:
The invention belongs to material and tubing technical field, relate more specifically to antistatic, self-cleaning carbon nanotube composition and Preparation method and application.
Background technique:
Plastic conduit refers to the common name of the pipe made of plastic material.From the difference for using polymer material, plastic conduit can It is divided into polyethylene (PE) pipe, polyvinyl chloride (PVC) pipe, polypropylene (PP) pipe, ABS pipe, polybutene (PB) pipe, nylon tube etc..Modeling Expects pipe material has energy-saving material-saving, environmental protection, high-strength light, resistance to compared with the pipelines such as traditional cast iron pipe, coating steel pipe, pipe of cement The advantages that burn into inner wall smooth non-scaling, construction and maintenance simplicity, long service life, it is widely used in building water supply and drainage, town and country Plumbing, gas, electric power and cable jacket, industrial fluids conveying, agricultural irrigation, mine field.
During pipeline medium, since rubbing action is easy to produce electrostatic, if electrostatic cannot eliminate possibility in time Cause dangerous hidden danger as generated fire and explosion, especially chemical industry, in terms of.Conventional method passes through addition conductive filler The antistatic property of polymer is improved such as conductive black, electrically conductive graphite, metal powder, but the additive amount of conductive filler generally exists 20%-30%, the addition of excessively high conductive filler cause tubing embrittlement, voltage endurance capability decline.104277279 A of Patent No. CN A kind of preparation method of the polyvinyl piping materials of flame-retardant and anti-static is disclosed, conductive black additive amount is 20%-40%, and fire retardant is 10%-20%, and base polyethylene only accounts for 40%-60%, since conductive black is granular subsphaeroidal structure, in order to reach resist it is quiet Electric effect, conductive black must form conductive network in the polymer can just good antistatic property, thus additive amount is high.
Carbon nanotube (CNTs) be made of the carbon atom of hexagonal arrangement several layers to tens of layers coaxial round tube it is one-dimensional Nano material.Carbon nanotube has good mechanical property, and it is 100 times of steel that CNTs tensile strength, which reaches 50~200GPa, close Degree but only has the 1/6 of steel, an order of magnitude at least higher than ordinary graphite fiber；Its elasticity modulus is up to 1TPa, with diamond Elasticity modulus it is suitable, about 5 times of steel.The P of carbon atom electronically forms large-scale delocalized pi-bond in carbon nanotube, due to altogether Yoke effect is significant, and carbon nanotube has excellent electric conductivity, but due to the inertia of carbon nano tube surface and the knot of high length-diameter ratio Structure, dispersion is extremely difficult, is often used for the ineffective of conductive filler.102850628 B of Patent No. CN discloses one kind The polyethylene pipe enhanced with carbon nanotube enhances the mechanical property of tubing by 1-10 parts of addition of carbon nanotube, It is also disclosed in the patent and antistatic effect is obtained using addition conductive acetylene carbon black, which is only increased using carbon nanotube Strength polyethylene is without improving electric conductivity using carbon nanotube.
In short, the conductive fillers additive amount such as the addition conductive black of the prior art, electrically conductive graphite, metal powder is excessive and causes Mechanical property deteriorates.Carbon nanotube is widely used as a kind of excellent nanoreinforcement material, but is limited due to its difficulties in dispersion The application in polymer anti static tubing is made.In addition, plastic conduit is during prolonged use, sedimentation, oil Dirt absorption easily causes line clogging, and the flow of pipeline becomes smaller.Summary of the invention:
To solve the above problems, overcome the deficiencies in the prior art, the present invention provides a kind of carbon nanotube polymer compositions, pipe Material and preparation method thereof, by using plastics as matrix, adding carbon nanotube, carbon nanotube is by self-cleaning dose of processing and ball milling point It dissipates, keeps its evenly dispersed in the polymer, so that polymer composition and its tubing have excellent antistatic effect.By the group The tubing of object preparation is closed because introducing the strong carbon nanotube of hydrophobicity and self-cleaning dose, surface does not adsorb dust, is not easy adhesive moisture, oil It is dirty and there is self-cleaning function.
The present invention solve above-mentioned technical problem the specific technical proposal is: antistatic, self-cleaning carbon nanotube composition, It is characterized by: being grouped as by the group of following mass fraction: 65-98.5 parts of polymeric matrix；0.5-6 parts of carbon nanotube；It is self-cleaning 0.5-4 parts of agent；0.5-25 parts of function additive.
