CN107099077A - The preparation method of conductive resin composition - Google Patents
The preparation method of conductive resin composition Download PDFInfo
- Publication number
- CN107099077A CN107099077A CN201710090051.1A CN201710090051A CN107099077A CN 107099077 A CN107099077 A CN 107099077A CN 201710090051 A CN201710090051 A CN 201710090051A CN 107099077 A CN107099077 A CN 107099077A
- Authority
- CN
- China
- Prior art keywords
- preparation
- resin composition
- conductive resin
- cnt
- masterbatch
- 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.)
- Granted
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0011—Combinations of extrusion moulding with other shaping operations combined with compression moulding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/04—Polymers of ethylene
- B29K2023/06—PE, i.e. polyethylene
- B29K2023/0608—PE, i.e. polyethylene characterised by its density
- B29K2023/065—HDPE, i.e. high density polyethylene
-
- 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
- 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
- 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
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
-
- 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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
Abstract
The present invention provides a kind of preparation method of conductive resin composition, according to an aspect of the present invention, the masterbatch of the conductive filler comprising high content is prepared by hybrid conductive filler and the first olefin polymer resin, mixed by the masterbatch and with the second olefin polymer resin of the identical or different species of the first olefin polymer resin, so as to, the mechanical performance of olefin polymer resin, which can be prevented, to be reduced, and assigns good electric conductivity.
Description
Technical field
The present invention relates to a kind of preparation method of conductive resin composition, in more detail, be related to by alleviate electric conductivity with
Compromise (tradeoff) between mechanical performance can balancedly realize the preparation method of both conductive resin compositions.
Background technology
Thermoplastic resin refers to by thermal softening in plasticity, the plastics of hardening by cooling.Above-mentioned thermoplastic resin has excellent
Processability and mouldability, therefore it is widely used in various daily necessitiess, business automation equipment, electrical and electronic product, automobile
Parts etc..
Also, the lasting additional special nature of species and characteristic carried out according to the product being made using above-mentioned thermoplastic resin
To be used as the trial of high added value material.
Especially, the situation of thermoplastic resin is applied in the field that friction is produced between naval stores or between other materials
Under, the damage and pollution of product occur due to electrification phenomenon, accordingly, it would be desirable to assign electric conductivity to thermoplastic resin.
As described above, in order to assign electric conductivity to existing thermoplastic resin, it is fine using such as CNT, carbon black, graphite, carbon
The conductive fillers such as dimension, metal dust, metal coating inorganic powder or metallic fiber.
However, assign significant result to electric conductivity to export, need to add about 10 relative to thermoplastic resin~
More than 20 weight % conductive filler, this result causes to reduce such as impact resistance of thermoplastic resin, elongation, wear resistance
Intrinsic mechanical performance.
Especially, the electric conductivity of thermoplastic resin and the field of mechanical performance are required at the same time, for example, in such as fuel tanks of automobile
Or the field such as fuel hose, due to the problem of keeping balancing between the two and product commercialization is restricted.
Moreover, in the case where needing to assign electric conductivity to high viscosity thermoplastic resin, due to the characteristic of thermoplastic resin,
The problem of thus presence can not realize the sufficient electric conductivity added according to conductive filler.
The content of the invention
The present invention is intended to provide a kind of mechanical performance for preventing thermoplastic resin is reduced, especially, high viscosity thermoplasticity is prevented
The mechanical performance of resin reduces and can realize the conductive resin composition of good electric conductivity.
An aspect of of the present present invention provides a kind of preparation method of conductive resin composition, and this method includes：Step (a), leads to
Extruding CNT and the first olefin polymer resin is crossed to prepare masterbatch；And step (b), mix the masterbatch and the second alkene
Fluoropolymer resin.
In one embodiment, the step (a) can be carried out at a temperature of 180~300 DEG C.
In one embodiment, in the step (a), the extruding can be carried out with 10~500 ㎏/hr speed.
In one embodiment, the content of CNT included in the masterbatch can be 10~30 weight %.
In one embodiment, the content of CNT included in the conductive resin composition can be 0.1~10
Weight %.
In one embodiment, the apparent density of the CNT can be 0.01~0.2g/ml.
In one embodiment, first olefin polymer resin and second olefin polymer resin can be respectively
Selected from by high density polyethylene (HDPE), low density polyethylene (LDPE), LLDPE, polyethylene and ethylene copolymers, polypropylene and its two kinds
Or one kind in the group of a variety of mixture compositions.
In one embodiment, the polyethylene and ethylene copolymers can be selected from by ethylene vinyl acetate, ethylene acrylic fourth
One kind in the group of ester, ethylene ethyl acrylate and its mixture composition of two or more.
In one embodiment, first olefin polymer resin can be by with 2~3:1 weight compares mix polyethylene
Formed with ethylene vinyl acetate.
