CN102675893B - Method for preparing polymer-based conducting composite material by melt blending - Google Patents
Method for preparing polymer-based conducting composite material by melt blending Download PDFInfo
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Abstract
A method for preparing polymer-based conducting composite material by melt blending comprises the steps of (1) selecting a carbon nano tube or graphite to serve as a conducting filler, or selecting a first polymer or a second polymer, and enabling the viscosity ratio between the first polymer and the second polymer to be not smaller than 100; or enabling the first polymer to be low in affinity with the conducting filler, enabling the second polymer to be high in affinity with the conducting filler, the theoretic infiltration coefficient omega a of a blending system formed by the conducting filler, the first polymer and the second polymer to be larger than 1, enabling gamma to represent interfacial tension between two phases, and enabling the first polymer and the second polymer to be incompatible in chemical property; (2) performing calcination or acidizing treatment to the conducting filler; and (3) enabling the conducting filler to first undergo melt blending with the first polymer, obtaining a master batch, enabling the master batch to undergo melt blending with the second polymer, and obtaining the polymer-based conducting composite material. According to the method, the consumed quantity of the conducting filler is low, and the prepared conducting composite material is good in conducting performance and strong in mechanical property.
Description
Technical field
The invention belongs to the preparing technical field of polymer base conductive composite material.
Background technology
Polymer base conductive composite material refers to conducting material (conductive filler material) such as adding carbon black, carbon fiber, carbon pipe, graphite, metal-powder in the nonconducting polymeric matrix of intrinsic and the matrix material with electroconductibility of preparation.This type of conductive polymers cost is low, stability is high, be easy to machine-shaping, and electric property is adjustable in a big way, has a wide range of applications in fields such as antistatic, electromagnetic wave shielding, fuel cell double polar plate, sensor, electrically conducting coatings.Its electrical conduction mechanism is, when conductive filler material content exceedes certain threshold value (conduct electricity excess effusion value), conductive filler material forms continuous network in polymkeric substance, and electronics transmits and makes polymkeric substance possess electroconductibility in network.Increase conductive filler material and can ensure its electroconductibility, but addition is crossed the viscosity of conference raising polymkeric substance, makes its processibility variation, also can damage other performances of system, as mechanical property.The key issue of preparing conducing composite material is that the consumption that reduces as far as possible conductive filler material obtains lower conduction excess effusion value in improving material conductivity, makes the combination that is optimized of the electrical property of material and other performances.
Conductive filler material kind, character, dispersing mode and directly determined the formation of conductive network with the interaction of polymeric matrix, and then affect material conductivity and conduction excess effusion value.In numerous conductive filler materials, the carbon nanotube of tubulose has high length-to-diameter ratio, and the graphite of sheet has high radius-thickness ratio.Than other conductive filler materials the two can be under lower aq, the continuous 3 D stereo network structure of dispersed formation in matrix; Its conduction threshold values is lower.Therefore be, more to utilize carbon nanotube, graphite to prepare the matrix material of low conduction excess effusion value at present.Its preparation method, mainly contains following two kinds of methods:
One, by filler being carried out to surface modification to improve its dispersion in matrix, the people such as such as Liu are at Appl Phys Lett 2003, in the report of 83:2928, utilize polymer graft modification carbon nanotube, strengthen the interaction of carbon nanotube and polymkeric substance, make carbon nanotube dispersed in matrix, thereby obtained lower conduction excess effusion value.But this method is usually directed to a large amount of chemical reactions, complicated operation, is unfavorable for industrial scale operation; And can introduce more defect in carbon nano tube surface, the structure of carbon nanotube is done great damage, cause the deterioration of the electrical property of carbon nanotube own and physical strength.
Two, by conductive filler material is directly dispersed in the inconsistent two-phase polymer while being bicontinuous structure with conductive filler material affinity stronger one mutually in, when conductive filler material is in the time that this is also network structure in mutually, can produce " two exceeding oozed effect ", the conduction threshold values of system reduces greatly.The method is simple to operate, is applicable to suitability for industrialized production.But conduction exceedes the size of oozing threshold values, the deployment conditions of a phase is relevant therein with filler, and filler can cause the change of course of processing melt strength in the gathering of a phase simultaneously, and then affects the form of processing characteristics and blend, and its application is limited to.
Summary of the invention
The object of this invention is to provide a kind of melt blending and prepare the method for polymer base conductive composite material, the conductive filler material consumption of the method is low, and the conducing composite material of preparation conducts electricity very well, and mechanical property is strong.