Preferably, the polymeric matrix is one of following polymer: polyethylene, gathers heat-proof polythene PERT Propylene, polybutene, polyvinyl chloride, nylon 6, nylon66 fiber, nylon 1010, nylon 11, nylon 12, acrylonitrile-butadiene-styrene (ABS) Terpolymer.
Preferably, the carbon nanotube be single-walled carbon nanotube, double-walled carbon nano-tube, in multi-walled carbon nanotube at least One kind, wherein the caliber of single-walled carbon nanotube is 1-2nm, and length is 0.01-500 μm；The caliber of double-walled carbon nano-tube is 2- 4nm, length are 0.01-500 μm；The caliber of multi-walled carbon nanotube is 4-100nm, and length is 0.01-500 μm.
Preferably, described self-cleaning dose is at least one of the following: dodecyltrimethoxysilane, dodecyl three Ethoxysilane, hexadecyl trimethoxy silane, hexadecyl, octadecyl trimethoxysilane, ten Eight alkyl triethoxysilanes, ten trifluoro octyl trimethoxy silanes, tridecafluoro-n-octyltriethoxysilane, 17 fluorine decyls three Methoxy silane, heptadecafluorodecyl triethoxysilane, fluorine-containing processing aid PPA.
Preferably, the function additive be at least one of the following: antioxidant, light stabilizer, filler, stabilizer, Toughener.
A kind of preparation method of carbon nanotube anti-static polymer composition, includes the following steps:
The processing of S1 carbon nano tube surface: carbon nanotube, self-cleaning dose are mixed using high-speed mixer, the high-speed mixer Revolving speed be 100~800r/min, the mixing temperature be 25 DEG C~100 DEG C, the incorporation time be 5~60min；
The ball milling of S2 carbon nanotube disperses: the carbon nanotube being surface-treated, part or all of polymeric matrix being mixed and carried out The time of ball milling dispersion, ball milling dispersion is 20-120min, is separated mixture with ball after dispersion, mixture is spare；
S3 antistatic polymer composite is granulated: by the carbon nano-tube/polymer mixture after ball milling, remaining polymer matrix Body, function additive are uniformly mixed, and carry out melt blending, extruding pelletization using double screw extruder, the temperature of extrusion is 160-300 DEG C, the revolving speed of extruder is 250-1000r/min, obtains carbon nanotube anti-static polymer composition.
A kind of pipeline preparation method of carbon nanotube anti-static polymer composition, includes the following steps:
Carbon nanotube anti-static polymer composition is squeezed out using tubular object extruding equipment to get antistatic pipes, institute is arrived It is 1.0 × 10 that tubing, which is obtained, by the sheet resistance of MT-181 standard testing3Ω-1.0×109Ω is adjustable.
The present invention has the advantage that as follows compared with the prior art:
1) present invention combines self-cleaning dose of surface treatment, solid-phase ball milling to disperse two kinds of technological means, by the carbon nanometer of surface treatment Pipe, polymer using ball milling shearing, roll, pulverization realizes carbon nanotube in the polymer evenly dispersed, success Solve the problems, such as that carbon nanotube is easy reunion, difficulties in dispersion in polymer.Ultrasonic disperse relative to existing carbon nanotube Technology, is without the use of any solvent, environment-friendly high-efficiency, and it is high that carbon nanotube disperses preparation efficiency, can achieve per hour 100kg with On；The chemical surface treatment dispersion technology of relatively existing carbon nanotube carries out carbon nano tube surface without the use of strong acid etc. Polar functional dough, utmostly remains the prototype structure of carbon nanotube, thus can utmostly play leading for carbon nanotube Electrical advantage.
2) carbon nanotube of the invention with high conductivity, high length-diameter ratio substitutes conductive black, relative to existing to lead Electric carbon black is the polymer composition and tubing of antistatic agent, and the fibrous structure of carbon nanotube is easier in extremely low additive amount Under form conductive network in the polymer, it is strong that the additive amount of low conductive agent remains the original mechanics of polymer to the greatest extent Degree, pressure-resistant performance avoid tubing because conductive agent adding too much causes tubing embrittlement, reduces pressure, processing difficulties, surface light The problems such as cleanliness difference, to improve the service life of antistatic pipes.