In one embodiment, before the step (b), it may also include and bead is made in the product of the step (a)
Step.
Another aspect of the present invention provides a kind of preparation method of fuel tanks of automobile, this method after the step (b),
Also include：Step (c), is molded to the conductive resin composition.
Another aspect of the invention provides a kind of preparation method of motor vehicle fuel flexible pipe, this method the step (b) it
Afterwards, in addition to：Step (c), is molded to the conductive resin composition.
According to an aspect of the present invention, contained by hybrid conductive filler and the first olefin polymer resin to prepare comprising height
The masterbatch of the conductive filler of amount, the second alkene by the masterbatch and with the identical or different species of the first olefin polymer resin
Hydrocarbon polymer mixed with resin, thus, it is possible to which preventing the mechanical performance of olefin polymer resin reduces, and assigns good conduction
Property.
The effect of the present invention is not limited to the effect, it will be appreciated that including the detailed description or power from the present invention
The institute reasoned out in the structure of invention described in sharp claim is effective.
Brief description of the drawings
Fig. 1 schematically shows the preparation method of conductive resin composition according to an aspect of the present invention.
Fig. 2 is the surface for the products formed for showing the resin combination preparation using embodiments in accordance with the present invention and comparative example
The chart of resistance value.
Fig. 3 is the impact for the products formed for showing the resin combination preparation using embodiments in accordance with the present invention and comparative example
The chart of intensity level.
Fig. 4 is the tension for the products formed for showing the resin combination preparation using embodiments in accordance with the present invention and comparative example
The chart of intensity level.
Fig. 5 is the elongation for the products formed for showing the resin combination preparation using embodiments in accordance with the present invention and comparative example
The chart of rate value.
Embodiment
The present invention is described below with reference to accompanying drawings.However, the present invention can be realized in many different forms, and not
It should be construed as limited to the embodiments set forth herein.
Through whole document, term " including or comprising " and/or " having " represent one or more other assemblies, step,
Operate and/or in addition to described component, step, operation and/or element, however not excluded that the presence or addition of its element.
Embodiments of the invention are described in detail next, with reference to accompanying drawing.
Fig. 1 schematically shows the preparation method of conductive resin composition according to an aspect of the present invention.Reference picture 1, root
Preparation method according to the conductive resin composition of an aspect of of the present present invention can include：Step (a), by extrude CNT and
First olefin polymer resin prepares masterbatch；And step (b), mix the masterbatch and the second olefin polymer resin.
Conductive resin composition substantially can be by mechanical performance and the fluoropolymer resin of mouldability with certain level
And the conductive material of electric conductivity can be assigned to the fluoropolymer resin, for example, metal and other inorganic matters etc. are constituted.On preparing
Conductive resin composition is stated, it is necessary to the process for mixed polymerization resin and conductive material.
In order to improve the electric conductivity of existing conductive resin composition, it is proposed that the skill of the content of the increase conductive material
Art.If however, the content of the conductive material of same type is increased to more than certain level, especially, if containing CNT
Amount increases to more than certain level, then there is the not only mechanical performance reduction of resin in itself, and processability, workability etc. and decline
The problem of.To solve these problems, carry out increasing the conductive material in conductive resin composition by and with carbon black etc.
Total content trial, carbon black electric conductivity compared with CNT, which is assigned, to have little effect, but with good processability and
Workability.
However, the above method only differently adjusts the species and content of conductive material, and with by single
One process realizes the common ground of the mixing of resin and conductive material.
In this regard, in the step (a), can be by the CNT as conductive filler and the first olefin polymer
Resin is mixed, extrudes to prepare high-concentration carbon nano tube masterbatch.
As used herein, term " masterbatch (master batch) " refers to, when preparing resin combination, in advance scattered height
The material of the additive of concentration.CNT can be improved by preparing above-mentioned masterbatch scattered in olefin polymer resin
Property, so as to assign uniform electric conductivity to the whole region of the conductive resin composition.
Now, spherical (sphere), pellet shapes (pellet) etc. can be made in the masterbatch, but as long as being in subsequent step
Suddenly the dispersiveness of the CNT can be improved by being mixed with thermoplastic resin, just its shape is not limited.
The CNT be for as idioelectric thermoplastic polymer resin assign electric conductivity material, especially
Its, the material for assigning electric conductivity to olefin polymer resin, it is reduced by the resin added with the CNT
The sheet resistance for the plastic-substrates that composition is molded to prepare, so as to lift electric conductivity.
The example of the synthetic method of the CNT includes arc discharge method, pyrolysismethod, laser deposition, plasma
Chemical vapour deposition technique, thermal chemical vapor deposition method etc., but synthetic method is unrestricted, and all CNTs being made all may be used
Use.