It is that a kind of melt blending is prepared the method for polymer base conductive composite material, the steps include: that the present invention realizes the technical scheme that its goal of the invention adopts
1) selection of raw material: first choose carbon nanotube or graphite as conductive filler material, then selective polymer one and polymkeric substance two: the wherein viscosity (η of polymkeric substance one
polymkeric substance one) with the viscosity (η of polymkeric substance two
polymkeric substance two) ratio be more than or equal to 100, i.e. η
polymkeric substance one/ η
polymkeric substance two>=100; Or polymkeric substance one is low with conductive filler material affinity, polymkeric substance two is high with conductive filler material affinity, the theoretical infiltration coefficient ω of the co-mixing system that conductive filler material and polymkeric substance one and polymkeric substance two form
a> 1, wherein
γ represents the interfacial tension between two-phase, and polymkeric substance one and polymkeric substance two are chemical property incompatible polymers;
2) pre-treatment of conductive filler material: by carbon nanotube or graphite is calcined or acidification;
3) melt blending: by first pretreated conductive filler material and polymkeric substance one melt blending, make masterbatch after cooling curing, then by masterbatch and polymkeric substance two melt blendings, obtain polymer base conductive composite material after cooling curing.
Compared with prior art, the invention has the beneficial effects as follows:
One, the present invention first forms masterbatch by conductive filler material and the higher polymkeric substance of viscosity one melt blending, again by masterbatch and lower polymkeric substance two melt blendings of viscosity, in this melting process, because the viscosity of polymkeric substance one is much larger than the viscosity of polymkeric substance two, conductive filler material in polymkeric substance one can move to polymkeric substance two from polymkeric substance one, in the time that conductive filler material moves at two-phase interface place in a large number, carry out cooling curing and can obtain conductive filler material mainly at the polymer base conductive composite material of interface distributions.Two polymkeric substance that are less than 100 times for viscosity ratio, first polymkeric substance one melt blending conductive filler material is same and that its affinity is poor forms masterbatch, then by same masterbatch polymkeric substance two melt blendings high with conductive filler material affinity; In this melt blending process, conductive filler material in polymkeric substance one can be to moving with the higher polymkeric substance two of its affinity, in the time that conductive filler material moves at two-phase interface place in a large number, cooling curing also can obtain conductive filler material mainly at the polymer base conductive composite material of interface distributions.Because conductive filler material is mainly distributed on the two-dimentional interface of two interfaces, than be evenly distributed in two-phase or one mutually in, can form the conductive network being communicated with few conductive filler material.The conduction excess effusion value of conductive filler material is low, and utilization ratio is high, the conducting electricity very well of matrix material.
Two, conductive filler material migration concentrates on the interface of two-phase, both avoided the reunion of conductive filler material, also avoided increase that conductive filler material concentrates on a course of processing melt strength causing in the mutually impact on processing characteristics, conductive filler material mainly distributes on interface simultaneously, there is again small part to be distributed among two-phase simultaneously, can also play bridge beam action, improve connection and interaction between incompatible two-phase polymer, thereby improve the mechanical property of blend matrix material.
The mean diameter of above-mentioned carbon nanotube is 10-200nm, and mean length is single wall or the multi-walled pipes of 100nm-20 μ m.The carbon nanotube length-to-diameter ratio of this size is high, can further ensure that carbon nanotube consumption is few, and the mixture making conducts electricity very well, and mechanical property is high.
Above-mentioned graphite is mean diameter 500nm-1 μ m, multi-disc layer or the monolithic layer graphite of mean length 3 μ m-30 μ m.The graphite radius-thickness ratio of this size is high, can further ensure that graphite consumption is few, and the mixture making conducts electricity very well, and mechanical property is high.
The above-mentioned concrete grammar by conductive filler material carbon nanotube or graphite acidification is to process with sulfuric acid, nitric acid or phosphoric acid, and temperature is 60-80 DEG C, and the time is 4-24h, and suction filtration is dry subsequently, and be 6-24h time of drying.
This acidation treatment method can be good at removing the impurity of conductive filler material, can generate hydroxyl activity group simultaneously, is conducive to the dispersion of conductive filler material in blend system.
The above-mentioned design parameter by conductive filler material carbon nanotube or graphite calcining is that temperature is 600-1000 DEG C, and the time is 1-6h.This method for calcinating can be good at removing the impurity of conductive filler material, can generate a small amount of hydroxyl activity group simultaneously, is conducive to the dispersion of conductive filler material in blend system.
Above-mentioned pretreated conductive filler material is first with the condition of polymkeric substance one melt blending is, temperature is melting or the above 20-40 DEG C of softening temperature of polymkeric substance one, and the blend time is 5-20min; The mass ratio of conductive filler material and polymkeric substance one is 1-20: 100.This processing conditions ensures dispersed in polymkeric substance one of conductive filler material, be conducive to its in next step to migration in polymkeric substance two.
The above-mentioned condition by masterbatch and polymkeric substance two melt blendings is: melting or the softening temperature of comparative polymers one and polymkeric substance two, using the melting of the higher person or the above 20-40 of softening temperature DEG C as blending temperature, the blend time is 5-20min, and the mass ratio of masterbatch and polymkeric substance two is 1: 0.25-4.This processing conditions can ensure that masterbatch and polymkeric substance two can evenly mix, and can ensure to form enough interfaces between polymkeric substance one and polymkeric substance two and conductive filler material can be concentrated distribution on interface, the conductive network of formation connection simultaneously.
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Brief description of the drawings
Fig. 1 is the polymer base conductive composite material that embodiment mono-makes, and adopts chemical process to etch away the scanning electron microscope picture of polymkeric substance one after mutually.