3) carbon nanotube of inertia, nonpolarity, good conductivity is introduced in polymer pipeline, the plastic pipe of preparation is not easy to inhale Attached dust；Self-cleaning dose of carbon nanotube introducing and the interaction of carbon nanotube are handled, so that the surface of the plastic pipe of preparation With hydrophobic, oleophobic property, greasy dirt, silt etc. are not easy to adhere to tube surfaces, thus tubing has self-cleaning function.
Specific embodiment:
Detail is used for the purpose of to fully understand the embodiment of the present invention in the description of the present invention, but as ability The technical staff in domain will be appreciated that implementation of the invention is not limited to these details.In addition, well known structure and function not by Detailed description or displaying, to avoid the main points for having obscured the embodiment of the present invention.For those of ordinary skill in the art and Speech, can understand the concrete meaning of above-mentioned term in the present invention with concrete condition.
A specific embodiment of the invention: antistatic, self-cleaning carbon nanotube composition, by the group of following mass fraction It is grouped as: 65-98.5 parts of polymeric matrix；0.5-6 parts of carbon nanotube；Self-cleaning dose 0.5-4 parts；0.5-25 parts of function additive；And Carbon nanotube composition is prepared with the component, steps are as follows:
The processing of S1 carbon nano tube surface: carbon nanotube, self-cleaning dose are mixed using high-speed mixer, the high-speed mixer Revolving speed be 100~800r/min, the mixing temperature be 25 DEG C~100 DEG C, the incorporation time be 5~60min；
The ball milling of S2 carbon nanotube disperses: the carbon nanotube being surface-treated, part or all of polymeric matrix being mixed and carried out The time of ball milling dispersion, ball milling dispersion is 20-120min, is separated mixture with ball after dispersion, mixture is spare；
S3 antistatic polymer composite is granulated: by the carbon nano-tube/polymer mixture after ball milling, remaining polymer matrix Body, function additive are uniformly mixed, and carry out melt blending, extruding pelletization using double screw extruder, the temperature of extrusion is 160-300 DEG C, the revolving speed of extruder is 250-1000r/min, obtains carbon nanotube anti-static polymer composition.
The carbon nanotube anti-static polymer composition of acquisition is used to be processed into tubing, specifically: it is set using tubular object extruding It is standby to be squeezed out to get antistatic pipes are arrived；
Further, the polymeric matrix are as follows: polyethylene, heat-proof polythene PERT, polypropylene, polybutene, polyvinyl chloride, Nylon 6, nylon66 fiber, nylon 1010, nylon 11, nylon 12, acrylonitrile-butadiene-styrene (ABS) terpolymer in polymer One kind.
Further, the carbon nanotube is single-walled carbon nanotube, double-walled carbon nano-tube, one in multi-walled carbon nanotube Kind or two or more mixtures.
Further, the caliber of the single-walled carbon nanotube is 1-2nm, and length is 0.01-500 μm；The double-walled carbon is received The caliber of mitron is 2-4nm, and length is 0.01-500 μm；The caliber of the multi-walled carbon nanotube is 4-100nm, and length is 0.01-500μm。
Further, self-cleaning dose is dodecyltrimethoxysilane, dodecyl triethoxysilane, cetyl three Methoxy silane, hexadecyl, octadecyl trimethoxysilane, octadecyltriethoxy silane, ten Trifluoro octyl trimethoxy silane, tridecafluoro-n-octyltriethoxysilane, 17 fluorine ruthenium trimethoxysilanes, 17 fluorine decyls One or more kinds of mixtures of triethoxysilane, fluorine-containing processing aid PPA.
In order to clarify the technical characteristics of the invention, below in conjunction with specific embodiment, the present invention will be described in detail.
Embodiment 1
The processing of S1 carbon nano tube surface:
By multi-walled carbon nanotube (NC7000, Belgian Nanocyl) 2.5%, ten trifluoro octyl trimethoxy silanes 1.5% are added High mixer, with the revolving speed mixing 30min of 500rpm, discharging is spare.
The ball milling of S2 carbon nanotube disperses:
By the carbon nano-mixture (carbon nanotube 2.5%, self-cleaning dose of ten trifluoro octyl trimethoxy silanes 1.5%) by S1 processing It is added in ball mill, agate ball is added with the revolving speed ball milling 30min of 150rpm, 100 grades of 40% are then added in ball grinder Polyethylene pipe material (PN049, middle sandstone), with the revolving speed ball milling 15min of 100rpm, polyethylene/carbon after being dispersed is received Nanotube mixture.