Also, the CNT can be selected from by single-walled carbon nanotube, double-walled carbon nano-tube, many wall carbon according to wall number
Hollow tubular carbon nano-fiber (the cup-stacked of nanotube, the conical graphene of the multiple truncateds of stacking
Carbon nanofiber) and its two or more mixture composition group in one kind, it is preferable that can be easily fabricated
And the good multi-walled carbon nanotube of economy, but not limited to this.
On the other hand, as the masterbatch mother metal olefin polymer resin in thermoplastic resin in relatively wide temperature
Degree scope has small change in physical, and mouldability, weatherability, resistance to chemical reagents etc. excellent.
First olefin polymer resin can be selected from by high density polyethylene (HDPE), low density polyethylene (LDPE), linear low close
One kind spent in the group of polyethylene, polyethylene and ethylene copolymers, polypropylene and its mixture composition of two or more, it is preferable that can
Polyethylene series is thought, it is highly preferred that can be high density polyethylene (HDPE), but not limited to this.
Also, the polyethylene and ethylene copolymers can be selected from by ethylene vinyl acetate, ethylene butyl acrylate, ethylene propylene
One kind in the group of olefin(e) acid ethyl ester and its mixture composition of two or more, but not limited to this.
That is, described first olefin polymer resin can for be polymerized by same monomers single polymers, by xenogenesis
Copolymer or its mixture that monomer is polymerized.The polymerized form of the copolymer is not limited, the copolymer can be with
For alternate copolymer, random copolymer, block copolymer or graft copolymer.
Especially, when preparing the masterbatch, compared with using the situation of the olefin polymer resin of identical type, using
In the case of different types of olefin polymer resin mixture, resin is preferably kept by the interaction between them
The electric conductivity of composition and the balance of mechanical performance.
Specifically, first olefin polymer resin can be by with 1~5:1 weight ratio, it is preferable that with 2~3:1
Weight formed than mix polyethylene (PE) and ethylene vinyl acetate (EVA).If weight ratio between the two exceeds the model
Enclose, then compared with using the situation of the resin of identical type, mechanical performance improves effect can be little.
On the other hand, the step (a) can be at 180~300 DEG C, it is preferable that 220~240 DEG C, it is highly preferred that 230 DEG C
At a temperature of carry out.If the process temperature of the step (a) is less than 180 DEG C, olefin polymer resin partial melting, so that meeting
The dispersiveness of extrusion forming and CNT is reduced, and if more than 300 DEG C olefin polymer can occur for the process temperature
The thermal decomposition or denaturation of resin.
Also, can be with 10~500 ㎏/hr in the step (a), it is preferable that 10~30 ㎏/hr speed extruding
The CNT and first olefin polymer resin.If the extrusion speed is less than 10 ㎏/hr, productivity ratio can drop
Low, if the extrusion speed is more than 500 ㎏/hr, the mixture homogeneity of CNT and the first olefin polymer resin can drop
It is low.
Masterbatch as the product of the step (a) can include the CNT of high content.For example, institute in the masterbatch
Including the content of CNT can be 10~30 weight %.
If the content of included CNT is less than 10 weight % in the masterbatch, CNT is concentrated on masterbatch
Degree it is little, if the content be more than 30 weight %, the composition of prepared masterbatch is uneven, so that processability can drop
It is low.
When preparing the masterbatch CNT used be by dusty material with machinery, physics mode system
Piece is processed into bead shape, and after the process the apparent density of CNT can be 0.01~0.2g/ml, it is preferable that
Can be 0.05~0.2g/ml.If the apparent density of the CNT exceeds the scope, it is difficult to prepare comprising 10 weights
Measure the concentration masterbatch of more than % CNT.Also, being processed into the CNT of bead shape prevents powder in the course of the work
End is dispersed, can improve working environment.
On the other hand, extruder used can be the list for possessing a screw rod when being extruded in the step (a)
Screw extruder or the multi-screw extruder for possessing multiple screw rods, it is preferable that for the uniform mixing and extruding between each composition,
The example can be the double screw extruder for possessing two screw rods.
Now, in the kneading process using the extruder, in order to suppress the breakage of CNT, it is preferable that can be with
Using using double screw extruder the olefin polymer resin and use side feeder (Side are put into from extrusion pusher side
Feeder) the method for carrying out melt kneading to extruder supply CNT.
In the step (b), by making the CNT and the second alkene of high content included in the masterbatch poly-
Polymer resin mixes to be diluted (let-down).The second olefin polymer tree of input in the step (b)
As long as the amount of fat using in the conductive resin composition as product the content of CNT be diluted to 0.1 to 10 weight % i.e.
Can.
