CN1704447A - Conductive composite materials with positive temperature coefficient effect and process for making same - Google Patents
Conductive composite materials with positive temperature coefficient effect and process for making same Download PDFInfo
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- CN1704447A CN1704447A CN 200410020607 CN200410020607A CN1704447A CN 1704447 A CN1704447 A CN 1704447A CN 200410020607 CN200410020607 CN 200410020607 CN 200410020607 A CN200410020607 A CN 200410020607A CN 1704447 A CN1704447 A CN 1704447A
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- 238000000034 method Methods 0.000 title claims description 17
- 230000008569 process Effects 0.000 title claims description 4
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 42
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 37
- 239000011231 conductive filler Substances 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- -1 polyethylene Polymers 0.000 claims abstract description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 7
- 239000004743 Polypropylene Substances 0.000 claims abstract description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920001155 polypropylene Polymers 0.000 claims abstract description 5
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- 239000004677 Nylon Substances 0.000 claims abstract description 4
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- 229920001778 nylon Polymers 0.000 claims abstract description 4
- 229920000573 polyethylene Polymers 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 24
- 239000002041 carbon nanotube Substances 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 18
- 239000011159 matrix material Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 14
- 239000006229 carbon black Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
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- 238000002156 mixing Methods 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
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- 238000011065 in-situ storage Methods 0.000 claims description 5
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- 238000007254 oxidation reaction Methods 0.000 claims description 5
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- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 3
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 claims description 3
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- 238000013329 compounding Methods 0.000 claims description 2
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- 239000012764 mineral filler Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 229920001577 copolymer Polymers 0.000 abstract 2
- 239000002033 PVDF binder Substances 0.000 abstract 1
- 239000002134 carbon nanofiber Substances 0.000 abstract 1
- 239000003822 epoxy resin Substances 0.000 abstract 1
- 239000002048 multi walled nanotube Substances 0.000 abstract 1
- 229920000647 polyepoxide Polymers 0.000 abstract 1
- 229920001903 high density polyethylene Polymers 0.000 description 22
- 239000004700 high-density polyethylene Substances 0.000 description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
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- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
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- 229920010741 Ultra High Molecular Weight Polyethylene (UHMWPE) Polymers 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
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Abstract
Disclosed is a conductive composite materials with positive temperature coefficient effect comprising conductive filler and polymer, wherein the conductive filler includes one-dimensional nano carbon having a diameter of 1-500nm, i.e. single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanofibers or their compounds, the weight content of the one-dimensional nano carbon material is 0.1-50%, preferably 1-15%. The polymer is selected from polyethylene, polypropylene, polyvinylidene fluoride, nylon, epoxy resin, ethane-vinyl acetate copolymer, ethene-ethyl acrylate copolymer and EPT rubber.
Description
Technical field:
The present invention relates to a kind of composition and technology of preparing of functional nano carbon material in one dimension conducing composite material.Particularly a kind of composition and technology of preparing with nano carbon material in one dimension/composite conducting polymer material of significant positive temperature coefficient effect.
Background technology:
(positive temperature coefficient, PTC) effect is meant the phenomenon that the resistivity of material raises and increases with temperature to positive temperature coefficient.Material (abbreviation ptc material) with PTC effect is widely used at aspects such as self-limiting heater temperature, overcurrent protective device, transmitters.Ptc material mainly contains ceramic base ptc material and polymer matrix PTC material.Mainly by constituting through adulterated barium titanate, the PTC transformation of barium titanate ceramics occurs near the crystalline curie transition temperature pottery ptc material.Polymer matrix PTC material is normally by polymkeric substance and carbon black, the charcoal fiber, and conductive filler material blend such as metal-powder form, and when temperature raise, near polymer crystallization fusing point or second-order transition temperature, the prominent of generating material resistivity got over, and presents the PTC effect.Compare with the ceramic base ptc material, ptc polymer has advantages such as preparation technology is simple, cost is low, and geomery is unrestricted, thereby obtains application more and more widely.At present ptc polymer mainly is to be conductive filler material with the carbon black, exists the shortcoming of short, poor stability of life-span, its reason, be on the one hand because carbon black is easy to agglomeration, make that sooty distributes in the polymkeric substance, in recycling process, change, cause the PTC strength degradation; Be because carbon black is easy to oxidation on the other hand, cause that the room temperature resistance of material increases gradually in the use.
Nano carbon material in one dimension then is one of forward position research direction in the nano material, is subjected to the extensive concern and the attention of countries in the world owing to its structure uniqueness, excellent performance.Nano carbon material in one dimension is meant the fibrous raw material of wood-charcoal material of diameter below 500 nanometers, comprises diameter at the CNT (carbon nano-tube) of 1-50nm and the diameter nano carbon fiber at 50-500nm, and wherein CNT (carbon nano-tube) is the newcomer of the early 1990s found carbon family.Have the hollow tubular structure that curls and form by graphite flake layer, can be divided into Single Walled Carbon Nanotube and multiple-wall carbon nanotube according to the carbon-coating number that constitutes the CNT (carbon nano-tube) tube wall.Nano carbon material in one dimension not only has excellent mechanical property, also has excellent conductive capability, heat conductivility, chemical stability and thermostability simultaneously.These characteristics of nano carbon material in one dimension make it aspect preparation high-performance ptc material, compare with other conductive filler material, have significant advantage.
Summary of the invention:
The object of the present invention is to provide a kind of conducing composite material with positive temperature coefficient effect and preparation method thereof, the conducing composite material that this kind has positive temperature coefficient effect has good materials processing performance and use properties.
The invention provides a kind of conducing composite material, constitute by conductive filler material and polymkeric substance with positive temperature coefficient effect; Described conductive filler material comprises the nano carbon material in one dimension of diameter range at 1～500nm, i.e. Single Walled Carbon Nanotube, multiple-wall carbon nanotube, nano carbon fiber or its mixture; The weight content of nano carbon material in one dimension is 0.1～50%, and optimized scope is 1～15%.
The present invention has in the conducing composite material of positive temperature coefficient effect, and described polymkeric substance is selected from one or more in polyethylene, polypropylene, polyvinylidene difluoride (PVDF), nylon, Resins, epoxy, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, the terpolymer EP rubber.
The present invention has in the conducing composite material of positive temperature coefficient effect, and described nano carbon material in one dimension can be handled through chemical modification.
The present invention has in the conducing composite material of positive temperature coefficient effect, and described nano carbon material in one dimension can cooperate the formation conductive filler material with carbon black, charcoal fiber etc.
The present invention has in the conducing composite material of positive temperature coefficient effect, can also contain auxiliary agents such as oxidation inhibitor, linking agent, mineral filler in addition.
The present invention also provides the preparation method of the above-mentioned conducing composite material with positive temperature coefficient effect, can adopt in-situ compounding process, is about to nano carbon material in one dimension homodisperse in polymer monomer, and re-initiation monomer in-situ polymerization generates polymer; Also can adopt the method for solution blending or melt blending, be about to polymkeric substance directly and the nano carbon material in one dimension blend with solution, emulsion, melt form.
The present invention has among the preparation method of conducing composite material of positive temperature coefficient effect, can adopt chemical method or high-energy ray irradiation method to make polymeric matrix crosslinked.
The used conductive filler material of the present invention can be a Single Walled Carbon Nanotube, also can be multiple-wall carbon nanotube, or nano carbon fiber.Can be independent use, also can be wherein two or more being used, or be used with other conductive filler materials such as carbon black, charcoal fiber etc.For improve nano carbon material in one dimension dispersed in polymkeric substance and with the interfacial interaction of polymkeric substance, can its pulverize, processing such as oxidation, coating and organic modification of surface.
The used polymkeric substance of the present invention can be the various polymeric matrixs that can produce the PTC effect such as high density polyethylene(HDPE), new LDPE (film grade), ultrahigh molecular weight polyethylene(UHMWPE), polypropylene, polyvinylidene difluoride (PVDF), nylon, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, polyphenylene sulfide, Resins, epoxy, terpolymer EP rubber.These polymeric matrixs can use separately, also can be wherein two or more being used.
The weight content of nano carbon material in one dimension is 0.1～50% among the present invention, and optimized scope is 1～15%.When selecting different polymeric matrixs, because nano carbon material in one dimension is different with the interaction energy of polymkeric substance, reach the seepage flow threshold value difference that begins to form conductive network in the polymkeric substance, the nano carbon material in one dimension consumption is with different.On the other hand, also can by changing the consumption of nano carbon material in one dimension, regulate the room temperature resistivity of mixture according to the requirement of use properties.
The preparation method of matrix material can adopt direct blend among the present invention, also can adopt original position compound.Directly blend be meant polymkeric substance with powder, solution, emulsion, melt form directly with the nano carbon material in one dimension blend, original position is compound to be with nano carbon material in one dimension homodisperse in polymer monomer, re-initiation monomer in-situ polymerization generation polymer.The former technology is simply easy to implement, and the latter more helps the nano carbon material in one dimension homodisperse.The dispersion state of control nano carbon material in one dimension in polymeric matrix is key problem in technology of the present invention.
Matrix material can adopt chemical method or high-energy ray irradiation method to make polymeric matrix crosslinked among the present invention, with the further PTC stability of improving material.
Nano carbon material in one dimension of the present invention/polymer positive-temperature-coefficient material mainly has the following advantages: (1) is because nano carbon material in one dimension has good electroconductibility and very high length-to-diameter ratio, adopt less nano carbon material in one dimension consumption just can reach the seepage flow threshold value, less to the mechanical property and the processing characteristics influence of material.And adopt the ptc polymer of carbon black as conductive filler material, because the sooty addition is bigger, the mechanical property and the processing characteristics of material caused bigger infringement.(2) nano carbon material in one dimension Stability Analysis of Structures is difficult for oxidation in air, so nano carbon material in one dimension/ptc polymer room temperature resistivity is more stable.(3) nano carbon material in one dimension is compared with carbon black and is difficult for agglomeration, makes the ptc material cyclical stability of preparation better, and negative temperature coefficient (NTC) effect is less.
Embodiment:
Be example with the high density polyethylene(HDPE) among the embodiment, but the polymeric matrix that the present invention was suitable for is not limited to high density polyethylene(HDPE) and polypropylene, the nano carbon material in one dimension that is adopted is a multiple-wall carbon nanotube, but the conductive filler material that the present invention was suitable for is not limited to multiple-wall carbon nanotube.The PTC intensity of the matrix material resistivity-resistivity at temperature relation curve upward peak place and the ratio value representation of room temperature resistivity among the embodiment.
Embodiment 1
Getting high density polyethylene(HDPE) 0.95g is dissolved in the dimethylbenzene, multiple-wall carbon nanotube 0.05g and an amount of other auxiliary agent add in the ethanol, ultra-sonic dispersion 30min, carry out at the same time under the ultrasonic and condition of stirring, polyethylene solution is added in the alcohol dispersion liquid of CNT (carbon nano-tube), continue to stir diel, use washing with alcohol, filtration, drying.After the mold pressing in flakes, carrying out absorption dose again is the gamma-radiation irradiation of 80KGy in vulcanizing press.The PTC intensity of the matrix material that obtains is 2.8 * 10
4
Comparative Examples 1
Method is identical with embodiment 1, and without gamma-radiation irradiation, the PTC intensity of matrix material is 1.1 * 10
4
Embodiment 2-4
Implementation method is identical with embodiment 1, changes the consumption of high density polyethylene(HDPE) and multiple-wall carbon nanotube, and the result is as shown in table 1.
Table 1
| Embodiment | High density polyethylene(HDPE) (g) | Multiple-wall carbon nanotube (g) | PTC intensity |
| ????2 ????3 ????4 | ??0.97 ??0.92 ??0.90 | ?0.03 ?0.08 ?0.10 | ??2.6×10 3??1.6×10 4??2.0×10 3 |
Embodiment 5
Multiple-wall carbon nanotube 5g adds in the ethanol, ultra-sonic dispersion 30min, adding 45g high density polyethylene(HDPE) powder and an amount of other auxiliary agent mix, remove by filter most of ethanol, under the loose condition (of surface) that CNT (carbon nano-tube) is soaked into by ethanol, grind with the high density polyethylene(HDPE) powder and to be dispersed to the raw material substantially dry, put into vacuum drying oven and thoroughly dry.Melt blending in Banbury mixer afterwards, blend mold pressing in vulcanizing press is in blocks, and carrying out absorption dose again is the gamma-radiation irradiation of 80KGy.The PTC intensity of matrix material is 4.9 * 10
6
Comparative Examples 2
Method is identical with embodiment 5, and with the graphitized carbon black replacement multiple-wall carbon nanotube of equivalent, matrix material does not have the PTC effect substantially.
Embodiment 6
Get high density polyethylene(HDPE) 37.5g, undressed multiple-wall carbon nanotube 12.5g reaches other auxiliary agent and adds together in the Banbury mixer, and in 150 ℃ of mixing 15min, blend 150 ℃ of mold pressings in vulcanizing press are in blocks, and its PTC intensity is 1.4 * 10
6
Embodiment 7
Implementation method is same as embodiment 6, and high density polyethylene(HDPE) and multiple-wall carbon nanotube are respectively 35g and 15g, and the PTC intensity of matrix material is 6.8 * 10
5
Embodiment 8
Implementation method is same as embodiment 6, and high density polyethylene(HDPE) and multiple-wall carbon nanotube are respectively 25g and 25g, and the PTC intensity of matrix material is 41.
Claims (10)
1. the conducing composite material with positive temperature coefficient effect is made of conductive filler material and polymkeric substance; It is characterized in that: described conductive filler material is the nano carbon material in one dimension of diameter range at 1～500nm, i.e. Single Walled Carbon Nanotube, multiple-wall carbon nanotube, nano carbon fiber or its mixture; The weight content of nano carbon material in one dimension is 0.1～50%.
2. according to the described conducing composite material with positive temperature coefficient effect of claim 1, it is characterized in that: described polymkeric substance is selected from one or more in polyethylene, polypropylene, polyvinylidene difluoride (PVDF), nylon, Resins, epoxy, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, the terpolymer EP rubber.
3. according to claim 1 or 2 described conducing composite materials with positive temperature coefficient effect, it is characterized in that: the weight content of described nano carbon material in one dimension is 1～15%.
4. according to claim 1 or 2 described conducing composite materials with positive temperature coefficient effect, it is characterized in that: described nano carbon material in one dimension is handled through chemical modification.
5. according to claim 1 or 2 described conducing composite materials with positive temperature coefficient effect, it is characterized in that: described conductive filler material is cooperated with carbon black, charcoal fiber etc. by nano carbon material in one dimension and constitutes.
6. according to the described conducing composite material with positive temperature coefficient effect of claim 4, it is characterized in that: described conductive filler material is cooperated with carbon black, charcoal fiber etc. by nano carbon material in one dimension and constitutes.
7. according to the described conducing composite material of claim 1, it is characterized in that: contain auxiliary agents such as oxidation inhibitor, linking agent, mineral filler in the described matrix material with positive temperature coefficient effect.
8. described preparation method of claim 1 with conducing composite material of positive temperature coefficient effect, it is characterized in that adopting in-situ compounding process, be about to nano carbon material in one dimension homodisperse in polymer monomer, re-initiation monomer in-situ polymerization generates polymer.
9. described preparation method of claim 1 with conducing composite material of positive temperature coefficient effect, it is characterized in that adopting the method for solution blending or melt blending, be about to polymkeric substance directly and the nano carbon material in one dimension blend with solution, emulsion, melt form.
10. according to claim 8 or 9 described preparation methods, it is characterized in that adopting chemical method or high-energy ray irradiation method to make polymeric matrix crosslinked with conducing composite material of positive temperature coefficient effect.
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| CNB2004100206072A CN1328309C (en) | 2004-05-26 | 2004-05-26 | Conductive composite materials with positive temperature coefficient effect and process for making same |
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| CNB2004100206072A CN1328309C (en) | 2004-05-26 | 2004-05-26 | Conductive composite materials with positive temperature coefficient effect and process for making same |
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