The preparation of S3 carbon nanotube polyethylene composition:
By polyethylene/carbon nanotube mixture 44%(carbon nanotubes 2.5%, self-cleaning dose 1.5%, PN049 by S2 dispersion 40%), 55.5% PN049,0.5% antioxidant 1010 are uniformly mixed with high mixer, are made with double screw extruder in 185 DEG C of extrusions Grain, obtains carbon nanotube anti-static polyethylene composition.
The preparation of S4 antistatic pipes:
By the carbon nanotube anti-static polyethylene composition pipe extruder in S3, prepared in 185-200 DEG C of processing temperature The polyvinyl piping materials of dn160 are existed by the sheet resistance of MT181 standard testing tubing using surface contact angle tester test water The contact angle of tubing characterizes hydrophilic, hydrophobic property, is detailed in table 1.
Embodiment 2
The processing of S1 carbon nano tube surface:
By single-walled carbon nanotube (TNSR, Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences) 0.5%, 17 fluorine decyl, three ethoxy High mixer is added in base silane 0.5%, and with the revolving speed mixing 60min of 800rpm, discharging is spare.
The ball milling of S2 carbon nanotube disperses:
By carbon nano-mixture (carbon nanotube 0.5%, self-cleaning dose of heptadecafluorodecyl triethoxysilane by S1 processing 0.5%) it is added in ball mill, agate ball is added with the revolving speed ball milling 60min of 200rpm, 50% is then added in ball grinder Polypropylene pipe material (4220, Yanshan Petrochemical), polypropylene/carbon nanometer with the revolving speed ball milling 10min of 100rpm, after being dispersed Pipe mixture.
The preparation of S3 carbon nanotube polypropene composition:
By the polypropylene/carbon nanotube mixture 51%(carbon nanotubes 0.5% dispersed by S2, self-cleaning dose 0.5%, 4220 50%), 48.5% 4220,0.2% antioxidant 1010,0.3% antioxidant 3114 are uniformly mixed with high mixer, use double screw extruder In 205 DEG C of extruding pelletizations, carbon nanotube anti-static polypropene composition is obtained.
The preparation of S4 antistatic pipes:
By the carbon nanotube anti-static polypropene composition pipe extruder in S3, prepared in 190-210 DEG C of processing temperature The polypropylene pipe of dn160 is existed by the sheet resistance of MT181 standard testing tubing using surface contact angle tester test water The contact angle of tubing characterizes hydrophilic, hydrophobic property, is detailed in table 1.
Embodiment 3
The processing of S1 carbon nano tube surface:
By multi wall wall carbon nano tube (GT360, Shandong great Zhan nano material Co., Ltd) 6%, heptadecafluorodecyl triethoxysilane 3%, fluorine-containing processing aid PPA(3M Dynamar, FX 5912) 1% addition high mixer, it is mixed with the revolving speed of 100rpm 40min, discharging are spare.
The ball milling of S2 carbon nanotube disperses:
It will be added in ball mill by the carbon nano-mixture (carbon nanotube 6%, self-cleaning dose 4%) of S1 processing, agate ball be added With the revolving speed ball milling 40min of 100rpm, 20% polyvinyl chloride (DG-1000, Tianjin Dagu are then added in ball grinder Work), polyvinyl chloride/carbon nanotube mixture with the revolving speed ball milling 45min of 120rpm, after being dispersed.
The preparation of S3 carbon nanotube polychloroethylene composition:
By polyvinyl chloride/carbon nanotube mixture 30%(carbon nanotubes 6%, self-cleaning dose 4%, DG-1000 by S2 dispersion 20%), 45% DG-1000, CPE3%, 1.5%, No. 52 chlorinated paraffin 1% of stearic acid, ACR toughener 3%, rare earth calcium zinc are compound steady Determine agent 3.5%, nanometer calcium carbonate 13% with high mixer be uniformly mixed, with conical-double -helical rod extruder in 175 DEG C of extruding pelletizations, obtain To carbon nanotube anti-static polychloroethylene composition.
The preparation of S4 antistatic pipes:
By the carbon nanotube anti-static polychloroethylene composition pipe extruder in S3, in 165-175 DEG C of processing temperature system The polychloroethylene pipes of standby dn160 are tested by the sheet resistance of MT181 standard testing tubing using surface contact angle tester Water characterizes hydrophilic, hydrophobic property in the contact angle of tubing, is detailed in table 1.
