CN106671386A - Conductive polymer tube with controllable axial conductivity and radial conductivity, and preparation method thereof - Google Patents
Conductive polymer tube with controllable axial conductivity and radial conductivity, and preparation method thereof Download PDFInfo
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- CN106671386A CN106671386A CN201611226753.XA CN201611226753A CN106671386A CN 106671386 A CN106671386 A CN 106671386A CN 201611226753 A CN201611226753 A CN 201611226753A CN 106671386 A CN106671386 A CN 106671386A
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- 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
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/90—Thermal treatment of the stream of extruded material, e.g. cooling with calibration or sizing, i.e. combined with fixing or setting of the final dimensions of the extruded article
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- 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
- B29C48/30—Extrusion nozzles or dies
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- 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
- B29C48/30—Extrusion nozzles or dies
- B29C48/32—Extrusion nozzles or dies with annular openings, e.g. for forming tubular articles
- B29C48/33—Extrusion nozzles or dies with annular openings, e.g. for forming tubular articles with parts rotatable relative to each other
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0856—Iron
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- 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
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- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
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- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
The invention belongs to the technical field of conductive polymers, and specifically relates to a conductive polymer tube with controllable axial conductivity and radial conductivity, and a preparation method thereof. The technical problem to be solved by the invention is to provide a preparation method for a conductive polymer tube with controllable axial conductivity and radial conductivity. The preparation method comprises the following steps: uniformly mixing a polymer with a conductive filler, then placing the mixture in a rotary extrusion device for the polymer tube and carrying out rotary melting extrusion, and cooling and sizing the extruded tube blank. The method disclosed by the invention is capable of inducing the one-dimensional orientation of the conductive filler to be changed into multi-dimensional orientation in a tube wall, and promoting to form a conductive network; and meanwhile, a hybridized conductive filler system with a higher connection degree is formed by virtue of the different shape response of the multi-dimensional conductive filler in a rotary flow field, so that the percolation threshold value of the conductive polymer tube is greatly lowered, the dosage of the expensive conductive filler is reduced, and the conductive polymer tube with high conductivity and excellent machinability and mechanical property is prepared.
Description
Technical field
The invention belongs to conducting polymer materials technical field, and in particular to a kind of two-way electrical conductivity controllable conductivity of the diameter of axle gathers
Compound pipe and preparation method thereof.
Background technology
Conducting polymer is a kind of to realize the compound of conducting polymer performance by adding one or more conductive fillers
Material, and there is very wide application prospect in fields such as antistatic, electromagnetic shielding, sensor and conductors.Conducting polymer
Pipe is the extraordinary conductive material that a class has high added value, specific use, especially diameter less than its special shape of the micro-pipe of 5mm
Shape has important use and is gradually paid close attention to (US4278835 with industrial quarters by academic in flexible sensor, medicine and hygiene fieldses
A).But, keep the electric conductivity of polymeric material but very difficult in the course of processing of polymer pipe.Prepare polymer to lead
It is critical only that for electric material can form conductive path, but traditional melting extrusion or injection molding process in polymeric matrix
In, polymer melt is subject to extremely strong shearing or stretching action, makes conductive filler one-dimensional in polymeric matrix height-oriented.
Uttandaraman Sundaraj(1.Al-Saleh M H and Sundararaj U.Electromagnetic
interference shielding mechanisms of CNT/polymer composites[J].Carbon,2009.47
(7):1738-1746.2.Arjmand M,Apperley T,Okoniewski M,and Sundararaj
U.Comparative study of electromagnetic interference shielding properties of
injection molded versus compression molded multi-walled carbon nanotube/
polystyrene composites[J].Carbon,2012.50(14):5126-5134.3.Arjmand M,Mahmoodi
M,Gelves G A,Park S,and Sundararaj U.Electrical and electromagnetic
interference shielding properties of flow-induced oriented carbon nanotubes
in polycarbonate[J].Carbon,2011.49(11):3430-3440.4.Mahmoodi M,Arjmand M,
Sundararaj U,and Park S.The electrical conductivity and electromagnetic
interference shielding of injection molded multi-walled carbon nanotube/
polystyrene composites[J].Carbon,2012.50(4):1455-1464.) have studied height-oriented conductive filler
Electric conductivity and find there is extremely thick polymer insulation layer between height-oriented conductive fiber, make to be difficult between conductive fiber
Contact with each other to form conductive path, the threshold value of oozing of material is greatly improved.In the production process of conducting polymer property management, polymer melt
By strongly tensile, conductive filler therein such as carbon fiber, CNT etc. is height-oriented, therefore its production difficulty is higher than tradition
Injected sample.Therefore, generally require to add substantial amounts of conductive filler or using more complicated production in conventional production practices
The such as long fine extrusion of technique.But these techniques have the obvious disadvantage that：Adding a large amount of conductive fillers will be greatly reduced polymer
Being failed during use, occurs in the mechanical performance of property management；Special production technology, such as by long conductive fiber such as carbon fiber, gold
Category silk is embedded in polymer and directly extrudes, high to extrusion machinery technical requirements, is unfavorable for extensive Traditional Industrialization production, pole
The earth limits the popularization of product.