Fig. 2 is the raw material that adopts embodiment mono-, but polymkeric substance in melt blending one and polymkeric substance two are exchanged to the polymer matrix composite making, then adopts chemical process to etch away the scanning electron microscope picture of polymkeric substance one phase.
Embodiment
Embodiment mono-
Melt blending is prepared a method for polymer base conductive composite material, the steps include:
1) selection of raw material: choosing mean diameter is 100nm, mean length be 10 μ m multi-walled carbon nano-tubes as conductive filler material, then choose viscosity=7.9 × 10
3the poly(lactic acid) (PLA) of PaS is as polymkeric substance one, by viscosities il=5.2 × 10
1the ethylene-vinyl acetate copolymer (EVA) of PaS is as polymkeric substance two (η
polymerization thing one/ η
polymkeric substance two> 100); Poly(lactic acid) and ethylene-vinyl acetate copolymer are chemical property incompatible polymers.
2) by the calcining of conductive filler material carbon nanotube, the parameter of calcining is: the time is 1h, and temperature is 1000 DEG C.
3) melt blending: by first the conductive filler material after calcining and polymkeric substance one melt blending, the melt temperature of polymkeric substance one (poly(lactic acid)) is 140-160 DEG C, blending condition is: blending temperature is 190 DEG C, the blend time is 10min, and the mass ratio of conductive filler material and polymkeric substance one is 10: 100.After conduction temperature cooling curing, make masterbatch.
By masterbatch and polymkeric substance two melt blendings, the melt temperature of polymkeric substance two (ethylene-vinyl acetate copolymer) is 70-90 DEG C, and blending condition is: blending temperature is 190 DEG C, and the time is 20min, and the mass ratio of masterbatch and polymkeric substance two is 1: 1.After cooling curing, obtain polymer base conductive composite material.
Fig. 1 is the polymer base conductive composite material that this example makes, and adopts chemical process to etch away the scanning electron microscope picture of polymkeric substance one (poly(lactic acid)) after mutually.As can be seen from Figure 1, at residual polymkeric substance two (poly(lactic acid)), though there is carbon nanotube mutually, content is few; Nearly all carbon nanotube is all distributed in PLA and EVA phase interface, and overlap joint forms conductive channel mutually.
In order to prove that conduction threshold values that carbon nanotube obtains in interface distributions is lower than a carbon nanotube conduction threshold values while distributing mutually therein, the inventor exchanges polymkeric substance one in this routine melt blending and polymkeric substance two to make polymer matrix composite.First carbon nanotube and EVA melt blending are prepared to masterbatch, then masterbatch and PLA melt blending are made to matrix material.Remove EVA phase through chemical solution etching, Fig. 2 is its scanning electron microscope picture.As can be seen from Figure 2, residual PLA mutually in carbon nanotube not, on PLA and EVA phase interface, there is no carbon nanotube yet.Obviously, carbon nanotube is to be arranged in EVA mono-mutually, after chemical etching, disappears with the dissolving of EVA matrix.
Table 1 is the resistivity of the bi-material of Fig. 1 and Fig. 2.
Table 1
As can be seen from Table 1, when content of carbon nanotubes is mass percent 1.0%, the carbon nanotube of interface distributions forms conductive network, makes 10 orders of magnitude of resistance decline of sample, conducts electricity excess effusion value lower than mass percent 1.0%; And when carbon nanotube be distributed in wherein one mutually in, when content of carbon nanotubes is also mass percent 1.0%, its resistance does not still change, until content of carbon nanotubes is increased to mass percent 3.0%, its electroconductibility is just significantly improved.This shows that carbon nano-tube material can improve the electroconductibility of material in the distribution at interface, the more important thing is that can obtain lower conduction exceedes and ooze threshold values.
Embodiment bis-
1) selection of raw material: choosing mean diameter is 500nm, mean length be 3 μ m graphite as conductive filler material, choose viscosities il=7.9 × 10
3the poly(lactic acid) (PLA) of PaS is as polymkeric substance one, by viscosities il=5.2 × 10
1the ethylene-vinyl acetate copolymer (EVA) of PaS is as polymkeric substance two (η
polymkeric substance one/ η
polymkeric substance two> 100); The chemical property of poly(lactic acid) and ethylene-vinyl acetate copolymer is incompatible.
2) conductive filler material graphite is calcined; The parameter of calcining is: the time is 3h, and temperature is 600 DEG C.
3) melt blending: by first the conductive filler material after calcining and polymkeric substance one melt blending, the melt temperature of polymkeric substance one (poly(lactic acid)) is 140-160 DEG C, blending condition is: temperature is 190 DEG C, and the time is 5min, and the mass ratio of conductive filler material and polymkeric substance one is 1: 100.After conduction temperature cooling curing, make masterbatch.
By masterbatch and polymkeric substance two melt blendings, the melt temperature of polymkeric substance two (ethylene-vinyl acetate copolymer) is 70-90 DEG C again, and blending condition is: temperature is 190 DEG C, and the time is 5mi n, and the mass ratio of masterbatch and polymkeric substance two is 1: 0.25.After cooling curing, obtain polymer base conductive composite material.