Embodiment 4
The processing of S1 carbon nano tube surface:
By multi-walled carbon nanotube (Flotube 7010, Jiangsu Tian Nai Science and Technology Co., Ltd.) 3.5%, three ethoxy of octadecyl High mixer is added in base silane 1%, tridecafluoro-n-octyltriethoxysilane 1.5%, and with the revolving speed mixing 40min of 300rpm, discharging is standby With.
The ball milling of S2 carbon nanotube disperses:
It will be added in ball mill by the carbon nano-mixture (carbon nanotube 3.5%, self-cleaning dose 2.5%) of S1 processing, Ma be added The ternary of 30% acrylonitrile-butadiene-styrene (ABS) is added with the revolving speed ball milling 25min of 120rpm, then in ball grinder for Nao ball Copolymer (PA-709S, the odd beauty in Zhenjiang), acrylonitrile-butadiene-benzene with the revolving speed ball milling 20min of 180rpm, after being dispersed Terpolymer/carbon nanotube mixture of ethylene.
The preparation of the terpolymer of S3 carbon nanotube acrylonitrile-butadiene-styrene (ABS):
By terpolymer/carbon containing nanometer of carbon nanotube mixture 36%(of the acrylonitrile-butadiene-styrene (ABS) by S2 dispersion Pipe 3.5%, self-cleaning dose 2.5%, PA-709S 30%), 63.5% PA-709S, 0.5% antioxidant 1098 be uniformly mixed with high mixer, With double screw extruder in 225 DEG C of extruding pelletizations, the ternary for obtaining carbon nanotube anti-static acrylonitrile-butadiene-styrene (ABS) is total Ionomer compositions.
The preparation of S4 antistatic pipes:
By the terpolymer composition pipe extruder of the carbon nanotube anti-static acrylonitrile-butadiene-styrene (ABS) in S3, The tubing of dn160 is prepared in 210-230 DEG C of processing temperature, by the sheet resistance of MT181 standard testing tubing, is connect using surface Feeler tester tests water and characterizes hydrophilic, hydrophobic property in the contact angle of tubing, is detailed in table 1.
Embodiment 5
The processing of S1 carbon nano tube surface:
By multi-walled carbon nanotube (CNTs10 type, Shenzhen three is along nanometer new material limited liability company) 1.5%, 17 fluorine decyls High mixer is added in triethoxysilane 1%, fluorine-containing processing aid PPA (3M Dynamar, FX 9614) 0.5%, with The revolving speed mixing 20min of 400rpm, discharging are spare.
The ball milling of S2 carbon nanotube disperses:
It will be added in ball mill by the carbon nano-mixture (carbon nanotube 1.5%, self-cleaning dose 1.5%) of S1 processing, Ma be added 25% nylon 11 (Rilsan is added with the revolving speed ball milling 50min of 150rpm, then in ball grinder for Nao ball® polyamide 11, French A Kema), nylon 11/carbon nanotube mixture with the revolving speed ball milling 20min of 130rpm, after being dispersed.
The preparation of S3 carbon nanotube nylon 11 composition:
By nylon 11/carbon nanotube mixture 28%(carbon nanotubes 1.5%, self-cleaning dose 1.5%, nylon 11 by S2 dispersion 25%), 71.5% nylon 11,0.5% antioxidant 1010 are uniformly mixed with high mixer, are made with double screw extruder in 225 DEG C of extrusions Grain, obtains carbon nanotube anti-static nylon 11 composition.
The preparation of S4 antistatic pipes:
By the carbon nanotube anti-static nylon composite pipe extruder in S3, prepared in 210-220 DEG C of processing temperature The nylon 11 tubing of dn20, by the sheet resistance of MT181 standard testing tubing, using surface contact angle tester test water in pipe The contact angle of material characterizes hydrophilic, hydrophobic property, is detailed in table 1.
Comparative example 1
The processing of S1 carbon nano tube surface:
By carbon nanotube (NC7000, Belgian Nanocyl) 2.5%, ten trifluoro octyl trimethoxy silanes 1.5% are added high mixed Machine, with the revolving speed mixing 30min of 500rpm, discharging is spare.
The preparation of S3 carbon nanotube polyethylene composition:
By by S1 dispersion carbon nanotube mixture 4%(carbon nanotubes 2.5%, self-cleaning dose 1.5%), 95.5% PN049, 0.5% antioxidant 1010 is uniformly mixed with high mixer, with double screw extruder in 185 DEG C of extruding pelletizations, obtain carbon nanotube resist it is quiet Voltolisation vinyl composition.