With the development and the fierce market competition of national economy, the production and performance proposition to conducting polymer property management is higher will
Ask, such as wish that it possesses high conductivity, excellent processability and mechanical property, but existing polymer pipe processing method is difficult to reality
It is existing.
The content of the invention
The present invention seeks to the shortcoming that process technology is not enough and conductive filler addition is big of prior art presence is directed to,
Two-way electrical conductivity controllable conductivity polymer pipe of a kind of diameter of axle and preparation method thereof is provided.
First technical problem to be solved by this invention is to provide a kind of two-way electrical conductivity controllable conductivity polymer of diameter of axle
The preparation method of pipe.The method is comprised the following steps：Polymer is mixed homogeneously with conductive filler, is then placed in compound poly-
Melting rotary extrusion, the pipe cooling sizing of extrusion are carried out in compound pipe rotary extrusion device.
Preferably, in the preparation method of the two-way electrical conductivity controllable conductivity polymer pipe of the above-mentioned diameter of axle, described polymer pipe
Rotary extrusion device is ZL200810045785.9 described devices；It is described rotate to be plug individually rotate relative to mouth mold, mouth mold
Individually rotate relative to plug, plug and mouth mold simultaneously in rotating Vortex or plug and mouth mold simultaneously reverse rotation any one
Rotation mode.
Further, it is described to rotate to be core in the preparation method of the two-way electrical conductivity controllable conductivity polymer pipe of the above-mentioned diameter of axle
Rod is reversely rotated simultaneously with mouth mold.
Further, in the preparation method of the two-way electrical conductivity controllable conductivity polymer pipe of the above-mentioned diameter of axle, described plug
When simultaneously rotating Vortex or plug reversely rotate mode simultaneously with mouth mold with mouth mold, plug is identical with mouth mold rotating speed or differs.
Preferably, in the preparation method of the two-way electrical conductivity controllable conductivity polymer pipe of the above-mentioned diameter of axle, the polymer with lead
It is 50~99.99 parts by weight polymer and 0.01~50 weight portion conductive filler that electric filler is adding proportion.
Further, in the preparation method of the two-way electrical conductivity controllable conductivity polymer pipe of the above-mentioned diameter of axle, the polymer with
It is 70~99.9 parts by weight polymer and 0.1~30 weight portion conductive filler that conductive filler is adding proportion.
Preferably, in the preparation method of the two-way electrical conductivity controllable conductivity polymer pipe of the above-mentioned diameter of axle, the polymer is poly-
In ethylene, polypropylene, polybutene, polrvinyl chloride, nylon, polyurethane, polyolefin elastomer or polyvinyl acetate at least one
Kind.
Further, in the preparation method of the two-way electrical conductivity controllable conductivity polymer pipe of the above-mentioned diameter of axle, the polyolefin bullet
Gonosome is ethylene and the high polymer of butylene, or the high polymer of ethylene and octene.
Preferably, in the preparation method of the two-way electrical conductivity controllable conductivity polymer pipe of the above-mentioned diameter of axle, the conductive filler is
At least one in carbon fiber, white carbon black, Graphene, CNT, iron powder or stainless steel fibre.
Further, in the preparation method of the two-way electrical conductivity controllable conductivity polymer pipe of the above-mentioned diameter of axle, the conductive filler
For carbon fiber and the mixture or carbon fiber and the mixture of white carbon black of Graphene.
Preferably, in the preparation method of the two-way electrical conductivity controllable conductivity polymer pipe of the above-mentioned diameter of axle, the rotary speed is 1
~60rpm/min.
Further, in the preparation method of the two-way electrical conductivity controllable conductivity polymer pipe of the above-mentioned diameter of axle, the rotary speed
For 10~40rpm/min.
Further, in the preparation method of the two-way electrical conductivity controllable conductivity polymer pipe of the above-mentioned diameter of axle, the rotation speed
Spend for 15~30rpm/min.
Preferably, in the preparation method of the two-way electrical conductivity controllable conductivity polymer pipe of the above-mentioned diameter of axle, it is added as needed
His auxiliary agent or filler.
Further, in the preparation method of the two-way electrical conductivity controllable conductivity polymer pipe of the above-mentioned diameter of axle, other described are helped
Agent is antioxidant, plasticizer, heat stabilizer, light stabilizer, fire retardant, antistatic additive, antifungus agent, coloring agent and brightening agent, fills out
At least one filled in agent, coupling agent, lubricant.
Further, in the preparation method of the two-way electrical conductivity controllable conductivity polymer pipe of the above-mentioned diameter of axle, described filler is
At least one in glass fibre, glass microballoon, Pulvis Talci, montmorillonite, Muscovitum, wollastonite, Calcium Carbonate.