Also, second olefin polymer resin can be with the first olefin polymer resin identical species,
As needed, it can be different species.However, in first olefin polymer resin and the second olefin polymer tree
Fat it is a different kind of in the case of, it is also considered that the compatibility between to them, the one kind being separately contained in them can be used
Single phase above is same or is separately contained in the resin identical olefin polymer resin of one or more of they.
For example, when first olefin polymer resin is the mixture of polyethylene and ethylene vinyl acetate, it is described
Second olefin polymer resin can be polyethylene, polyethylene and ethylene copolymers or its mixture.
The conductive resin composition prepared by the step (a) and the step (b) is by high viscosity olefin polymer tree
Fat is used as mother metal, and compared with the conductive resin composition according to existing preparation method, for example, with being prepared without masterbatch
Conductive resin composition is compared, and is improved electric conductivity and is kept mechanical performance, so as to balancedly realize both.
Specifically, it can be diluted by mixing the masterbatch and the second olefin polymer resin so that described to lead
The content of included CNT is 0.1~10 weight % in electric resin combination.
If the content of included CNT is less than 0.1 weight %, electric conductivity meeting in the conductive resin composition
Reduction, and if the content is more than 10 weight %, mechanical performance can significantly reduce.
In the step (b), the mixing of the masterbatch and second olefin polymer resin can be mixed using melting
Refining method, situ aggregation method, solution mixing method etc., it is preferable that can use melting mixing method, the melting mixing method by using
Extruder etc. can evenly spread to CNT in resin under high temperature, high shear, can realize high capacity and system
Make cost savings.Species, feature and the selection benchmark of the extruder etc. are identical with the above.
In the step (a) or step (b), according to the application target of the conductive resin composition, choosing can be also added
Free fire retardant, impact modifier, flame retardant aid, lubricant, plasticiser, heat stabilizer, anti-drip agents, antioxidant, increase-volume
At least one of the group that agent, light stabilizer, pigment, dyestuff, inorganic additive and anti-dripping agent are constituted additive.
Based on the gross weight of the conductive resin composition, the content of the additive can be 0.1~10 weight %.If
The content of the additive is less than 0.1 weight %, then can not obtain being adapted to the effect of application target, if the content of the additive
More than 10 weight %, then the intrinsic physical property of olefin polymer resin can be reduced.
Plastic molded article can be made by injection, extrusion molding etc. in the conductive resin composition, moreover, by can
Wide variety of polyvinyl resin is used as mother metal to can be used for various daily necessitiess, business automation equipment, electric and electronic production
Product, auto parts and components etc..
Especially, the conductive resin composition can apply to need to keep the machinery more than certain level of balance
The auto parts and components of electric conductivity more than performance and certain level, specifically, can apply to fuel tanks of automobile (fuel tank)
Or motor vehicle fuel flexible pipe (fuel hose).By the step (a) and step (b), the change needed for above-mentioned products formed can be met
, electrochemistry, mechanical performance, therefore, are molded that final production can be obtained by mould to the conductive resin composition
Product.
Also, the plastic molded article prepared using the conductive resin composition according to application field by differently adjusting
The content of the CNT can be made with 102~1010Ω/sq sheet resistance scope, especially, is needing antistatic
With the field of good conductivity-imparting ability, it can be made with 102~108Ω/sq sheet resistance scope.
Embodiment 1
Multi-walled carbon nanotube (MWCNT) is put into the side feeder of double screw extruder, with 25 ㎏/hr input speed
To main hopper input polyethylene (HDPE, melt index is 5.0g/10min, ASTMD 1238), then in 200rpm kneading speed
Melt kneading is carried out under the conditions of degree and 230 DEG C of processing temperature, so that the mother that the content for preparing CNT is 10 weight %
Material.
By prepared masterbatch and different types of polyethylene, (HDPE, melt index is 0.3g/10min, ASTM D
1238) while putting into double screw extruder, melted under the conditions of 200rpm kneading speed and 250 DEG C of processing temperature
Melt kneading, so that the resin combination that the content for preparing CNT is 6 weight %.
Embodiment 2
Except the content of CNT contained in masterbatch is adjusted into 10 weight %, and will be contained in resin combination
The content of some CNTs is adjusted to outside 5 weight %, and resin has been made according to the identical method of embodiment 1 in remaining
Composition.
Embodiment 3
Except the content of CNT contained in masterbatch is adjusted into 10 weight %, and will be contained in resin combination
The content of some CNTs is adjusted to outside 4 weight %, and resin has been made according to the identical method of embodiment 1 in remaining
Composition.
Embodiment 4
Except the content of CNT contained in masterbatch is adjusted into 10 weight %, and will be contained in resin combination
The content of some CNTs is adjusted to outside 3 weight %, and resin has been made according to the identical method of embodiment 1 in remaining
Composition.