The preparation of S4 antistatic pipes:
By the carbon nanotube anti-static polyethylene composition pipe extruder in S3, prepared in 185-200 DEG C of processing temperature The polyvinyl piping materials of dn160 are existed by the sheet resistance of MT181 standard testing tubing using surface contact angle tester test water The contact angle of tubing characterizes hydrophilic, hydrophobic property, is detailed in table 1.
Comparative example 2
The processing of S1 carbon nano tube surface:
High mixer is added in carbon nanotube (NC7000, Belgian Nanocyl) 2.5%, with the revolving speed mixing 30min of 500rpm, Discharging, it is spare.
The ball milling of S2 carbon nanotube disperses:
It will be added in ball mill by the carbon nano-mixture (carbon nanotube 2.5%) of S1 processing, agate ball be added with 150rpm Revolving speed ball milling 30min, then in ball grinder be added 40% 100 grades of polyethylene pipe material (PN049, middle sandstone), with The revolving speed ball milling 15min of 100rpm, polyethylene/carbon nanotube mixture after being dispersed.
The preparation of S3 carbon nanotube polyethylene composition:
Will be by the polyethylene/carbon nanotube mixture 42.5%(carbon nanotubes 2.5%, PN049 40% of S2 dispersion), 57% PN049,0.5% antioxidant 1010 are uniformly mixed with high mixer, with double screw extruder in 185 DEG C of extruding pelletizations, obtain carbon nanometer Pipe anti-static polyethylene composition.
The preparation of S4 antistatic pipes:
By the carbon nanotube anti-static polyethylene composition pipe extruder in S3, prepared in 185-200 DEG C of processing temperature The polyvinyl piping materials of dn160 are existed by the sheet resistance of MT181 standard testing tubing using surface contact angle tester test water The contact angle of tubing characterizes hydrophilic, hydrophobic property, is detailed in table 1.
Comparative example 3
The preparation of S3 ordinary carbon black polyethylene composition:
The PN049 of carbon black (N22O) 2.5%, 97%, 0.5% antioxidant 1010 high mixer are uniformly mixed, double screw extruder is used In 185 DEG C of extruding pelletizations, ordinary carbon black polyethylene composition is obtained.
The preparation of S4 common tubing:
By the ordinary carbon black polyethylene composition pipe extruder in S3, prepare dn160's in 185-200 DEG C of processing temperature Polyvinyl piping materials test water connecing in tubing using surface contact angle tester by the sheet resistance of MT181 standard testing tubing Feeler characterizes hydrophilic, hydrophobic property, is detailed in table 1.
Through the foregoing embodiment and the obtained performance data of the sheet resistance of carbon nanotube anti-static tubing of comparative example is shown in Shown in table 1:
Embodiment Sheet resistance (Ω) Contact angle (°)
Embodiment 1 2.0*104 156
Embodiment 2 6.0*108 162
Embodiment 3 1.0*103 149
Embodiment 4 4.0*105 137
Embodiment 5 3.0*107 126
Comparative example 1 5.0*1011 133
Comparative example 2 8.0*1010 104
Comparative example 3 7*1014 41
It was found from the performance data of the embodiment 1-5 and comparative example 1,2,3 that are shown in above-mentioned table: adding the polyethylene of ordinary carbon black Tubing does not have antistatic property, and contact angle of the water on tube material surface only has 41 °, water energy wet tube material surface；Addition carbon is received Mitron antistatic agent and self-cleaning dose, the hydrophobicity of carbon nanotube with there is hydrophobic, oleophobic property self-cleaning dose of collective effect so that water Become larger in the contact angle of tube surfaces, water can not soak tube surfaces, and water is tumbled in tube surfaces in pearl, the mistake that droplet tumbles Journey can take away the pollutant of tube surfaces and self-cleaning function is presented；Disperse by ball milling, realizes carbon nanotube and self-cleaning Agent is evenly dispersed in polymer composition and tubing；
Carbon nanotube polymer composition of the present invention, tubing sheet resistance only pass through self-cleaning dose of surface treatment and ball The processing means that mill dispersed phase combines can just make to reach MT181 standard requirements no more than 1.0*109Ω；Carbon is only added simultaneously Self-cleaning dose of collective effect in nanotube and claims, can just have larger contact angle, contact angle is bigger, and hydrophobicity is got over Good, self-cleaning function is stronger.
