CN102837430A - Preparation method of designable polymer-based conductive composite material - Google Patents
Preparation method of designable polymer-based conductive composite material Download PDFInfo
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Abstract
The invention discloses a preparation method of a designable polymer-based conductive composite material. The preparation method consists of: utilizing a microlayer coextrusion device to prepare a fiber layer and conductive layer alternately arranged multilayer conductive composite material, and preparing a three-dimensional conductive network equipped composite material melt blending; putting the raw materials of the fiber layer and the conductive layer respectively into an extruder to conduct coextrusion so as to form two layers of melts, which then flow through n layer multipliers to obtain an alternating layer structure with 2<(n+1)> layers; with the increase of layers, making the dispersion phase in the fiber layer form microfibers with a high length-diameter ratio; letting conductive particles in the conductive layer gradually migrate to microfibers at an adjacent layer so as to form a conductive channel through a lap joint of the microfibers in the direction of a parallel layer interface; and finally subjecting the layered product to melt blending, thus forming the composite material with the three-dimensional conductive network. Compared with traditional preparation methods, the equipment involved in the invention is easily available and simple to operate, and has high efficiency. The prepared conductive composite material has the characteristics of low percolation value and high breaking elongation, etc.
Description
Technical field
The present invention relates to polymer processing field, in particular, the present invention relates to design the preparation of polymer base conductive composite material.
Background technology
Conduction is an important research direction of polymers functionization; Its mainly realization means are in polymeric matrix, to add conducting particles (like carbon black, CNT, metallic etc.), finally reach the purpose that improves polymer conductivity through concentration and the dispersing mode of controlling particle.Exceed that to ooze phenomenon be the most significant characteristic of polymer/conducting particles composite, promptly when the content of conducting particles is increased to a certain critical zone, the phenomenon that system resistance sharply descends.Corresponding at this moment critical particle concentration is called to exceed oozes threshold values.Exceed that to ooze threshold values low more, show that to set up the required conducting particles of conductive path few more, thereby it is an important parameter of measurement system electric conductivity.In fact, because the influence of factors such as polarity, interface, processing mode, conventional polymer/conducting particles blended compound material often has higher exceeding and oozes threshold values, promptly will reach to use required electrical conductivity, needs to add too much conducting particles.Yet higher particle concentration often can be brought the reduction of whole compound system toughness and the deterioration of processing characteristics again, but also possibly in process, cause bigger dust pollution and higher production cost.
Recently; People such as Guo Shaoyun are with microbedding coextrusion system [Chinese invention patent; The patent No.: ZL200610022348.6] be incorporated in the preparation of polymer/conducting particles composite, attempt to solve the directional profile of conducting particles and the problem that continuous restricted clearance is difficult to regulate and control.They carry out the microbedding coextrusion with carbon black and polypropene blended back with virgin pp, have prepared the laminar composite that a kind of conductive layer and insulating barrier are alternately arranged.Hope to utilize the layered distribution of conducting particles to set up continuous conductive channel.Discover that compare with traditional co-mixing system, this layered system has lower exceeding and oozes threshold values.But, thereby cause the reduction [Shuangxi Xu et al., Polymer, vol.49 (22): 4861-4870.] of system electric conductivity along with the increase of the number of plies will destroy the probability that conducting particles overlaps each other.And the special layer structure of this material makes its many performance have anisotropy, limits its application in some fields.
Summary of the invention
The objective of the invention is to the present situation of preparation polymer base conductive composite material and a kind of new method for preparing polymer base conductive composite material is provided, be difficult to the control phase morphology to solve prior art, construct the continuous conduction network, technical problems such as design electric conductivity.
The preparation method who designs polymer base conductive composite material disclosed by the invention is characterized at first will preparing conductive layer material and fibrage material respectively, and they all are polymer and filler or prepare through the melt blending mode with another kind of polymer.
Conductive layer material: by obtaining as the filler of conductive materials with as polymer granulation behind melt blending of matrix.The weight content of conductive materials in the conductive layer material generally is controlled in 0.01-50% the scope.Conductive materials can be at least a in carbon black, graphite, Graphene, carbon fiber, CNT, metal and the metal oxide.Matrix polymer can be at least a in polyethylene, polypropylene, polystyrene, polymethyl methacrylate, acrylonitrile-styrene-butadiene copolymer, polyphenylene oxide, polysulfones, Merlon, synthetic rubber and the thermoplastic elastomer (TPE).