Embodiment 5
Multi-walled carbon nanotube (MWCNT) is put into the side feeder of double screw extruder, with 25 ㎏/hr input speed
To main hopper input by with 7:Than mix polyethylene, (HDPE, melt index is 5.0g/10min, ASTM D to 3 weight
1238) with the resin of ethylene vinyl acetate (EVA), then in 200rpm kneading speed and 230 DEG C of processing temperature
Under the conditions of carry out melt kneading so that prepare CNT content be 10 weight % masterbatch.
Then, according to prepared with the identical method of embodiment 1 CNT content be 6 weight % resin group
Compound.
Embodiment 6
Except the content of CNT contained in masterbatch is adjusted into 10 weight %, and will be contained in resin combination
The content of some CNTs is adjusted to outside 5 weight %, and resin has been made according to the identical method of embodiment 5 in remaining
Composition.
Embodiment 7
Except the content of CNT contained in masterbatch is adjusted into 10 weight %, and will be contained in resin combination
The content of some CNTs is adjusted to outside 4 weight %, and resin has been made according to the identical method of embodiment 5 in remaining
Composition.
Embodiment 8
Except the content of CNT contained in masterbatch is adjusted into 10 weight %, and will be contained in resin combination
The content of some CNTs is adjusted to outside 3 weight %, and resin has been made according to the identical method of embodiment 5 in remaining
Composition.
Comparative example 1
Multi-walled carbon nanotube (MWCNT) is put into the side feeder of double screw extruder, with 25 ㎏/hr input speed
To double screw extruder input polyethylene (HDPE, melt index is 0.3g/10min, ASTM D 1238), then in 200rpm
Kneading speed and 250 DEG C of processing temperature under the conditions of carry out melt kneading so that prepare CNT content be 6 weights
Measure % masterbatch.
Comparative example 2
In addition to the content of CNT contained in resin combination is adjusted into 5 weight %, remaining according to
Resin combination has been made in the identical method of comparative example 1.
Comparative example 3
In addition to the content of CNT contained in resin combination is adjusted into 4 weight %, remaining according to
Resin combination has been made in the identical method of comparative example 1.
Comparative example 4
In addition to the content of CNT contained in resin combination is adjusted into 3 weight %, remaining according to
Resin combination has been made in the identical method of comparative example 1.
Experimental example 1:Determined according to the electric conductivity of preparation method and content of carbon nanotubes
Using hydraulic injection molding machine at 210 DEG C to being entered according to the resin combination of the embodiment 1~8 and comparative example 1~4
Row injection, so as to be made with width 30cm, the injecting products of long 20cm rectangular shape.
Determined by sheet resistance tester (SIMCO, ST-4) each prepared injecting products sheet resistance (Ω/
Sq), as a result as shown in Figure 2.
Reference picture 2, it may be determined that be diluted the carbon to prepare to content of carbon nanotubes after masterbatch preparation process and receive
Nanotube-polymer nano-complex and the carbon nano tube-polymer nano-complex phase prepared without masterbatch preparation process
Than the table with equal (embodiment 4, embodiment 8 and comparative example 4) or reduction (embodiment 1~3,5~7 and comparative example 1~3)
Surface resistance, specifically, with minimum 105The sheet resistance value (embodiment 1 and embodiment 5) of Ω/sq degree.
Especially, increase to 5 weight % interval from 4 weight % with reference to the content of CNT, it is observed that with without
The situation (comparative example 2 and comparative example 3) for crossing masterbatch preparation process is compared, after masterbatch preparation process to content of carbon nanotubes
In the situation (embodiment 2~3 and embodiment 6~7) being diluted, sheet resistance is drastically reduced, and be may thereby determine that and is only passed through
Content of carbon nanotubes adjusts the effect that can be also significantly improved by a small margin.
In addition, when preparing masterbatch, compared with the situation (embodiment 3) of polyethylene is used alone as thermoplastic resin,
In the case where using the situation (embodiment 7) of the mixture of polyethylene and ethylene vinyl acetate as thermoplastic resin, it is seen that including
The conductive resin composition of the CNT of certain content has the sheet resistance of more reduction.
It is also conductive when preparing even if the CNT as conductive filler including same amount from the above results
During resin combination, good electric conductivity can be assigned, moreover, female when preparing by preparing masterbatch and it being diluted
During material electric conductivity just can be further improved using different types of thermoplastic resin intermixture.
Comparative example 5
The polyethylene (HDPE, melt index is 0.3g/10min, ASTM D1238) of not carbon nanotubes is used as resin
Composition.
Experimental example 2:According to the Measuring Mechanical Properties of preparation method and content of carbon nanotubes
Using injection machine at 250 DEG C to being noted according to the resin combination of the embodiment 1~8 and comparative example 1~5
Modeling, so that the sample for determining mechanical performance is prepared, cantilever beam impact strength by the following method to each sample, tension
Intensity and elongation are measured, as a result as shown in Figures 3 to 5.