Second technical problem to be solved by this invention is to provide the two-way electrical conductivity controllable conductivity polymer of the above-mentioned diameter of axle
The two-way electrical conductivity controllable conductivity polymer pipe of the diameter of axle that the preparation method of pipe is prepared.
Preferably, the two-way electrical conductivity controllable conductivity polymer pipe of the above-mentioned diameter of axle, the conductivity of axial direction is 1.0 × 10-4
~1.0S/cm, the electrical conductivity of radial direction is 1.0 × 10-11~1.0 × 10-1S/cm。
3rd technical problem to be solved by this invention is to provide the two-way electrical conductivity controllable conductivity polymer of the above-mentioned diameter of axle
Purposes of the pipe as strain transducer.
The inventive method has the advantage that compared with prior art：
1) the inventive method applies to rotate the field of force during conducting polymer property management is prepared, and can change rotation by simple
Rotary-die type and rotary speed, make conductive filler that multidimensional orientation is formed in polymer tube wall, and control the degree of orientation, form connection close
Controllable conductive network structure is spent, so as to realize the conducting polymer property management that electrical conductivity can be controlled freely.
2) the rotary extrusion technology that the inventive method is adopted has in the melting extrusion course of processing produces in bath surface
Generating layer stream, melt inside produces the characteristic of eddy-currents, thus in the regular arrangement of contact tube surface conductance filler, controllable contact tube
The conductive capability of wall surface, prepares high-performance special contact tube conductive with sandwich layer and that cortex insulate；Further, with rotation
Rotary speed is improved, and the conductive filler of multidimensional orientation hands over lid scope gradually to expand in tube wall, also can prepare with diameter of axle bi directional conductibility
Extraordinary contact tube.Two kinds of different contact tubes can be applicable to multiple fields, and regulation and control are simple, with competitive advantage.
3) conductivity of the conducting polymer property management prepared by the inventive method is to tubular change such as bending, stretching, distortion tool
There are response, i.e. polymer pipe conductivity to change with its deformation, such that it is able to be applied to the fields such as DEFORMATION RESPONSE sensor.
4) the rotary extrusion hydridization conductive filler system technology that the inventive method is adopted, it is low that conductive filler oozes threshold value, adds
Dosage is few, and production efficiency is high, thus not only makes prepared tubing both possess the competitive advantage of high-quality, and because of low cost more
Tool price competitiveness.
5) the inventive method is processed using melting extrusion, thus process velocity is fast, yield is high, meets industrialization and gives birth on a large scale
The requirement of product；The method process is simple that the present invention is provided is ripe, it is easy to grasps control, also allows for popularization and application.
Description of the drawings
Fig. 1 is the inventive method gained contact tube conducting position schematic diagram；
Fig. 2 be the inventive method in process conductive filler formed conductive path principle schematic；
In the inside and outside wall surface of conducting polymer property management, conductive filler is arranged parallel to each other, and makes polymer pipe in radial direction
With insulating properties, and in pipe intermediate layer, conductive filler multidimensional orientation, between contact with each other, form conductive path, make pipe in axial direction
Direction has high electrical conductivity；With the raising of rotary speed, gradually inside outer wall surface expands middle multidimensional oriented layer, most
Make conducting polymer property management that also there is good electric conductivity in radial direction eventually.
Fig. 3 passes through 30r/ for conventional extrusion with the parts by weight of carbon fibers of the inventive method 15 and 85 weight portion Low Density Polyethylenes
Min plugs reversely rotate the scanning electron microscope comparison diagram after the inside and outside wall etching of extrusion contact tube with mouth mold simultaneously；
Wherein, a, b figure is respectively the inside and outside wall of conventional extruding pipe, and c, d figure is respectively the inside and outside wall of contact tube of the present invention,
The direction of arrow is that pipeline extrudes direction in figure；It can be seen that the inventive method deviates carbon fiber by rotary extrusion
Axially arrange and inside and outside wall offset direction is conversely, therefore carbon fiber is internally formed the conductive path of three-dimensional, realization in polymer pipe
Electrical conductivity fast lifting.
Specific embodiment
Conventional melt is extruded or injection molding is prepared in polymer conducting material method, because polymer melt is subject to extremely strong
Shearing or stretching action, make conductive filler one-dimensional in polymeric matrix height-oriented, so as to reduce conducting polymer energy
Power.And add a large amount of conductive fillers or using more complicated production technology be all individually present as the cost that wastes raw material, complex operation,
The defect such as time-consuming.