Embodiment tri-
1) selection of raw material: choosing mean diameter is 200nm, mean length is that 20 μ m Single Walled Carbon Nanotube are as conductive filler material.Choose the ethylene-vinyl acetate copolymer low with the affinity of conductive filler material as polymkeric substance one, with the high poly(lactic acid) of conductive filler material affinity as polymkeric substance two, the theoretical infiltration coefficient ω of the co-mixing system that these three kinds of raw materials form
a=3.52 > 1, wherein
γ represents the interfacial tension between two-phase; And selected polymkeric substance one and polymkeric substance two are chemical property incompatible polymers.
2) conductive filler material carbon nanotube is calcined; The parameter of calcining is: the time is 6h, and temperature is 1000 DEG C.
3) melt blending: by first the conductive filler material after calcining and polymkeric substance one melt blending, the melt temperature of polymkeric substance one (ethylene-vinyl acetate copolymer) is 70-90 DEG C, blending condition is: temperature is 120 DEG C, time is 20min, and the mass ratio of conductive filler material and polymkeric substance one is 20: 100.After conduction temperature cooling curing, make masterbatch.
By masterbatch and polymkeric substance two melt blendings, the melt temperature of polymkeric substance two (poly(lactic acid)) is 140-160 DEG C again, and blending condition is: temperature is 190 DEG C, and the time is 20min, and the mass ratio of masterbatch and polymkeric substance two is 1: 4.After cooling curing, obtain polymer base conductive composite material.
Embodiment tetra-
1) selection of raw material: choosing mean diameter is 0.5nm, mean length be 10 μ m multi-walled carbon nano-tubes as conductive filler material, then choose viscosities il=7.5 × 10
4the polyethylene (PE) of PaS is as polymkeric substance one, by viscosities il=5.2 × 10
2the nylon 6 (Nyl on6) of PaS is as polymkeric substance two (η
polymkeric substance one/ η
polymkeric substance two> 100); The chemical property of polyethylene and nylon 6 is incompatible.
2) conductive filler material carbon nanotube is calcined; The parameter of calcining is: the time is 1h, and temperature is 600 DEG C.
3) melt blending: by first the conductive filler material after calcining and polymkeric substance one melt blending, the melt temperature of polymkeric substance one (polyethylene) is 120-140 DEG C, blending condition is: temperature is 160 DEG C, and the time is 5min, and the mass ratio of conductive filler material and polymkeric substance one is 10: 100.After conduction temperature cooling curing, make masterbatch.
By masterbatch and polymkeric substance two melt blendings, the melt temperature of polymkeric substance two (nylon 6) is 210-230 DEG C again, and blending condition is: temperature is 250 DEG C, and the time is 10min, and the mass ratio of masterbatch and polymkeric substance two is 1: 2.After cooling curing, obtain polymer base conductive composite material.
Embodiment five
1) selection of raw material: choosing mean diameter is 10nm, mean length is that 100nm multi-walled carbon nano-tubes is as conductive filler material, choose the acrylonitrile-butadiene-styrene copolymer low with conductive filler material affinity as polymkeric substance one, choose the polycarbonate high with conductive filler material affinity as polymkeric substance two, the theoretical infiltration coefficient ω of the co-mixing system that these three kinds of raw materials form
a=11.24 > 1, wherein
γ represents the interfacial tension between two-phase; And polymkeric substance one and polymkeric substance two are chemical property incompatible polymers.
2) conductive filler material carbon nanotube is calcined; The parameter of calcining is: the time is 1h, and temperature is 800 DEG C.
3) melt blending: by first the conductive filler material after calcining and polymkeric substance one melt blending, the softening temperature of polymkeric substance one (acrylonitrile-butadiene-styrene copolymer) is 100-120 DEG C, blending condition is: temperature is 140 DEG C, time is 5min, and the mass ratio of conductive filler material and polymkeric substance one is 1: 100.After conduction temperature cooling curing, make masterbatch.
By masterbatch and polymkeric substance two melt blendings, the melt temperature of polymkeric substance two (polycarbonate) is 230-250 DEG C again, and blending condition is: temperature is 270 DEG C, and the time is 20min, and the mass ratio of masterbatch and polymkeric substance two is 1: 4.After cooling curing, obtain polymer base conductive composite material.
Embodiment six
1) selection of raw material: choosing mean diameter is 1 μ m, mean length is that 30 μ m graphite are as conductive filler material.Choose the polyethylene low with conductive filler material affinity as polymkeric substance one and with the high nylon 6 of conductive filler material affinity as polymkeric substance two, the theoretical infiltration coefficient ω of the co-mixing system that these three kinds of raw materials form
a=1.75 > 1, wherein
γ represents the interfacial tension between two-phase; And polymkeric substance one and polymkeric substance two are chemical property incompatible polymers.
2) conductive filler material graphite is calcined; The parameter of calcining is: the time is 1h, and temperature is 1000 DEG C.
3) melt blending: by first the conductive filler material after calcining and polymkeric substance one melt blending, the melt temperature of polymkeric substance one (polyethylene) is 120-140 DEG C, blending condition is: temperature is 180 DEG C, and the time is 20min, and the mass ratio of conductive filler material and polymkeric substance one is 15: 100.After conduction temperature cooling curing, make masterbatch.
By masterbatch and polymkeric substance two melt blendings, the melt temperature of polymkeric substance two (nylon 6) is 210-230 DEG C again, and blending condition is: temperature is 260 DEG C, and the time is 20min, and the mass ratio of masterbatch and polymkeric substance two is 1: 3.After cooling curing, obtain polymer base conductive composite material.
Embodiment seven
1) selection of raw material: choosing mean diameter is 200nm, mean length is that 20 μ m Single Walled Carbon Nanotube are as conductive filler material, choose the ethylene-vinyl acetate copolymer low with conductive filler material affinity as polymkeric substance one, with the high poly(lactic acid) of conductive filler material affinity as polymkeric substance two, the theoretical infiltration coefficient ω of the co-mixing system that these three kinds of raw materials form
a=3.52 > 1, wherein
γ represents the interfacial tension between two-phase; And polymkeric substance one and polymkeric substance two are chemical property incompatible polymers.
2) by conductive filler material carbon nanotube sulfuric acid acidation; The parameter of acidifying is: the mass concentration of sulfuric acid is 98%, and acidificatoin time is 4h, and temperature is 80 DEG C, and it is dry that reaction finishes rear suction filtration, and be 24h time of drying.
3) melt blending: by first the conductive filler material after calcining and polymkeric substance one melt blending, the melt temperature of polymkeric substance one (ethylene-vinyl acetate copolymer) is 70-90 DEG C, blending condition is: temperature is 130 DEG C, time is 20min, and the mass ratio of conductive filler material and polymkeric substance one is 20: 100.After conduction temperature cooling curing, make masterbatch.
By masterbatch and polymkeric substance two melt blendings, the melt temperature of polymkeric substance two (poly(lactic acid)) is 140-160 DEG C again, and blending condition is: temperature is 200 DEG C, and the time is 20min, and the mass ratio of masterbatch and polymkeric substance two is 1: 4.After cooling curing, obtain polymer base conductive composite material.
Embodiment eight
1) selection of raw material: choosing mean diameter is 200nm, mean length be 15 μ m graphite as conductive filler material, then choose the poly(lactic acid) that viscosity is larger (PLA) (η=7.9 × 10
3paS) as polymkeric substance one, by ethylene-vinyl acetate copolymer less viscosity (EVA) (η=5.2 × 10
1paS) as polymkeric substance two; Poly(lactic acid) and ethylene-vinyl acetate copolymer are that chemical property is inconsistent.
2) by the nitric acid acidifying of conductive filler material graphite; The parameter of acidifying is: the mass concentration of nitric acid is 66%, and acidificatoin time is 24h, and temperature is 60 DEG C, and it is dry that reaction finishes rear suction filtration, and be 6h time of drying.
3) melt blending: by first the conductive filler material after calcining and polymkeric substance one melt blending, the melt temperature of polymkeric substance one (poly(lactic acid)) is 140-160 DEG C, blending condition is: temperature is 180 DEG C, and the time is 5min, and the mass ratio of conductive filler material and polymkeric substance one is 10: 100.After conduction temperature cooling curing, make masterbatch.
By masterbatch and polymkeric substance two melt blendings, the melt temperature of polymkeric substance two (ethylene-vinyl acetate copolymer) is 70-90 DEG C again, and blending condition is: temperature is 180 DEG C, and the time is 5min, and the mass ratio of masterbatch and polymkeric substance two is 1: 0.5.After cooling curing, obtain polymer base conductive composite material.
Embodiment nine
1) selection of raw material: choosing mean diameter is 1 μ m, mean length is that 30 μ m graphite are as conductive filler material, choose the polyethylene low with conductive filler material affinity as polymkeric substance one, with the high nylon 6 of conductive filler material affinity as polymkeric substance two, the theoretical infiltration coefficient ω of the co-mixing system that these three kinds of raw materials form
a=1.75 > 1, wherein
γ represents the interfacial tension between two-phase; And polymkeric substance one and polymkeric substance two are chemical property incompatible polymers.
2) by the phosphoric acid acidifying of conductive filler material graphite; The parameter of acidifying is: the mass concentration of phosphoric acid is 85%, and acidificatoin time is 12h, and temperature is 70 DEG C, and it is dry that reaction finishes rear suction filtration, and be 12h time of drying.
3) melt blending: the melt temperature of polymkeric substance one (polyethylene) is 120-140 DEG C, by first the conductive filler material after calcining and polymkeric substance one melt blending, blending condition is: temperature is 160 DEG C, and the time is 20min, and the mass ratio of conductive filler material and polymkeric substance one is 15: 100.After conduction temperature cooling curing, make masterbatch.
By masterbatch and polymkeric substance two melt blendings, the melt temperature of polymkeric substance two (nylon 6) is 210-230 DEG C again, and blending condition is: temperature is 250 DEG C, and the time is 20min, and the mass ratio of masterbatch and polymkeric substance two is 1: 3.After cooling curing, obtain polymer base conductive composite material.
In the present invention with the high polymkeric substance one of conductive filler material affinity and with the affinity height in the low polymkeric substance two of conductive filler material affinity be a relative concept, but not absolute probability; Also with respect to polymkeric substance two, polymkeric substance one is higher with the avidity of conductive filler material than polymkeric substance two with the avidity of conductive filler material.Polymkeric substance one in the present invention and polymkeric substance two are not limited to the polymkeric substance relating to one and the polymkeric substance two in embodiment, and can be various can melt-processed and meet formula η
polymkeric substance one/ η
polymkeric substance two> 10
2or meet formula
polymkeric substance one, two.
In the present invention, polymkeric substance one and polymkeric substance two are that chemical property incompatible polymers refers to: two kinds of polymkeric substance only the infiltration on a small amount of molecular level can occur under melt blending state, and the material after cooling curing can form obvious interface between two kinds of polymkeric substance.
Claims (9)
1. melt blending is prepared a method for polymer base conductive composite material, the steps include:
1) selection of raw material: choosing mean diameter is 100nm, mean length be 10 μ m multi-walled carbon nano-tubes as conductive filler material, then choose viscosity=7.9 × 10
3the poly(lactic acid) of PaS is as polymkeric substance one, by viscosities il=5.2 × 10
1the ethylene-vinyl acetate copolymer of PaS is as polymkeric substance two, η
polymkeric substance one/ η
polymkeric substance two>100; Poly(lactic acid) and ethylene-vinyl acetate copolymer are chemical property incompatible polymers;
2) by the calcining of conductive filler material carbon nanotube, the parameter of calcining is: the time is 1h, and temperature is 1000 DEG C;
3) melt blending: by first the conductive filler material after calcining and polymkeric substance one melt blending, the melt temperature of polymkeric substance one-poly(lactic acid) is 140-160 DEG C, blending condition is: blending temperature is 190 DEG C, and the blend time is 10min, and the mass ratio of conductive filler material and polymkeric substance one is 10:100; After conduction temperature cooling curing, make masterbatch;
By masterbatch and polymkeric substance two melt blendings, the melt temperature of polymkeric substance two-ethylene-vinyl acetate copolymer is 70-90 DEG C, and blending condition is: blending temperature is 190 DEG C, and the time is 20min, and the mass ratio of masterbatch and polymkeric substance two is 1:1; After cooling curing, obtain polymer base conductive composite material.
2. melt blending is prepared a method for polymer base conductive composite material, the steps include:
1) selection of raw material: choosing mean diameter is 500nm, mean length be 3 μ m graphite as conductive filler material, choose viscosities il=7.9 × 10
3the poly(lactic acid) of PaS is as polymkeric substance one, by viscosities il=5.2 × 10
1the ethylene-vinyl acetate copolymer of PaS is as polymkeric substance two, η
polymkeric substance one/ η
polymkeric substance two>100; The chemical property of poly(lactic acid) and ethylene-vinyl acetate copolymer is incompatible;
2) conductive filler material graphite is calcined; The parameter of calcining is: the time is 3h, and temperature is 600 DEG C;
3) melt blending: by first the conductive filler material after calcining and polymkeric substance one melt blending, the melt temperature of polymkeric substance one-poly(lactic acid) is 140-160 DEG C, blending condition is: temperature is 190 DEG C, and the time is 5min, and the mass ratio of conductive filler material and polymkeric substance one is 1:100; After conduction temperature cooling curing, make masterbatch;
By masterbatch and polymkeric substance two melt blendings, the melt temperature of polymkeric substance two-ethylene-vinyl acetate copolymer is 70-90 DEG C again, and blending condition is: temperature is 190 DEG C, and the time is 5min, and the mass ratio of masterbatch and polymkeric substance two is 1:0.25; After cooling curing, obtain polymer base conductive composite material.
3. melt blending is prepared a method for polymer base conductive composite material, the steps include:
1) selection of raw material: choosing mean diameter is 200nm, mean length is that 20 μ m Single Walled Carbon Nanotube are as conductive filler material; Choose the ethylene-vinyl acetate copolymer low with the affinity of conductive filler material as polymkeric substance one, with the high poly(lactic acid) of conductive filler material affinity as polymkeric substance two, the theoretical infiltration coefficient ω of the co-mixing system that these three kinds of raw materials form
a=3.52>1, wherein
γ represents the interfacial tension between two-phase; And selected polymkeric substance one and polymkeric substance two are chemical property incompatible polymers;
2) conductive filler material carbon nanotube is calcined; The parameter of calcining is: the time is 6h, and temperature is 1000 DEG C;
3) melt blending: by first the conductive filler material after calcining and polymkeric substance one melt blending, the melt temperature of polymkeric substance one-ethylene-vinyl acetate copolymer is 70-90 DEG C, blending condition is: temperature is 120 DEG C, and the time is 20min, and the mass ratio of conductive filler material and polymkeric substance one is 20:100; After conduction temperature cooling curing, make masterbatch;
By masterbatch and polymkeric substance two melt blendings, the melt temperature of polymkeric substance two-poly(lactic acid) is 140-160 DEG C again, and blending condition is: temperature is 190 DEG C, and the time is 20min, and the mass ratio of masterbatch and polymkeric substance two is 1:4; After cooling curing, obtain polymer base conductive composite material.
4. melt blending is prepared a method for polymer base conductive composite material, the steps include:
1) selection of raw material: choosing mean diameter is 0.5nm, mean length be 10 μ m multi-walled carbon nano-tubes as conductive filler material, then choose viscosities il=7.5 × 10
4the polyethylene of PaS is as polymkeric substance one, by viscosities il=5.2 × 10
2the nylon 6 of PaS is as polymkeric substance two, η
polymkeric substance one/ η
polymkeric substance two>100; The chemical property of polyethylene and nylon 6 is incompatible;
2) conductive filler material carbon nanotube is calcined; The parameter of calcining is: the time is 1h, and temperature is 600 DEG C;
3) melt blending: by first the conductive filler material after calcining and polymkeric substance one melt blending, polymkeric substance one-poly melt temperature is 120-140 DEG C, blending condition is: temperature is 160 DEG C, and the time is 5min, and the mass ratio of conductive filler material and polymkeric substance one is 10:100; After conduction temperature cooling curing, make masterbatch;
By masterbatch and polymkeric substance two melt blendings, the melt temperature of polymkeric substance two-nylon 6 is 210-230 DEG C again, and blending condition is: temperature is 250 DEG C, and the time is 10min, and the mass ratio of masterbatch and polymkeric substance two is 1:2; After cooling curing, obtain polymer base conductive composite material.
5. melt blending is prepared a method for polymer base conductive composite material, the steps include:
1) selection of raw material: choosing mean diameter is 10nm, mean length is that 100nm multi-walled carbon nano-tubes is as conductive filler material, choose the acrylonitrile-butadiene-styrene copolymer low with conductive filler material affinity as polymkeric substance one, choose the polycarbonate high with conductive filler material affinity as polymkeric substance two, the theoretical infiltration coefficient ω of the co-mixing system that these three kinds of raw materials form
a=11.24>1, wherein
γ represents the interfacial tension between two-phase; And polymkeric substance one and polymkeric substance two are chemical property incompatible polymers;
2) conductive filler material carbon nanotube is calcined; The parameter of calcining is: the time is 1h, and temperature is 800 DEG C;
3) melt blending: by first the conductive filler material after calcining and polymkeric substance one melt blending, the softening temperature of polymkeric substance one-acrylonitrile-butadiene-styrene copolymer is 100-120 DEG C, blending condition is: temperature is 140 DEG C, time is 5min, and the mass ratio of conductive filler material and polymkeric substance one is 1:100; After conduction temperature cooling curing, make masterbatch;
By masterbatch and polymkeric substance two melt blendings, the melt temperature of polymkeric substance two-polycarbonate is 230-250 DEG C again, and blending condition is: temperature is 270 DEG C, and the time is 20min, and the mass ratio of masterbatch and polymkeric substance two is 1:4; After cooling curing, obtain polymer base conductive composite material.
6. melt blending is prepared a method for polymer base conductive composite material, the steps include:
1) selection of raw material: choosing mean diameter is 1 μ m, mean length is that 30 μ m graphite are as conductive filler material; Choose the polyethylene low with conductive filler material affinity as polymkeric substance one and with the high nylon 6 of conductive filler material affinity as polymkeric substance two, the theoretical infiltration coefficient ω of the co-mixing system that these three kinds of raw materials form
a=1.75>1, wherein
γ represents the interfacial tension between two-phase; And polymkeric substance one and polymkeric substance two are chemical property incompatible polymers;
2) conductive filler material graphite is calcined; The parameter of calcining is: the time is 1h, and temperature is 1000 DEG C;
3) melt blending: by first the conductive filler material after calcining and polymkeric substance one melt blending, polymkeric substance one-poly melt temperature is 120-140 DEG C, blending condition is: temperature is 180 DEG C, and the time is 20min, and the mass ratio of conductive filler material and polymkeric substance one is 15:100; After conduction temperature cooling curing, make masterbatch;
By masterbatch and polymkeric substance two melt blendings, the melt temperature of polymkeric substance two-nylon 6 is 210-230 DEG C again, and blending condition is: temperature is 260 DEG C, and the time is 20min, and the mass ratio of masterbatch and polymkeric substance two is 1:3; After cooling curing, obtain polymer base conductive composite material.
7. melt blending is prepared a method for polymer base conductive composite material, the steps include:
1) selection of raw material: choosing mean diameter is 200nm, mean length is that 20 μ m Single Walled Carbon Nanotube are as conductive filler material, choose the ethylene-vinyl acetate copolymer low with conductive filler material affinity as polymkeric substance one, with the high poly(lactic acid) of conductive filler material affinity as polymkeric substance two, the theoretical infiltration coefficient ω of the co-mixing system that these three kinds of raw materials form
a=3.52>1, wherein
γ represents the interfacial tension between two-phase; And polymkeric substance one and polymkeric substance two are chemical property incompatible polymers;
2) by conductive filler material carbon nanotube sulfuric acid acidation; The parameter of acidifying is: the mass concentration of sulfuric acid is 98%, and acidificatoin time is 4h, and temperature is 80 DEG C, and it is dry that reaction finishes rear suction filtration, and be 24h time of drying;
3) melt blending: by first the conductive filler material after calcining and polymkeric substance one melt blending, the melt temperature of polymkeric substance one-ethylene-vinyl acetate copolymer is 70-90 DEG C, blending condition is: temperature is 130 DEG C, and the time is 20min, and the mass ratio of conductive filler material and polymkeric substance one is 20:100; After conduction temperature cooling curing, make masterbatch;
By masterbatch and polymkeric substance two melt blendings, the melt temperature of polymkeric substance two-poly(lactic acid) is 140-160 DEG C again, and blending condition is: temperature is 200 DEG C, and the time is 20min, and the mass ratio of masterbatch and polymkeric substance two is 1:4; After cooling curing, obtain polymer base conductive composite material.
8. melt blending is prepared a method for polymer base conductive composite material, the steps include:
1) selection of raw material: choosing mean diameter is 200nm, mean length be 15 μ m graphite as conductive filler material, then choose the poly(lactic acid) that viscosity is larger, η=7.9 × 10
3paS is as polymkeric substance one, by ethylene-vinyl acetate copolymer less viscosity, η=5.2 × 10
1paS is as polymkeric substance two; Poly(lactic acid) and ethylene-vinyl acetate copolymer are that chemical property is inconsistent;
2) by the nitric acid acidifying of conductive filler material graphite; The parameter of acidifying is: the mass concentration of nitric acid is 66%, and acidificatoin time is 24h, and temperature is 60 DEG C, and it is dry that reaction finishes rear suction filtration, and be 6h time of drying;
3) melt blending: by first the conductive filler material after calcining and polymkeric substance one melt blending, the melt temperature of polymkeric substance one-poly(lactic acid) is 140-160 DEG C, blending condition is: temperature is 180 DEG C, and the time is 5min, and the mass ratio of conductive filler material and polymkeric substance one is 10:100; After conduction temperature cooling curing, make masterbatch;
By masterbatch and polymkeric substance two melt blendings, the melt temperature of polymkeric substance two-ethylene-vinyl acetate copolymer is 70-90 DEG C again, and blending condition is: temperature is 180 DEG C, and the time is 5min, and the mass ratio of masterbatch and polymkeric substance two is 1:0.5; After cooling curing, obtain polymer base conductive composite material.
9. melt blending is prepared a method for polymer base conductive composite material, the steps include:
1) selection of raw material: choosing mean diameter is 1 μ m, mean length is that 30 μ m graphite are as conductive filler material, choose the polyethylene low with conductive filler material affinity as polymkeric substance one, with the high nylon 6 of conductive filler material affinity as polymkeric substance two, the theoretical infiltration coefficient ω of the co-mixing system that these three kinds of raw materials form
a=1.75>1, wherein
γ represents the interfacial tension between two-phase; And polymkeric substance one and polymkeric substance two are chemical property incompatible polymers;
2) by the phosphoric acid acidifying of conductive filler material graphite; The parameter of acidifying is: the mass concentration of phosphoric acid is 85%, and acidificatoin time is 12h, and temperature is 70 DEG C, and it is dry that reaction finishes rear suction filtration, and be 12h time of drying;
3) melt blending: polymkeric substance one-poly melt temperature is 120-140 DEG C, by first the conductive filler material after calcining and polymkeric substance one melt blending, blending condition is: temperature is 160 DEG C, and the time is 20min, and the mass ratio of conductive filler material and polymkeric substance one is 15:100; After conduction temperature cooling curing, make masterbatch;
By masterbatch and polymkeric substance two melt blendings, the melt temperature of polymkeric substance two-nylon 6 is 210-230 DEG C again, and blending condition is: temperature is 250 DEG C, and the time is 20min, and the mass ratio of masterbatch and polymkeric substance two is 1:3; After cooling curing, obtain polymer base conductive composite material.
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| CN104844820B (en) * | 2015-04-24 | 2016-11-16 | 暨南大学 | A kind of carbon nanotube conducting master batch and its preparation method and application |
| CN106046721B (en) * | 2016-05-30 | 2018-11-23 | 郑州大学 | A kind of polymer-based temperature sensing material and its preparation method and application |
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| CN108314859B (en) * | 2018-03-26 | 2019-06-18 | 四川大学 | Ternary blends based composites with high dielectric property and preparation method thereof |
| CN110157211A (en) * | 2019-06-05 | 2019-08-23 | 上海宇之赫新材料测试有限公司 | A kind of conducing composite material and preparation method thereof |
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| CN101974179A (en) * | 2010-11-02 | 2011-02-16 | 华东理工大学 | High-conductivity composite material and preparation method thereof |
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