Fibrage material: obtain by granulation behind two kinds of polymer melt blendings.The weight content of decentralized photo in the fibrage material is 0.5-50%.Dispersed phase polymer can be at least a in polyamide, polyester, ethylene-vinyl alcohol copolymer, the thermoplastic liquid crystal polymer.Matrix polymer can be at least a in polyethylene, polypropylene, polystyrene, polymethyl methacrylate, acrylonitrile-styrene-butadiene copolymer, polyphenylene oxide, polysulfones, Merlon, synthetic rubber and the thermoplastic elastomer (TPE).In order to improve the bonding interface of decentralized photo and matrix polymer, can add compatilizer in the melt blending stage.The compatilizer type is confirmed according to polymer property.
The preparation method who designs polymer base conductive composite material disclosed by the invention: respectively with the fibrage material of method for preparing and the middle fusion plastification of two extruders (A, B) of conductive layer material input microbedding co-extrusion device; Two strands of melts are located to be overlapped into two-layer at convergence device (C); Through the cutting of n layer multiplier (D) and superimposed after, obtain 2 from exporting mould (E)
(n+1)The multilayer materials (F) of layer.Wherein, the decentralized photo in the fibrage is repeatedly cutting streamwise elongation gradually in the lamination process, and original position forms the fento with high length-diameter ratio; Conducting particles in the conductive layer is then along with near the increase of the number of plies migration of the fento in the adjacent fiber layer bed boundary gradually, and forms conductive channel through the overlap joint of fento direction at the parallel layers interface.At last layered article is carried out melt blending, destroy the orientation of fento, form polymer base conductive composite material with three-dimensional conductive network.
In technique scheme, the number of plies of the alternate multiple goods that obtain through the microbedding coextrusion can be regulated through changing a layer multiplier number, and bed thickness is than regulating through the rotating ratio that changes two extruders.These goods can both can directly use for sheet, membranaceous, strip, tubulose, different form, a kind of in granular, also can after second melting machine-shaping, use.
In technique scheme, the second melting processing molding method of said microbedding coextrusion goods can be selected for use and extrude, a kind of in the curtain coating, banburying, injection moulding, blowing.Processing temperature is between the fusing point of matrix phase and fibrage decentralized photo.Goods after the second melting processing can be sheet, membranaceous, strip, tubulose, different form, a kind of in granular.
The preparation method who designs polymer base conductive composite material disclosed by the invention; Be characterized in both can making anisotropic alternate multiple conducing composite material, also can be processed to form isotropic polymer-matrix electric conduction blended compound material through the second melting of traditional polymer forming method through the microbedding coextrusion.
Experimental result shows that the polymer base conductive composite material that adopts the inventive method to prepare is compared with the polymer base conductive composite material that conventional method makes, and the draw ratio of fento is bigger, overlap joint is more perfect; Carbon black is only moved to the fento surface, exceedes that to ooze threshold values lower; The alternately stratiform conducing composite material that can design the anisotropic with one-dimensional electric path according to actual needs perhaps has the blend conducing composite material of the isotropic of three-dimensional conductive network.
The present invention has following advantage: 1, equipment involved in the present invention is simple and easy to, and only needs the logical extruder of two Daeporis is connect through convergence device, and adds the several layers multiplier at mouth mould place; Needed raw material is commercially available, need not synthesize other chemicals.This method has simple to operation, and production cost is low, characteristics such as efficient height.
2, through the polymer base conductive composite material of the inventive method preparation, compare with the traditional preparation process method, fento is to form through the field of force that runner provides, and draw ratio is bigger, overlap joint is more perfect.
3, through the polymer base conductive composite material of the inventive method preparation, fento and carbon black are distributed in respectively in the adjacent layer in the alternating laminated structure, thereby can pass through the regulating course structure, make carbon black only move to the fento surface, exceed that to ooze threshold values lower.
4, through the polymer base conductive composite material of the inventive method preparation, the alternately stratiform conducing composite material that can design the anisotropic with one-dimensional electric path according to actual needs perhaps has the blend conducing composite material of the isotropic of three-dimensional conductive network.
5, through the prepared polymer base conductive composite material of method provided by the invention, its elongation at break increases substantially.
The present invention also has more otherwise advantages.
Description of drawings
Fig. 1 is the structural representation of layering co-extrusion device involved in the present invention.In the drawings, A, B: extruder, C: convergence device D: layer multiplier E: outlet mould F: conductive layer/fibrage alternate multiple composite structure sketch map.
Fig. 2 is the sketch map that conducting particles distributes and the fento form develops in the polymer-matrix electric conduction blended compound material that makes after prepared alternate multiple polymer base conductive composite material of the present invention and the second melting blend processing.
The specific embodiment
Below through embodiment the present invention is further specifically described.In following each embodiment, the consumption of each component is weight consumption.Be necessary to be pointed out that at this following examples only are used for the present invention is done further explanation; Can not be interpreted as restriction to protection domain of the present invention; This art skilled person makes some nonessential improvement and adjustment according to the invention described above content to the present invention, still belongs to protection scope of the present invention.
The good effect that the present invention produces can describe with embodiment.
Embodiment 1
Raw material is polypropylene, nylon 6 and carbon black.The conductive layer pellet is the blend of polypropylene and carbon black, and content of carbon black is 8%.The fibrage pellet is the blend of polypropylene, nylon 6 and maleic anhydride inoculated polypropylene, and nylon 6 content are 19%, and maleic anhydride inoculated polypropylene is 1% as the addition of compatilizer.After two kinds of pellet dryings, (the extruder speed ratio is 1:1, and each section of extruder temperature is at 130-240 to drop in the two extruders of microbedding co-extrusion device fusion plastification respectively
oBetween the C), (layer multiplier temperature is 240 to pass through 0-8 layer multiplier respectively
oC), after cooling, make 2 to 512 layers alternately laminar composite.The resistivity measurement result shows that when the number of plies was lower than 64 layers, the specific insulation of streamwise was basicly stable 10
10Near the Ω .cm.Along with the further increase of the number of plies, resistivity reduces gradually, when the number of plies reaches 512 layers, reduces to 910 Ω .cm.As relatively, do not add the nylon phase, but the resistivity with 512 layers of compound system of identical content of carbon black is 1.2 * 10
10Ω .cm.On the other hand, the variation of the number of plies does not cause that decline along perpendicular flow direction specific insulation is (all 10
10About Ω .cm), therefore, the increase of the number of plies makes the anisotropy of system electrical property be tending towards obvious.
Embodiment 2
The microbedding coextrusion goods that make among the embodiment 1 are carried out second melting blend and hot-forming in banbury, processing temperature is 195
OCThe resistivity measurement result shows that the specific insulation of layered article after second melting processing that the number of plies is high more is low more, and for example the resistivity of 2 laminates after second melting processing is 3.4 * 10
10Ω .cm, and the resistivity of 512 laminates behind second melting is 9.1 * 10
3Ω .cm.As comparing, the resistivity of 512 laminates behind second melting that does not add nylon is 4.3 * 10
5Ω .cm.In addition, through the goods that the second melting banburying obtains, the anisotropy of electrical property disappears basically, and the resistivity of all directions is basic identical.
Embodiment 3
Raw material is polyethylene, thermoplastic liquid crystal polymer, CNT.The conductive layer pellet is the blend of polyethylene and CNT, and content of carbon nanotubes is 2%.The fibrage pellet is the blend of polyethylene, thermoplastic liquid crystal polymer, maleic anhydride grafted polyethylene, and thermoplastic liquid crystal polymer content is 15%, and maleic anhydride grafted polyethylene is 1% as the addition of compatilizer.After two kinds of pellet dryings, (the extruder speed ratio is 1:1, and each section of extruder temperature is at 130-250 to drop in the two extruders of microbedding co-extrusion device fusion plastification respectively
oBetween the C), (layer multiplier temperature is 250 to pass through 0-6 layer multiplier respectively
oC), after cooling, make the alternately laminar composite of 2-128 layer.The resistivity measurement result shows that along with the increase of the number of plies, resistivity reduces gradually, when the number of plies reaches 128 layers, reduces to 1050 Ω .cm.As relatively, annex solution crystalline phase not, but the resistivity with 128 layers of compound system of identical content of carbon nanotubes is 3.2 * 10
5Ω .cm.On the other hand, the variation of the number of plies does not cause that decline along perpendicular flow direction specific insulation is (all 10
9About Ω .cm), therefore, the increase of the number of plies makes the anisotropy of system electrical property be tending towards obvious.
Embodiment 4
With after the microbedding coextrusion goods granulation that makes among the embodiment 3 215
OCCarry out injection mo(u)lding.The resistivity measurement result shows that the specific insulation of layered article after second melting processing that the number of plies is high more is low more, and for example the resistivity of 2 laminates after second melting processing is 5.2 * 10
5Ω .cm, and the resistivity of 128 laminates behind second melting is 720 Ω .cm.As comparing, the resistivity of 128 laminates behind second melting that does not add liquid crystal is 1.4 * 10
4Ω .cm.
Claims (10)
1. preparation method that can design polymer base conductive composite material; It is characterized in that the pellet of fibrage and conductive layer drops into fusion plastification in the two extruders of microbedding co-extrusion device (A, B) respectively; Two strands of melts are located to be overlapped into two-layer at convergence device (C); The cutting of process n layer multiplier (D) and superimposed obtains 2
(n+1)The alternate multiple conducing composite material of layer carries out melt blending with layered article at last, destroys the orientation of fento, forms the polymer-matrix electric conduction blended compound material with three-dimensional conductive network.
2. according to the said preparation method who designs polymer base conductive composite material of claim 1; It is characterized in that the conductive layer pellet is obtained by conductive materials and polymeric matrix granulation behind melt blending, the weight content of conductive materials in the conductive layer material is 0.01-50%.
3. according to the preparation method of the said conductive layer pellet of claim 2, it is characterized in that conductive materials is at least a in carbon black, graphite, Graphene, carbon fiber, CNT, metal and the metal oxide; Polymeric matrix is to be selected from least a in polyethylene, polypropylene, polystyrene, polymethyl methacrylate, acrylonitrile-styrene-butadiene copolymer, polyphenylene oxide, polysulfones, Merlon, synthetic rubber and the thermoplastic elastomer (TPE).
4. according to the said preparation method who designs polymer base conductive composite material of claim 1, it is characterized in that the fibrage pellet is obtained by two kinds of polymer granulations behind melt blending, the weight content of decentralized photo in the fibrage material is 0.5-50%.
5. according to the preparation method of the said fibrage pellet of claim 4, it is characterized in that polymer that its decentralized photo is selected for use is at least a in polyamide, polyester, ethylene-vinyl alcohol copolymer, the thermoplastic liquid crystal polymer; Polymeric matrix is to be selected from least a in polyethylene, polypropylene, polystyrene, polymethyl methacrylate, acrylonitrile-styrene-butadiene copolymer, polyphenylene oxide, polysulfones, Merlon, synthetic rubber and the thermoplastic elastomer (TPE).
6. according to the said preparation method who designs polymer base conductive composite material of claim 1, the bed thickness of the alternate multiple goods that it is characterized in that obtaining through the microbedding coextrusion is than regulating with layer multiplier quantity through the rotating ratio of extruder respectively with the number of plies.
7. according to the said preparation method who designs polymer base conductive composite material of claim 1, it is characterized in that to be sheet, membranaceous, strip, tubulose, different form, a kind of in granular through alternate multiple goods that the microbedding coextrusion obtains.
8. according to the said preparation method who designs polymer base conductive composite material of claim 1, it is characterized in that the alternate multiple goods that obtain through the microbedding coextrusion can directly use, and also can use after second melting machine-shaping.
9. according to the said preparation method who designs polymer base conductive composite material of claim 8, the second melting blend processing molding method that it is characterized in that the alternate multiple goods can be selected for use and extrude, a kind of in the curtain coating, banburying, injection moulding, blowing.
10. according to the said preparation method who designs polymer base conductive composite material of claim 9, it is characterized in that the alternate multiple goods can be sheet, membranaceous, strip, tubulose, different form, a kind of in granular after second melting blend processing.
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| CN103333394B (en) * | 2013-07-15 | 2015-12-09 | 四川大学 | A kind of preparation method designing polymer-based carbon functional membrane |
| CN103342027B (en) * | 2013-07-15 | 2016-03-30 | 四川大学 | A kind of preparation method of programmable polymer based multilayer dielectric composite material |
| CN106413367B (en) * | 2016-09-05 | 2019-07-26 | 四川大学 | A kind of multifunctional macromolecule Quito layer electromagnetic shielding material and preparation method thereof |
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| CN107629383A (en) * | 2017-09-08 | 2018-01-26 | 深圳市通产丽星股份有限公司 | A kind of graphene composite thin film material and preparation method thereof, application |
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| CN108440840A (en) * | 2018-03-24 | 2018-08-24 | 郑州大学 | A kind of preparation method of anisotropic conductive polymer composite |
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| CN111081423A (en) * | 2019-12-27 | 2020-04-28 | 暨南大学 | Oriented conductive composite material and preparation method and application thereof |
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Application publication date: 20121226 |