Contact tube institute produced problem is prepared for above-mentioned prior art, the present inventor has found through numerous studies test,
Using polymer pipe rotary extrusion device (ZL200810045785.9), the polymer pipe rotary extrusion device, plug and mouth mold
Independent adjustable, rotating speed and directionally independent adjustable individually rotates, mouth mold is relative to plug list so as to be capable of achieving plug relative to mouth mold
Solely simultaneously rotating Vortex or plug and mouth mold reversely rotate these four different rotary modes simultaneously for rotation, plug and mouth mold, with
Axially extrusion/pulling motion superposition, regulates and controls polymer melt flow pattern, formed along the different VELOCITY DISTRIBUTION in thickness of pipe wall direction with
Stress distribution, produces the stress and velocity gradient distribution that lid is mutually handed in tube wall, and induction conductive filler forms multidimensional in tube wall
Orientation mutually hands over the arrangement mode of lid, so as to promote conductive network to be formed.Various dimensions conductive filler (one-dimensional filler is utilized simultaneously：
Carbon fiber, two-dimentional filler：Graphene, three-dimensional filler：White carbon black) morphological grad image different in rotational flow field, i.e., one-dimensional filler
The characteristics of easily deviation, hardly possible deviation of two three-dimensional fillers, promote conductive filler to contact with each other, form the hydridization with bigger contiguity
Conductive filler system, is greatly reduced the threshold value of oozing of conducting polymer property management, reduces the consumption of expensive conductive filler, leads so as to prepare height
The conducting polymer property management of electric rate, excellent processability and mechanical property.
So, the invention provides a kind of preparation method of the two-way electrical conductivity controllable conductivity polymer pipe of diameter of axle, including with
Lower step：50~99.99 parts by weight polymer are mixed homogeneously with 0.01~50 weight portion conductive filler, then puts compound
Melting rotary extrusion is carried out with the rotating speed of 1~60rpm/min in polymer pipe rotary extrusion device, the pipe of extrusion is in traction
Cooling sizing is carried out under the traction of machine；It is described to rotate to be that plug individually rotates relative to mouth mold, mouth mold is relative to plug list
Solely rotation, plug and mouth mold are while any one rotation mode in the reverse rotation simultaneously of rotating Vortex or plug and mouth mold.This
Polymer and conductive filler also can be put into polymer pipe rotary extrusion dress by place using after conventional method melting extrusion, pelletizing
Put.
Preferably, the plug that rotates to be is reversely rotated simultaneously with mouth mold.
Preferably, described plug and mouth mold be when simultaneously rotating Vortex or plug reversely rotate mode simultaneously with mouth mold, core
Rod is identical with mouth mold rotating speed or differs.
In order to take into account conductive effect and energy consumption saving, preferred rotary speed is 10~40rpm/min.The further rotation
Rotary speed is 15~30rpm/min.
In order to take into account conductive effect and energy consumption saving, preferred polymers are that adding proportion is 70~99.9 weights with conductive filler
Amount part polymer and 0.1~30 weight portion conductive filler.
Preferably, the polymer is polyethylene, polypropylene, polybutene, polrvinyl chloride, nylon, polyurethane, polyolefin bullet
At least one in gonosome or polyvinyl acetate.
Preferably, the conductive filler is in carbon fiber, white carbon black, Graphene, CNT, iron powder or stainless steel fibre
It is at least one.Further, in order to ensure conductive effect, conductive filler should be the mixture of one-dimensional filler and two-dimentional filler, or
The mixture of one-dimensional filler and three-dimensional filler.Further, the conductive filler be carbon fiber and Graphene mixture or
The mixture of carbon fiber and white carbon black.
Further, in actual industrial metaplasia product, according to application to polymer pipe performance need, other can be added
Known antioxidant, plasticizer, heat stabilizer, light stabilizer, fire retardant, antistatic additive, antifungus agent, coloring agent and brightening agent,
The processing aids such as filler, coupling agent, lubricant, and some other contributes to the filler that pipe performance is further enhanced, such as
Glass fibre, glass microballoon, Pulvis Talci, montmorillonite, Muscovitum, wollastonite, Calcium Carbonate etc..
Inventor has found, by the controllable conduction of the rotary speed and conductive filler content of adjusting apparatus in the inventive method
The conducting position of pipe.Under low rotary speed, pipe inside and outside wall surface conductance fibers parallel one dimensional arrangement is non-conductive, and inside is due to rotation
Turn the speed difference being extruded into, form the three-dimensional conductive network handed over and cover, therefore axial direction is conductive, and radial direction is non-conductive.
As rotary speed increases, three-dimensional hands over the scope of cover net network gradually to expand, and finally also forms conductive network in the inside and outside wall surface of pipe,
That is diameter of axle direction bi directional conductibility.As conductive filler content increases, realize critical speed required for Axial and radial bi directional conductibility by
Gradually reduce.
Inventor also has found that the factor of conductivity is affected in the inventive method has rotary speed, rotary mode, filler to add
Amount, filling kind etc..When not up to threshold value, can be by adjustment rotary speed, rotary mode, filling adding amount, filling kind
To control threshold value；When threshold value is reached, filling adding amount affects little to conductivity, increases conductive filler addition conductivity
Slow rising finally tends to constant, now can control the size of conductivity by adjusting rotary speed, rotary mode.
By the inventive method, each influence factor can reasonably be controlled, so as to prepare according to the demand of application
Conducting position is controllable, the contact tube that conductivity is controllable.
Present invention also offers the two-way electrical conductivity controllable conductivity polymer pipe of the diameter of axle that said method is prepared.Further
, the conductivity of axial direction is 1.0 × 10-4~1.0S/cm, the electrical conductivity of radial direction is 1.0 × 10-11~1.0 × 10- 1S/cm。
Inventor such as also has found the two-way electrical conductivity controllable conductivity polymer pipe of the diameter of axle is curved, is stretched, distorted at the shape
Become, it there is response, i.e. pipe conductivity to change with deformation deformation and changes, so as to the contact tube can be applied to DEFORMATION RESPONSE
The fields such as sensor.
Therefore, present invention also offers the two-way electrical conductivity controllable conductivity polymer pipe of the above-mentioned diameter of axle is used as strain transducer
Purposes.
The present invention is specifically described below by embodiment.It is important to point out that following examples are served only for this
Invention is further described, it is impossible to be interpreted as limiting the scope of the invention, and the person skilled in the art in the field can be with
Some nonessential modifications and adaptations are made to the present invention according to foregoing invention content.
What deserves to be explained is：1) number of material is weight portion in following examples and comparative example.2) following examples
Test what is carried out according to GB1410-78 with the electrical conductivity of tubing prepared by comparative example, electrical conductivity is more than 10-6S/cm is regarded as
Conductor.
Embodiment 1
First by the 99.99 weight account polyethylene LDPE (trades mark：2420H) with 0.01 parts by weight CNT twin-screw extrusion
Melting extrusion, pelletizing in machine, are then placed in gained pellet in polymer pipe rotary extrusion device, using the independent side of rotation of plug
Formula, with the rotating speed of 10rpm/min rotary extrusion is melted, and the pipe of extrusion carries out cooling down the prepared ￠ of sizing under the traction of traction machine
The polymer pipe of 3 calibers.
The axial electrical conductivity of the present embodiment gained tubing is 1.92 × 10-3S/cm, Radial Conductivity is 1.5 × 10-11S/
cm。
Embodiment 2
First by the 99.9 weight account polyethylene LDPE (trades mark：2420H) and in 0.1 parts by weight Graphene double screw extruder
Melting extrusion, pelletizing, are then placed in gained pellet in polymer pipe rotary extrusion device, using the independent rotation mode of mouth mold,
Rotary extrusion is melted with the rotating speed of 20rpm/min, the pipe of extrusion carries out the prepared ￠ 3 of cooling sizing under the traction of traction machine and manages
The polymer pipe in footpath.
The axial electrical conductivity of the present embodiment gained tubing is 3.92 × 10-2S/cm, Radial Conductivity is 4.2 × 10-11S/
cm。
Embodiment 3
First by the 90 weight account polyethylene LDPE (trades mark：It is 2420H) molten with 10 parts by weight carbon fiber double screw extruders
Melt extrusion, pelletizing, then gained pellet is placed in polymer pipe rotary extrusion device, using plug and mouth mold reverse rotation side
Formula, with the rotating speed of 60rpm/min rotary extrusion is melted, and the pipe of extrusion carries out cooling down the prepared ￠ of sizing under the traction of traction machine
The polymer pipe of 3 calibers.
The axial electrical conductivity of the present embodiment gained tubing is 4.1 × 10-1S/cm, Radial Conductivity is 6.41 × 10-3S/
cm。
Embodiment 4
First by the 50 weight account polyethylene LDPE (trades mark：2420H) with melting in 50 parts by weight white carbon black double screw extruders
Extrusion, pelletizing, are then placed in gained pellet in polymer pipe rotary extrusion device, using plug and mouth mold rotating Vortex side
Formula, with the rotating speed of 10rpm/min rotary extrusion is melted, and the pipe of extrusion carries out cooling down the prepared ￠ of sizing under the traction of traction machine
The polymer pipe of 3 calibers.
The axial electrical conductivity of the present embodiment gained tubing is 3.92 × 10-3S/cm, Radial Conductivity is 7 × 10-11S/cm。
Embodiment 5
First by melting extrusion, pelletizing in 60 parts by weight of polybutene and 40 parts by weight stainless steel fibre double screw extruders,
Then gained pellet is placed in polymer pipe rotary extrusion device, mode is reversely rotated using plug and mouth mold, with 1rpm/
The rotating speed melting rotary extrusion of min, the pipe of extrusion carries out cooling down the polymerization that sizing is obtained the calibers of ￠ 3 under the traction of traction machine
Property management.
The axial electrical conductivity of the present embodiment gained tubing is 1.12 × 10-4S/cm, Radial Conductivity is 6.86 × 10-11S/
cm。
Embodiment 6
First by melting extrusion, pelletizing in 90 parts by weight of polypropylene and 10 parts by weight iron powder double screw extruders, then will
Gained pellet is placed in polymer pipe rotary extrusion device, using plug and mouth mold rotating Vortex mode, turning with 5rpm/min
Fast thawing melts rotary extrusion, and the pipe of extrusion carries out cooling down the polymer pipe that sizing is obtained the calibers of ￠ 3 under the traction of traction machine.
The axial electrical conductivity of the present embodiment gained tubing is 2.92 × 10-3S/cm, Radial Conductivity is 9.11 × 10-11S/
cm。
Embodiment 7
First by the 60 weight account polyethylene LDPE (trades mark：2420H) with 40 parts by weight stainless steel fibre double screw extruders
Middle melting extrusion, pelletizing, are then placed in gained pellet in polymer pipe rotary extrusion device, the side individually rotated using plug
Formula, with the rotating speed of 60rpm/min rotary extrusion is melted, and the pipe of extrusion carries out cooling down the prepared ￠ of sizing under the traction of traction machine
The polymer pipe of 3 calibers.
The axial electrical conductivity of the present embodiment gained tubing is 4.82 × 10-1S/cm, Radial Conductivity is 1 × 10-1S/cm。
Embodiment 8
First will melt in 85 parts by weight of polypropylene and the parts by weight of graphite alkene double screw extruder of 10 parts by weight carbon fiber 5 and squeeze
Go out, pelletizing, then gained pellet is placed in polymer pipe rotary extrusion device, using the independent rotation mode of mouth mold, with
The rotating speed melting rotary extrusion of 50rpm/min, the pipe of extrusion carries out cooling down the prepared calibers of ￠ 3 of sizing under the traction of traction machine
Polymer pipe.
The axial electrical conductivity of the present embodiment gained tubing is 9.24 × 10-1S/cm, Radial Conductivity is 8.11 × 10-2S/
cm。
Embodiment 9
First will melt in 85 parts by weight of polybutene and 10 parts by weight carbon fibers and 5 weight fraction white carbon black double screw extruders
Extrusion, pelletizing, are then placed in gained pellet in polymer pipe rotary extrusion device, using plug and mouth mold rotating Vortex side
Formula, with the rotating speed of 30rpm/min rotary extrusion is melted, and the pipe of extrusion carries out cooling down the prepared ￠ of sizing under the traction of traction machine
The polymer pipe of 3 calibers.
The axial electrical conductivity of the present embodiment gained tubing is 1.34 × 10-1S/cm, Radial Conductivity is 7.51 × 10-11S/
cm。
Embodiment 10
First by 75 parts by weight of polyurethane and 20 parts by weight stainless steel fibres and 5 parts by weight of carbon nanotubes double screw extruders
Middle melting extrusion, pelletizing, are then placed in gained pellet in polymer pipe rotary extrusion device, are reversely revolved with mouth mold using plug
Turn mode, rotary extrusion is melted with the rotating speed of 20rpm/min, the pipe of extrusion carries out cooling down sizing system under the traction of traction machine
Obtain the polymer pipe of the calibers of ￠ 3.
The axial electrical conductivity of the present embodiment gained tubing is 7.83 × 10-2S/cm, Radial Conductivity is 7.21 × 10-11S/
cm。
Embodiment 11
First by the parts by weight polyurethane of 50 weight portion polyvinyl acetate 20 and 30 parts by weight carbon fiber twin-screw extrusions
Melting extrusion, pelletizing in machine, are then placed in gained pellet in polymer pipe rotary extrusion device, in the same direction with mouth mold using plug
Rotation mode, with the rotating speed of 5rpm/min rotary extrusion is melted, and the pipe of extrusion carries out cooling sizing under the traction of traction machine
The polymer pipe of the calibers of prepared ￠ 3.
The axial electrical conductivity of the present embodiment gained tubing is 5.12 × 10-4S/cm, Radial Conductivity is 3.21 × 10-2S/
cm。
Embodiment 12
First by melting extrusion, pelletizing in 85 parts by weight of polybutene and 15 parts by weight carbon fiber double screw extruders, then
Gained pellet is placed in polymer pipe rotary extrusion device, mode is reversely rotated using plug and mouth mold, with 10rpm/min's
Rotating speed melts rotary extrusion, and the pipe of extrusion carries out cooling down the polymer pipe that sizing is obtained the calibers of ￠ 3 under the traction of traction machine.
The axial electrical conductivity of the present embodiment gained tubing is 1.12 × 10-4S/cm, Radial Conductivity is 1.941 × 10-11S/
cm。
Embodiment 13
First by melting extrusion, pelletizing in 90 parts by weight of polyurethane and 10 parts by weight Graphene double screw extruders, then
Gained pellet is placed in polymer pipe rotary extrusion device, it is molten with the rotating speed of 40rpm/min using the independent rotation mode of plug
Melt rotary extrusion, the pipe of extrusion carries out cooling down the polymer pipe that sizing is obtained the calibers of ￠ 3 under the traction of traction machine.
The axial electrical conductivity of the present embodiment gained tubing is 1.24S/cm, and Radial Conductivity is 1.18 × 10-1S/cm。
Embodiment 14
First will melt in 90 parts by weight of polyurethane and the parts by weight of carbon fibers double screw extruder of 5 parts by weight Graphene 5 and squeeze
Go out, pelletizing, then gained pellet is placed in polymer pipe rotary extrusion device, using the independent rotation mode of plug, with
The rotating speed melting rotary extrusion of 15rpm/min, the pipe of extrusion carries out cooling down the prepared calibers of ￠ 3 of sizing under the traction of traction machine
Polymer pipe.
The axial electrical conductivity of the present embodiment gained tubing is 3.74 × 10-1S/cm, Radial Conductivity is 5.73 × 10-4S/
cm。
Comparative example 1
First by melting extrusion, pelletizing in 90 parts by weight of polyurethane and 10 parts by weight Graphene double screw extruders, then
Gained pellet is placed in polymer pipe routine extrusion device, the pipe of extrusion carries out cooling down sizing system under the traction of traction machine
Obtain the polymer pipe of the calibers of ￠ 3.
The axial electrical conductivity of gained tubing is 2.39 × 10-10S/cm, Radial Conductivity is 2.21 × 10-11S/cm。
Comparative example 2
First by melting extrusion, pelletizing in 70 weight portion LDPE and 30 parts by weight carbon fiber double screw extruders, then will
Gained pellet be placed in polymer pipe routine extrusion device in extrude pipe carry out under the traction of traction machine cool down sizing be obtained
The polymer pipe of the calibers of ￠ 3.
The axial electrical conductivity of gained tubing is 5.09 × 10-9S/cm, Radial Conductivity is 1.24 × 10-11S/cm。
Comparative example 3
First by melting extrusion, pelletizing in 50 weight portion polyvinyl acetate and 50 parts by weight white carbon black double screw extruders,
Then gained pellet is placed in polymer pipe routine extrusion device, the pipe of extrusion carries out cooling down under the traction of traction machine to be determined
Footpath is obtained the polymer pipe of the calibers of ￠ 3.
The axial electrical conductivity of gained tubing is 9.09 × 10-9S/cm, Radial Conductivity is 5.1 × 10-11S/cm。
Comparative example 4
First by melting extrusion, pelletizing in 60 parts by weight of polyurethane and 40 parts by weight iron powder double screw extruders, then will
Gained pellet is placed in polymer pipe routine extrusion device, and the pipe of extrusion carries out cooling sizing under the traction of traction machine and is obtained
The polymer pipe of the calibers of ￠ 3.
The axial electrical conductivity of gained tubing is 3.93 × 10-10S/cm, Radial Conductivity is 3.81 × 10-11S/cm。
Comparative example 5
First by melting extrusion, pelletizing in 90 parts by weight of polybutene and 10 parts by weight CNT double screw extruders, so
Gained pellet is placed in polymer pipe routine extrusion device afterwards, the pipe of extrusion carries out cooling sizing under the traction of traction machine
The polymer pipe of the calibers of prepared ￠ 3.
The axial electrical conductivity of gained tubing is 8.21 × 10-9S/cm, Radial Conductivity is 1.76 × 10-11S/cm。
Comparative example 6
First by melting extrusion, pelletizing in 80 parts by weight of polypropylene and 20 parts by weight stainless steel fibre double screw extruders,
Then gained pellet is placed in polymer pipe routine extrusion device, the pipe of extrusion carries out cooling down under the traction of traction machine to be determined
Footpath is obtained the polymer pipe of the calibers of ￠ 3.
The axial electrical conductivity of gained tubing is 4.49 × 10-11S/cm, Radial Conductivity is 4.12 × 10-11S/cm。
Comparative example 7
First by 80 parts by weight of polyurethane and the weight fraction CNT double screw extruder of 10 parts by weight Graphene 10
Melting extrusion, pelletizing, are then placed in gained pellet in polymer pipe routine extrusion device, pipe the leading in traction machine of extrusion
Carry out cooling down the polymer pipe that sizing is obtained the calibers of ￠ 3 under drawing.
The axial electrical conductivity of gained tubing is 8.81 × 10-9S/cm, Radial Conductivity is 5.12 × 10-11S/cm。
Comparative example 8
First by the weight fraction polyvinyl acetate of 70 parts by weight of polyurethane 20 and 10 parts by weight Graphene twin-screw extrusions
Melting extrusion, pelletizing in machine, are then placed in gained pellet in polymer pipe routine extrusion device, and the pipe of extrusion is in traction machine
Traction under carry out cooling down the polymer pipe that sizing is obtained ￠ 3 calibers.
The axial electrical conductivity of gained tubing is 6.11 × 10-9S/cm, Radial Conductivity is 1.51 × 10-11S/cm。
In summary it can be seen, the conducting polymer property management prepared using the inventive method, it is axially, radial method leads
The conducting polymer property management that electric rate can be prepared than traditional method is higher by several orders of magnitude, and can be according to the difference of different field
Demand, reasonably controls rotary speed, the usage amount of conductive filler to adjust conductive capability, conducting position.The present invention is difference
Field conducting polymer property management provides a kind of preferably selection.