- cantilever beam impact strength (kgf ㎝/㎝):The sample of 1/8 " thickness is measured according to ASTM D256.
- tensile strength (kgf/cm2) and elongation (%):It is measured according to ASTM D638 under the conditions of 20 ㎜/min.
Reference picture 3 is visible, compared with the thermoplastic resin (comparative example 5) for being not added with CNT, by adding carbon nanometer
Pipe is reduced come the impact strength of the thermoplastic resin composition's (embodiment 1~8 and comparative example 1~4) prepared.
However, compared with the resin combination (comparative example 1~4) prepared without masterbatch preparation process, it is female preparing
The amount of decrease of the impact strength for the resin combination (embodiment 1~8) for being diluted to prepare to it after material is lower.
Especially, it may be determined that in the case where content of carbon nanotubes is 5 weight %, single thermoplastic resin is included with being made
Resin combination situation (embodiment 2) or situation (comparative example 2) phase of the resin combination without masterbatch preparation process
Than high by about 2 in the impact strength that the resin combination (embodiment 6) for causing masterbatch to include different types of thermoplastic resin is made
Times.
Reference picture 4 is it was determined that thermoplastic resin (comparative example 5) phase with being not added with the CNT as conductive filler
Than with the increase of CNT addition, the tensile strength of resin combination also improves (embodiment 1~8 and comparative example 1 therewith
~4), especially, by the resin combination (embodiment 1~4) obtained by the masterbatch preparation process comprising single thermoplastic resin
Tensile strength with the resin combination (comparative example 1~4) prepared without masterbatch preparation process is with content of carbon nanotubes
Increase is in similar increase trend.
Also, reference picture 5, in the situation of the resin combination (embodiment 1~8) prepared by masterbatch preparation process
Under, even if content of carbon nanotubes increase, also keep thermoplastic resin (comparative example 5) intrinsic elongation, in contrast, without
In the case of the resin combination (comparative example 1~4) crossed masterbatch preparation process and prepared, elongation is significantly reduced.
From the above results, even if the conductive filler comprising same amount, also according to whether by masterbatch preparation process
And somewhat occur the difference in mechanical performance, specifically, content of carbon nanotubes is diluted to prepare after masterbatch is prepared
Resin combination be in more excellent mechanical performance.
Above-mentioned explanation of the invention is simply exemplary, as long as the ordinary skill people of the technical field of the invention
Member, is just understood that in the case where not changing the technological thought or essential feature of the present invention, other can be also deformed into easily specific
Form.Therefore, embodiment described above is only exemplary in every respect, but is not limited thereto.For example, being used as single type
Each structure member illustrated can also disperse to be implemented, equally, also can be with using the scattered structure member illustrated
With reference to form implemented.
The scope of the present invention is represented by appended claims, and not by above-mentioned detailed description, and by
The meaning, scope and its derived form for having altered or deforming of impartial concept of claims should be interpreted that and be included in this hair
In bright scope.
Claims (12)
1. a kind of preparation method of conductive resin composition, it is characterised in that including：
Step (a), masterbatch is prepared by extruding CNT and the first olefin polymer resin；And
Step (b), mixes the masterbatch and the second olefin polymer resin.
2. the preparation method of conductive resin composition according to claim 1, it is characterised in that the step (a) is 180
DEG C~300 DEG C at a temperature of carry out.
3. the preparation method of conductive resin composition according to claim 2, it is characterised in that in the step (a),
The extruding is carried out with 10 ㎏/hr~500 ㎏/hr speed.
4. the preparation method of conductive resin composition according to claim 1, it is characterised in that included in the masterbatch
The content of CNT be the weight % of 10 weight %~30.
5. the preparation method of conductive resin composition according to claim 4, it is characterised in that the electroconductive resin composition
The content of included CNT is the weight % of 0.1 weight %~10 in thing.
6. the preparation method of conductive resin composition according to claim 1, it is characterised in that the table of the CNT
Sight density is 0.01g/ml~0.2g/ml.
7. the preparation method of conductive resin composition according to claim 1, it is characterised in that first olefinic polymerization
Resin and second olefin polymer resin are respectively to be selected from by high density polyethylene (HDPE), low density polyethylene (LDPE), linear low close
The one kind spent in the group of polyethylene, polyethylene and ethylene copolymers, polypropylene and its mixture composition of two or more.
8. the preparation method of conductive resin composition according to claim 7, it is characterised in that the polyethylene and ethylene copolymers
For selected from by ethylene vinyl acetate, ethylene butyl acrylate, ethylene ethyl acrylate and its mixture group of two or more
Into group in one kind.