Above-mentioned specific embodiment cannot function as limiting the scope of the invention, for the technology people of the art For member, any alternate modification or transformation made to embodiment of the present invention are fallen within the scope of protection of the present invention.
Place is not described in detail by the present invention, is the well-known technique of those skilled in the art of the present technique.

Claims (10)

1. antistatic, self-cleaning carbon nanotube composition, it is characterised in that: be grouped as by the group of following mass fraction: polymerization 65-98.5 parts of object matrix；0.5-6 parts of carbon nanotube；Self-cleaning dose 0.5-4 parts；0.5-25 parts of function additive.
2. antistatic, self-cleaning carbon nanotube composition according to claim 1, it is characterised in that the polymer Matrix are as follows: polyethylene, heat-proof polythene PERT, polypropylene, polybutene, polyvinyl chloride, nylon 6, nylon66 fiber, nylon 1010, Buddhist nun Dragon 11, nylon 12, acrylonitrile-butadiene-styrene (ABS) terpolymer in polymer one kind.
3. antistatic, self-cleaning carbon nanotube composition according to claim 1, it is characterised in that the carbon nanometer Pipe is the mixture of one or more of single-walled carbon nanotube, double-walled carbon nano-tube, multi-walled carbon nanotube.
4. antistatic, self-cleaning carbon nanotube composition according to claim 3, it is characterised in that the single wall carbon is received The caliber of mitron is 1-2nm, and length is 0.01-500 μm；The caliber of the double-walled carbon nano-tube is 2-4nm, length 0.01- 500μm；The caliber of the multi-walled carbon nanotube is 4-100nm, and length is 0.01-500 μm.
5. antistatic, self-cleaning carbon nanotube composition according to claim 1, it is characterised in that self-cleaning dose are as follows: ten Dialkyl group trimethoxy silane, dodecyl triethoxysilane, hexadecyl trimethoxy silane, cetyl triethoxy Silane, octadecyl trimethoxysilane, octadecyltriethoxy silane, ten trifluoro octyl trimethoxy silanes, ten trifluoros Octyltri-ethoxysilane, 17 fluorine ruthenium trimethoxysilanes, heptadecafluorodecyl triethoxysilane, fluorine-containing processing aid One or more kinds of mixtures of PPA.
6. a kind of preparation method of carbon nanotube composition, with antistatic, self-cleaning carbon nanotube described in claim 1-5 Prepared by composition component, it is characterised in that the preparation method of composition includes the following steps:
The processing of S1 carbon nano tube surface: carbon nanotube, self-cleaning dose are mixed using high-speed mixer, the high-speed mixer Revolving speed be 100~800r/min, the mixing temperature be 25 DEG C~100 DEG C, the incorporation time be 5~60min；
The ball milling of S2 carbon nanotube disperses: the carbon nanotube being surface-treated, part or all of polymeric matrix being mixed and carried out The time of ball milling dispersion, ball milling dispersion is 20-120min, is separated mixture with ball after dispersion, mixture is spare；
S3 antistatic polymer composite is granulated: by the carbon nano-tube/polymer mixture after ball milling, remaining polymer matrix Body, function additive are uniformly mixed, and carry out melt blending, extruding pelletization using double screw extruder, the temperature of extrusion is 160-300 DEG C, the revolving speed of extruder is 250-1000r/min, obtains carbon nanotube anti-static polymer composition.
7. antistatic, self-cleaning carbon nanotube composition described in claim 1-5, it is characterised in that the carbon nanotube group Object is closed for being processed into tubing.
8. the preparation method of carbon nanotube composition as claimed in claim 6, it is characterised in that the carbon nanotube composition is used In being processed into tubing.
9. antistatic, self-cleaning carbon nanotube composition according to claim 7, it is characterised in that the tubing adds Work method are as follows: squeeze out carbon nanotube anti-static polymer composition to get antistatic pipe is arrived using tubular object extruding equipment Material.
10. the preparation method of carbon nanotube composition according to claim 8, it is characterised in that the processing side of the tubing Method are as follows: squeeze out carbon nanotube anti-static polymer composition to get antistatic pipes are arrived using tubular object extruding equipment.
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CN113881166B (en) * 2021-11-03 2022-11-01 江西铜业技术研究院有限公司 Multifunctional paste and preparation method thereof

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