Claims (10)
1. the preparation method of the two-way electrical conductivity controllable conductivity polymer pipe of the diameter of axle, it is characterised in that：Comprise the following steps：Will polymerization
Thing is mixed homogeneously with conductive filler, and then compound is placed in polymer pipe rotary extrusion device carries out melting rotary extrusion,
The pipe cooling sizing of extrusion.
2. the preparation method of the two-way electrical conductivity controllable conductivity polymer pipe of the diameter of axle according to claim 1, it is characterised in that：
Described polymer pipe rotary extrusion device is ZL200810045785.9 described devices；The plug that rotates to be is relative to mouth mold
Individually rotate, mouth mold individually rotates relative to plug, plug and mouth mold are while the reversely rotation simultaneously of rotating Vortex or plug and mouth mold
Any one rotation mode in turning；It is preferred that rotation mode is plug reversely rotate with mouth mold simultaneously.
3. the preparation method of the two-way electrical conductivity controllable conductivity polymer pipe of the diameter of axle according to claim 1, it is characterised in that：
The polymer is filled out for 50~99.99 parts by weight polymer for adding proportion with conductive filler with 0.01~50 weight portion conduction
Material；Further, the polymer is that adding proportion is 70~99.9 parts by weight polymer and 0.1~30 weight with conductive filler
Part conductive filler.
4. the preparation method of the two-way electrical conductivity controllable conductivity polymer pipe of the diameter of axle according to claim 1, it is characterised in that：
The polymer is polyethylene, polypropylene, polybutene, polrvinyl chloride, nylon, polyurethane, polyolefin elastomer or poly-vinegar acid second
At least one in alkene ester.
5. the preparation method of the two-way electrical conductivity controllable conductivity polymer pipe of the diameter of axle according to claim 1, it is characterised in that：
The conductive filler is at least one in carbon fiber, white carbon black, Graphene, CNT, iron powder or stainless steel fibre；Further
, the conductive filler is the mixture of one-dimensional filler and two-dimentional filler, or the mixture of one-dimensional filler and three-dimensional filler；More enter
One step, the conductive filler is carbon fiber and the mixture or carbon fiber of Graphene and the mixture of white carbon black.
6. the preparation method of the two-way electrical conductivity controllable conductivity polymer pipe of the diameter of axle according to claim 1, it is characterised in that：
The rotary speed is 1~60rpm/min；Further, the rotary speed is 10~40rpm/min；Further, institute
Rotary speed is stated for 15~30rpm/min.
7. the preparation method of the two-way electrical conductivity controllable conductivity polymer pipe of the diameter of axle according to any one of claim 1~6, its
It is characterised by：Other auxiliary agents or filler are added as needed；Further, other described auxiliary agents are antioxidant, plasticizer, heat
In stabilizer, light stabilizer, fire retardant, antistatic additive, antifungus agent, coloring agent and brightening agent, filler, coupling agent, lubricant
At least one；Described filler is in glass fibre, glass microballoon, Pulvis Talci, montmorillonite, Muscovitum, wollastonite, Calcium Carbonate
It is at least one.
8. the two-way electrical conductivity controllable conductivity polymer pipe of the diameter of axle, it is characterised in that：Axle by described in any one of claim 1~7
The preparation method of the two-way electrical conductivity controllable conductivity polymer pipe in footpath is prepared.
9. the two-way electrical conductivity controllable conductivity polymer pipe of the diameter of axle according to claim 8, it is characterised in that：Axial direction
Conductivity is 1.0 × 10-4~1.0S/cm, the electrical conductivity of radial direction is 1.0 × 10-11~1.0 × 10-1S/cm。
10. purposes of the two-way electrical conductivity controllable conductivity polymer pipe of the diameter of axle described in claim 8 or 9 as strain transducer.
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| CN110903652A (en) * | 2019-12-13 | 2020-03-24 | 深圳市中金岭南科技有限公司 | Flexible stretchable conductive composite material of fishing net structure and preparation method and application thereof |
| CN111251568A (en) * | 2020-01-16 | 2020-06-09 | 四川大学 | Polymer micro-catheter with microcosmic two-dimensional flaky fillers regularly arranged and preparation method thereof |
| CN113306059A (en) * | 2021-05-31 | 2021-08-27 | 四川大学 | Terahertz modulation material with gradient modulation amplitude and preparation method thereof |
| CN115105633A (en) * | 2022-07-27 | 2022-09-27 | 四川大学 | Chemical etching open-pore porous polypropylene pipe and preparation method thereof |
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| CN111251568A (en) * | 2020-01-16 | 2020-06-09 | 四川大学 | Polymer micro-catheter with microcosmic two-dimensional flaky fillers regularly arranged and preparation method thereof |
| CN113306059A (en) * | 2021-05-31 | 2021-08-27 | 四川大学 | Terahertz modulation material with gradient modulation amplitude and preparation method thereof |
| CN115105633A (en) * | 2022-07-27 | 2022-09-27 | 四川大学 | Chemical etching open-pore porous polypropylene pipe and preparation method thereof |
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