9. the preparation method of conductive resin composition according to claim 7, it is characterised in that first olefinic polymerization
Resin passes through with 1~5:1 weight is formed than mix polyethylene and ethylene vinyl acetate.
10. the preparation method of conductive resin composition according to claim 1, it is characterised in that the step (b) it
Before, in addition to the step of the product of the step (a) is made into bead.
11. a kind of preparation method of fuel tanks of automobile, it is characterised in that using the electroconductive resin group described in claim 1
The step of preparation method of compound prepares conductive resin composition,
After the step (b), in addition to：Step (c), is molded to the conductive resin composition.
12. a kind of preparation method of motor vehicle fuel flexible pipe, it is characterised in that using the electroconductive resin described in claim 1
The step of preparation method of composition prepares conductive resin composition,
After the step (b), in addition to：Step (c), is molded to the conductive resin composition.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2016-0020000 | 2016-02-19 | ||
| KR1020160020000A KR101830957B1 (en) | 2016-02-19 | 2016-02-19 | Method for manufacturing conductive resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107099077A true CN107099077A (en) | 2017-08-29 |
| CN107099077B CN107099077B (en) | 2020-07-31 |
Family
ID=59675922
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710090051.1A Active CN107099077B (en) | 2016-02-19 | 2017-02-20 | Method for preparing conductive resin composition |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6386114B2 (en) |
| KR (1) | KR101830957B1 (en) |
| CN (1) | CN107099077B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109161087A (en) * | 2018-07-17 | 2019-01-08 | 广州润锋科技股份有限公司 | A kind of preparation method of carbon nanotube composite polyethylene anti-static material |
| CN109971026A (en) * | 2017-12-14 | 2019-07-05 | 锦湖石油化学株式会社 | Conductive foaming bead and preparation method thereof |
| CN113272380A (en) * | 2019-01-29 | 2021-08-17 | 三井—陶氏聚合化学株式会社 | Resin composition and molded article |
| CN114729149A (en) * | 2019-11-27 | 2022-07-08 | 韩华思路信株式会社 | Conductive resin composition for anti-slip and molded article comprising same |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102220403B1 (en) * | 2017-09-14 | 2021-02-24 | 주식회사 엘지화학 | Preparing Method of Concentrated Conductive Resin and Polyamide Resin Composition Using the Same |
| KR102453804B1 (en) | 2020-09-03 | 2022-10-12 | 주식회사 투디엠 | Filler for polymer composites and the process for producing the same |
| KR102477947B1 (en) * | 2020-12-29 | 2022-12-15 | 한국신발피혁연구원 | Sponge-forming composition for absorbing static electricity |
| KR102399883B1 (en) | 2021-02-09 | 2022-05-20 | 재단법인대구경북과학기술원 | Composite polymer pellets for extrusion and manufacturing method thereof |
| KR102514631B1 (en) * | 2021-03-08 | 2023-03-27 | 주식회사 이루켐 | Manufacturing Method of Carbon Nanotube Masterbatch and Manufacturing Method of Electroconductive Polymer Composite by Using the Same |
| CN114736444B (en) * | 2022-03-25 | 2023-07-28 | 四川大学 | Polymer-based conductive composite material for heat tracing belt and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006501354A (en) * | 2002-10-02 | 2006-01-12 | ダウ グローバル テクノロジーズ インコーポレイティド | Polymer composition comprising a low viscosity homogeneously branched ethylene / α-olefin extender |
| CN101831103A (en) * | 2010-05-24 | 2010-09-15 | 哈尔滨理工大学 | High-conductivity polyolefin composite material and preparation method thereof |
| US20110168425A1 (en) * | 2010-01-08 | 2011-07-14 | Ahmed Ali Basfar | Clean flame retardant compositions with carbon nano tube for enhancing mechanical properties for insulation of wire and cable |
| CN102617918A (en) * | 2012-04-11 | 2012-08-01 | 四川大学 | Method for preparing high-ductility conductive polymer composite material |
| EP2660284A1 (en) * | 2012-05-04 | 2013-11-06 | Université Catholique De Louvain | Electroconductive nanocomposite |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003100147A (en) * | 2001-09-25 | 2003-04-04 | Nagase & Co Ltd | Conductive material containing carbon nanotube and its manufacturing method |
| JP4878832B2 (en) * | 2005-12-26 | 2012-02-15 | 株式会社プライムポリマー | Molded body and manufacturing method thereof |
| JP2007217633A (en) * | 2006-02-20 | 2007-08-30 | Prime Polymer:Kk | Molded product and its production process |
| JP2009074072A (en) * | 2007-08-30 | 2009-04-09 | Hodogaya Chem Co Ltd | Method for improving conductivity of resin molded body comprising carbon nanotube by heat treatment |
| EP2184316B1 (en) * | 2008-11-06 | 2016-08-31 | Clariant International Ltd | Composition comprising propylene-olefin-copolymer waxes and carbon black |
| JP5998581B2 (en) * | 2012-03-30 | 2016-09-28 | 東洋インキＳｃホールディングス株式会社 | Resin composition |
| JP6121742B2 (en) | 2013-02-15 | 2017-04-26 | 株式会社フジクラ | Conductive thermoplastic resin composition and cable |
| JP2016108524A (en) * | 2014-12-04 | 2016-06-20 | 東洋インキＳｃホールディングス株式会社 | Conductive resin composition, conductive master batch, molded body, and production method of the same |
-
2016
- 2016-02-19 KR KR1020160020000A patent/KR101830957B1/en active IP Right Grant
-
2017
- 2017-02-20 CN CN201710090051.1A patent/CN107099077B/en active Active
- 2017-02-20 JP JP2017029481A patent/JP6386114B2/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006501354A (en) * | 2002-10-02 | 2006-01-12 | ダウ グローバル テクノロジーズ インコーポレイティド | Polymer composition comprising a low viscosity homogeneously branched ethylene / α-olefin extender |
| US20110168425A1 (en) * | 2010-01-08 | 2011-07-14 | Ahmed Ali Basfar | Clean flame retardant compositions with carbon nano tube for enhancing mechanical properties for insulation of wire and cable |
| CN101831103A (en) * | 2010-05-24 | 2010-09-15 | 哈尔滨理工大学 | High-conductivity polyolefin composite material and preparation method thereof |
| CN102617918A (en) * | 2012-04-11 | 2012-08-01 | 四川大学 | Method for preparing high-ductility conductive polymer composite material |
| EP2660284A1 (en) * | 2012-05-04 | 2013-11-06 | Université Catholique De Louvain | Electroconductive nanocomposite |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109971026A (en) * | 2017-12-14 | 2019-07-05 | 锦湖石油化学株式会社 | Conductive foaming bead and preparation method thereof |
| CN109161087A (en) * | 2018-07-17 | 2019-01-08 | 广州润锋科技股份有限公司 | A kind of preparation method of carbon nanotube composite polyethylene anti-static material |
| CN113272380A (en) * | 2019-01-29 | 2021-08-17 | 三井—陶氏聚合化学株式会社 | Resin composition and molded article |
| CN113272380B (en) * | 2019-01-29 | 2023-12-08 | 三井—陶氏聚合化学株式会社 | Resin composition and molded article |
| CN114729149A (en) * | 2019-11-27 | 2022-07-08 | 韩华思路信株式会社 | Conductive resin composition for anti-slip and molded article comprising same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101830957B1 (en) | 2018-02-22 |
| KR20170098083A (en) | 2017-08-29 |
| JP2017145414A (en) | 2017-08-24 |
| JP6386114B2 (en) | 2018-09-05 |
| CN107099077B (en) | 2020-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107099077A (en) | The preparation method of conductive resin composition | |
| CN105504503B (en) | A kind of resistance to scratching, anti-precipitation PP composite material and preparation method thereof | |
| CA2394955C (en) | Oriented nanofibers embedded in polymer matrix | |
| KR101851952B1 (en) | Electrically conductive resin composition and method of preparing the same | |
| CN103013060B (en) | Polyethylene toughening thermoplastic polyester composite material and preparation method thereof | |
| EP3268415B1 (en) | Process for the preparation of composite articles having enhanced electrical properties | |
| KR102085939B1 (en) | A expanded bead having electrical conductivity and a method for manufacturing the same | |
| CN103342859B (en) | A kind of low smell, low VOC glass fiber reinforced polypropylene composite material and preparation method thereof | |
| KR101799573B1 (en) | Conductive resin composition and plastic article using the same | |
| WO2021072357A1 (en) | Melt-compounded polyamide graphene composites | |
| EP2660284A1 (en) | Electroconductive nanocomposite | |
| CN108192218A (en) | A kind of three-dimensional interpenetrating polymer network structural conductive alloy material and preparation method thereof | |
| CN102432947A (en) | Composite fiber reinforcement polypropylene material and preparation method thereof | |
| CN110317407A (en) | A kind of scratch-resistant PP composite material and preparation method | |
| US11749421B2 (en) | Electrically conductive resin composition and method for producing same | |
| TWI721556B (en) | Electrically conductive resin composition and preparation method thereof | |
| CN110885505A (en) | Conductive resin composition and method for preparing same | |
| KR102579779B1 (en) | Resin composition and molded body | |
| CN104861355A (en) | Polyvinyl chloride and polyethylene composition with heat and electricity conduction functions | |
| WO2021035202A1 (en) | Graphene reinforced hybrid composites | |
| JP2023128688A (en) | conductive mixture | |
| CN109423017A (en) | A kind of PET composition and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |