CN104497394B - Polymer-matrix thermo-sensitive resistor material with negative temperature coefficient effect and preparation method thereof - Google Patents
Polymer-matrix thermo-sensitive resistor material with negative temperature coefficient effect and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The invention belongs to the manufacturing technology field of conductive polymer composite, be specifically related to the preparation method that one has the conductive polymer composite of negative temperature resistance coefficient (NTC) feature.A kind of polymer-matrix thermo-sensitive resistor material with negative temperature coefficient effect of disclosure, its raw material and weight content thereof be: 288.5～96.9 parts of polymer 1+ polymer, conductive filler 0.1～1.5 part, compatilizer 3～10 parts；Further, conductive filler selective distribution is in polymer 2 phase；MFI≤the 7g/10min of polymer 1, the MFI >=12g/10min of polymer 2；The thermal coefficient of expansion of polymer 2 is more than the thermal coefficient of expansion of polymer 1, and conductive filler is two dimension conductive filler；The quality proportioning of polymer 1 and polymer 2 is 3 7～7 3.Gained resistance material excess effusion value of the present invention is low；And the NTC characteristic favorable repeatability of gained resistance material, it is simple to life-time service.
Description
Technical field
The invention belongs to the manufacturing technology field of conductive polymer composite, be specifically related to the preparation method that one has the conductive polymer composite of negative temperature resistance coefficient (NTC) feature.
Background technology
Conductive polymer composite (ConductivePolymerComposites, CPCs) refers to and conductive filler (such as graphite, white carbon black (CB), CNT (CNTs), Graphene etc.) is joined the functional high molecule material made in macromolecule matrix.
At present, the temperature-sensing property of CPCs material has caused the extensive concern of academia and industrial circle.Generally, CPC resistivity is gradually increased with the rising of temperature, and raises rapidly near macromolecule fusing point, namely shows positive temperature coefficient (PTC) impedance operator.Based on the ptc characteristics of CPCs, CPCs is widely used in manufacturing self limiting temperature heating, electric current and temperature overload protection device.The dominant mechanism of ptc characteristics is as the rising of temperature, and polymer-based volume expansion, when, near fusing point, polymer crystal melts, and causes macromolecule volume sharply to increase, thus destroying the conductive network that conductive filler is formed.In recent years, researcher reports the temperature-sensing property phenomenon of some novelties.Such as Chen etc. are prepared for CB/ nylon 6 (PA6)/polypropylene (PP) CPCs, wherein CB selective distribution is in PA6 phase, find that CPCs resistivity does not vary with temperature (ChenGS, etal.JournalofAppliedPolymerScicence, 2008 substantially；114:1848-1855)；The volumetric expansion that the temperature-sensing property of this novelty is attributed to PP by them is less on the impact property of conductive network in PA6 phase.
In recent years, have been reported that proposition a kind of polymer-matrix negative temperature coefficient (being called for short NTC) thermo-sensitive resistor material, it is with polymeric material for matrix, add the conductive fillers such as white carbon black, metal powder, metal-oxide, the heterogeneous compound system formed after the dispersion mode such as compound, lamination compound processes, its resistivity has the advantages that to raise with temperature and reduce；NTC thermo-sensitive resistor is mainly used in the temperature-compensating of measurement and electronic circuit, is widely used in temperature sensing and the control of household electrical appliance, automobile and the equipment of industrial product；Owing to polymer-matrix NTC material raw material is easy to get, machine-shaping is simple, and room temperature resistivity is low, has again many excellent properties of macromolecular material simultaneously, thus is increasingly subject to the attention of people.If publication number is the CN102796333A preparation method disclosing a kind of polyvinylidene fluoride thermo-sensitive resistor material with negative temperature coefficient effect, it is prepared for polyvinylidene fluoride thermo-sensitive resistor material with the Graphene of poly (sodium 4-styrenesulfonate) grafting or the Graphene of loading nano silvery for conductive filler；To solve the problem that conductive phase inserts is high, room temperature resistivity is bigger than normal, sensitivity is on the low side that existing polymer-matrix temperature sensing material exists.
Summary of the invention
The present invention provides a kind of new polymer-matrix thermo-sensitive resistor material with negative temperature coefficient effect, and gained resistance material stable electrical properties, excess effusion value is low；And the NTC characteristic favorable repeatability of gained resistance material, it is simple to life-time service.
First technical problem to be solved by this invention is to provide a kind of polymer-matrix thermo-sensitive resistor material with negative temperature coefficient effect, and its raw material and weight content thereof be:
288.5～96.9 parts of polymer 1+ polymer
Conductive filler 0.1～1.5 part
Compatilizer 3～10 parts；
Further, in described polymer-matrix thermo-sensitive resistor material, conductive filler is distributed in polymer 2 phase；
Wherein, the melt index≤7g/10min of described polymer 1, the melt index >=12g/10min of polymer 2, melt index measures according to GB/T3682-2000；The thermal coefficient of expansion of polymer 2 is more than the thermal coefficient of expansion of polymer 1, and conductive filler is two dimension conductive filler；The quality proportioning of polymer 1 and polymer 2 is (3:7)～(7:3).Preferably, the melt index≤6g/10min of described polymer 1, the melt index >=20g/10min of polymer 2.
Further, the described polymer 1 at least one in ultra-high molecular weight polyethylene (UHMWPE), polymethyl methacrylate (PMMA), Merlon (PC) or polystyrene (PS)；The described polymer 2 at least one in nylon 6 (PA6), nylon66 fiber (PA66), nylon 1010 (PA1010), NYLON610 (PA610), nylon 1212 (PA1212), polyformaldehyde (POM) or polyethylene terephthalate (PET)；Described compatilizer at least one in maleic anhydride grafted polyethylene (MAH-g-PE), maleic anhydride graft ultra-high molecular weight polyethylene or maleic anhydride inoculated polypropylene；Described conductive filler at least one in Graphene, graphite or nano graphite flakes.
Further, polymer 1+ polymer 2 is 95.5 parts, and the weight proportion of polymer 1 and polymer 2 is 73, and the parts by weight of compatilizer are 3 parts, and the parts by weight of conductive filler are 1.5 parts.
Preferably, in the above-mentioned polymer-matrix thermo-sensitive resistor material with negative temperature coefficient effect, described polymer 1 is UHMWPE, and polymer 2 is PA6, and conductive filler is Graphene, and compatilizer is MAH-g-PE.
It is furthermore preferred that in the above-mentioned polymer-matrix thermo-sensitive resistor material with negative temperature coefficient effect, the weight average molecular weight of UHMWPE is 100～8,000,000, and particle diameter is 5～200 μm；The weight average molecular weight of PA6 is 2～50,000；The thickness of Graphene is 0.55～3.74nm, and specific surface area is 400～1000m2/ g, length is 0.5～3 μm；The percent grafting of MAH-g-PE is 0.5～2%.
Preferably, the percent grafting of described maleic anhydride grafted polyethylene is 1%.
The preparation method that second technical problem to be solved by this invention is to provide the above-mentioned polymer-matrix thermo-sensitive resistor material with negative temperature coefficient effect: first by polymer 2 and conductive filler stirring and evenly mixing in formic acid, sequentially add compatilizer powder and polymer 2 is mixed to get composite through solution, after flocculation, formic acid is volatilized, then by gained composite through the hot-forming polymer-matrix thermo-sensitive resistor material that can obtain there is negative temperature coefficient effect.
In said method, described polymer 1 is UHMWPE, and polymer 2 is PA6, and conductive filler is Graphene, and compatilizer is MAH-g-PE；The preparation method of wherein said MAH-g-PE powder is: mixed with dimethylbenzene by MAH-g-PE pellet, when temperature be 120～140 DEG C (preferably 135 DEG C), rotating speed is 180～230 (preferably 200) r/min, mechanical agitation 0.5～2 (preferably 1) hour, makes MAH-g-PE be completely dissolved in dimethylbenzene；Then by MAH-g-PE/ xylene solution natural air drying 80-120 hour (preferably 100 hours) until being completely dried；Finally dried material block is crushed to Powdered, obtains MAH-g-PE powder；Wherein, MAH-g-PE pellet and the ratio of dimethylbenzene are that every 100ml dimethylbenzene adds 5～15gMAH-g-PE pellet (preferred, every 100ml dimethylbenzene adds 10gMAH-g-PE pellet).
Further, in above-mentioned preparation method, the preparation method of described composite is: is first dissolved in by PA6 in the formic acid of 50～80 DEG C and obtains PA6/ formic acid solution, is placed in formic acid by Graphene and ultrasonic disperse obtains uniform graphene dispersing solution；After graphene dispersing solution poured into stirring and evenly mixing in the PA6/ formic acid solution of cooling；Sequentially adding MAH-g-PE powder and UHMWPE powder, stir 20～50min, supersound process 20～50min obtains mixed liquor；Afterwards gained mixed liquor is added dropwise in dehydrated alcohol or methanol, stirs the mixture that flocculates；Finally by vacuum filtration, dry obtain composite.
Preferably, in the preparation method of above-mentioned composite, gained mixed liquor is added dropwise in dehydrated alcohol, stirs 20～40min when 700～1000r/min, and flocculate mixture.
In above-mentioned preparation method, hot-forming process conditions are: preheating 5～30min below the above decomposition temperature of melt temperature of polymer 1, polymer 2, then hot pressing 5～20min under 5～15MPa pressure, finally colds pressing to room temperature under 5～15MPa pressure.
Preferably, described polymer 1 is UHMWPE, and polymer 2 is PA6, and conductive filler is Graphene, when compatilizer is MAH-g-PE；Hot-forming process conditions are: preheating 8min at 240 DEG C, then hot pressing 5min under 14MPa pressure, finally colds pressing to room temperature under 14MPa pressure.
Beneficial effects of the present invention:
1, the inventive method make conductive filler selective distribution a certain macromolecule mutually in, stable electrical properties, excess effusion value is low.
2, the inventive method is relative to the preparation method of conventional CPCs material, adopts 2 dimension conductive fillers and unique selective distribution structure, and this makes CPCs present NTC impedance operator.
3, the NTC characteristic favorable repeatability of macromolecular material prepared by the inventive method, it is simple to life-time service.
4, compared with the inventive method is prepared with existing ceramic base NTC thermistor, processing temperature is low, and device therefor such as hot press is all conventional polymer process equipment, it is easy to processing, molding.
Accompanying drawing illustrates:
Fig. 1 is the polarizing microscope photo of the embodiment of the present invention 3 (a), comparative example 3 (b), comparative example 11 (c) gained composite.
Fig. 2 oozes curve at embodiment of the present invention 1-5 (Graphene is conductive filler), comparative example 1-7 (CNTs is conductive filler) and comparative example 8-14 (when CB is conductive filler) exceeding of gained composite.
Fig. 3 oozes curve exceeding of embodiment of the present invention 1-5 gained composite.
Fig. 4 is the embodiment of the present invention 3 gained Graphene/PA6/UHMWPE composite temperature programmed control schematic diagram, wherein heats up and rate of temperature fall is 2 DEG C/min.
Fig. 5 is the embodiment of the present invention 3, comparative example 3, the temperature-resistance rate behavior in the first circulation temperature-rise period of the comparative example 11 gained composite.
Fig. 6 is the time m-resistivity behavior in continuous four Circularly liftable temperature processes of the embodiment of the present invention 3 gained composite.
Detailed description of the invention
First technical problem to be solved by this invention is to provide a kind of polymer-matrix thermo-sensitive resistor material with negative temperature coefficient effect, and its raw material and weight content thereof be:
288.5～96.9 parts of polymer 1+ polymer
Conductive filler 0.1～1.5 part
Compatilizer 3～10 parts；
Further, in described polymer-matrix thermo-sensitive resistor material conductive filler selective distribution in polymer 2 phase；
Wherein, the melt index≤7g/10min of described polymer 1, the melt index >=12g/10min of polymer 2, melt index is measured according to GB/T3682-2000；The thermal coefficient of expansion of polymer 2 is more than the thermal coefficient of expansion of polymer 1, and conductive filler is two dimension conductive filler；The quality proportioning of polymer 1 and polymer 2 is (3:7)～(7:3).
Preferably, the melt index≤6g/10min of described polymer 1, the melt index >=20g/10min of polymer 2.
In the present invention, melt index MFI refers to that thermoplastic is under uniform temperature and pressure, the melt weight that melt is flowed out by the aperture of tester in 10 minutes, unit be with gram/within 10 minutes, represent, experimental technique carries out according to GB/T3682-2000 (ISO1133).In the present invention, MFI=0, PMMA and the UHMWPE of UHMWPE are close, MFI=5.26g/10min, the PA6 series of MFI=6.76g/10min, the PS of PC, MFI=25.1g/10min, the MFI=12g/10min of MFI=16.1g/10min, the POM of PET.
Further, the described polymer 1 at least one in ultra-high molecular weight polyethylene (UHMWPE), polymethyl methacrylate (PMMA), Merlon (PC) or polystyrene (PS)；The described polymer 2 at least one in nylon 6 (PA6), nylon66 fiber (PA66), nylon 1010 (PA1010), NYLON610 (PA610), nylon 1212 (PA1212), polyformaldehyde (POM) or polyethylene terephthalate (PET)；
The preparation method that second technical problem to be solved by this invention is to provide the above-mentioned polymer-matrix thermo-sensitive resistor material with negative temperature coefficient effect: first by polymer 2 powder and conductive filler stirring and evenly mixing in formic acid, sequentially add compatilizer powder and polymer 2 is mixed to get composite through solution, after flocculation, formic acid is volatilized, then by gained composite through the hot-forming polymer-matrix thermo-sensitive resistor material that can obtain there is negative temperature coefficient effect.Making suspended particulates in water or liquid gather change big, or form floc sedimentation, thus adding the coagulation of fast particle, reaching the purpose of solid-liquid separation, this phenomenon or operation are called flocculation.The flocculation of the present invention is that PA6 strand precipitates out from formic acid under lean solvent ethanol or methanol solvate effect, reaches the phenomenon of solid-liquid separation.
In the present invention, the interpolation of formic acid is for solvent polymerization thing 2, and makes conductive filler and polymer 2 mix homogeneously, must reach good mixed effect during use；Compatilizer powder and polymer 1 powder are not had solute effect by formic acid, act only as disperse medium, and therefore formic acid addition must flood compatilizer powder and polymer 1 powder completely.
In the present invention, conductive filler must select the lamellar i.e. conductive filler of 2 dimensions, and to reach to raise with temperature, in system, conductive filler bends and overlaps gradually, and conductive network is reset, the effect of composite material resistance reduction and NTC effect；According to the conductive filler such as CNTs etc. of conductive filler such as CB and 1 dimension of 0 dimension, raising conductive network in composite with temperature and destroy serious, material list reveals positive temperature and resistance effect but not NTC.Selection for macromolecule matrix, select a kind of polarity macromolecule with conductive filler with good interaction as macromolecule matrix (polymer 2), and this macromolecule must have relatively low melt viscosity, so that two dimension conductive filler can optionally be distributed in this macromolecule matrix, and this in hot pressing by another phase that viscosity is higher, as UHMWPE effectively pushes, produce good there is isolation structure conductive network；And another phase of macromolecule matrix (polymer 1) selection has the macromolecule of viscosity higher, selective distribution can be had another phase of conductive filler to produce to push preferably and isolation effect by it in hot pressing.Meanwhile, the thermal coefficient of expansion of the thermal coefficient of expansion such as PA6 with low melt viscosity macromolecule matrix (is about 8.30 × 10-4Mm/ DEG C) thermal coefficient of expansion that must be significantly greater than the macromolecule matrix such as UHMWPE with high melt viscosity (is about 1.50 × 10-4Mm/ DEG C), with in temperature-rise period, high viscosity effectively limit mutually the low viscosity that causes due to volumetric expansion mutually in conductive network destroy.
In addition, the present invention adopts hot press forming technology, the heat pressing process of low sheraing effectively constructs the conductive network structure of conductive filler selective distribution, and can prevent the alternate of conductive filler that high shear causes from migrating, namely the conductive network keeping this composite special is not destroyed, and the microstructure of this conductive network produces the key of NTC effect just.
Below in conjunction with embodiment, the specific embodiment of the present invention is further described, does not therefore limit the present invention among described scope of embodiments.
In embodiments of the invention, conductive filler used is the aqueous solution (concentration is 0.5wt.%) of graphene-containing, and thickness is 0.55～3.74nm, and specific surface area is 400～1000m2/ g, length is 0.5～3 μm, purchased from Chengdu organic chemistry institute of the Chinese Academy of Sciences；MAH-g-PE: model RG1001, percent grafting 1%, Asia, Suzhou match plasticizing company limited；PA6: model M2500I, Chinese Guangdong Xin Huimeida chinlon limited company, fusing point is about 220 DEG C, and thermal coefficient of expansion is about 8.30 × 10-4mm/℃；UHMWPE: model M-II, Beijing second auxiliary factory produces, density 0.94g/cm3, fusing point is about 137 DEG C, and thermal coefficient of expansion is about 1.50 × 10-4mm/℃。
Embodiment 1 has the preparation of the polymer-matrix thermo-sensitive resistor material of negative temperature coefficient effect
Raw material: each raw material dosage proportion relation is as shown in table 1.
Preparation method: concrete preparation process is as follows:
(1) raw material drying: under 80 DEG C of conditions, dries PA6 and MAH-g-PE pellet 8 hours in vacuum drying oven；
(2) MAH-g-PE preparation: 25gMAH-g-PE pellet is mixed in the round-bottomed flask of 500ml with 250ml dimethylbenzene, temperature be 135 DEG C, rotating speed be 200r/min when, mechanical agitation 1 hours；Then being taken out by the MAH-g-PE solution after being completely dissolved in dimethylbenzene pours in culture dish, places 100 hours in ventilation to being completely dried；Finally dried block disintegrating machine is smashed to Powdered, obtain MAH-g-PE powder；
(3) prepared by composite material: according to the proportioning in table 1, and it is in 60 DEG C of formic acid solutions that PA6 is first dissolved in temperature, simultaneously by graphene solution ultrasonic disperse 10min in formic acid solution；Then the graphene solution that ultrasonic disperse is good is poured in the PA6/ formic acid solution of cooling, mechanical agitation 30min, sequentially add MAH-g-PE powder, UHMWPE, mechanical agitation 30min, ultrasonic 30min；Joining in ethanol solution by the dropwise obtained, when rotating speed is 1000r/min, mechanical agitation 30min, flocculate mixture；Then pass through vacuum filtration, dry 48 hours in 80 DEG C of vacuum drying ovens, obtain composite material；
(4) hot-forming: the material obtained in (3) is preheated 8min at 240 DEG C, then hot pressing 5min under 14MPa pressure, namely finally cold pressing under 14MPa pressure to room temperature obtains the present invention and has the polymer-matrix thermo-sensitive resistor material of negative temperature coefficient effect.
Embodiment 2-5 has the preparation of the polymer-matrix thermo-sensitive resistor material of negative temperature coefficient effect
Each proportioning raw materials of embodiment 2-5 is as shown in table 1.Concrete preparation method is all identical with embodiment 1.
Performance test:
Fig. 1 a is the polarizing microscope figure of embodiment 3 gained composite, and wherein the region of white is UHMWPE phase, and black region is Graphene/PA6 phase, and as shown in Figure 1, PA6 is scattered carrier and the interparticle binding agent of polymer UHMWPE of conductive filler Graphene.
Electric property: in order to investigate the electricity percolation of Graphene/PA6/UHMWPE composite, adopting the sample that embodiment 1-5 gained is of a size of 1cm × 4cm by TH2683 insulation tester (Changzhou is with sending us JIANMEI ELECTRONICS CO LTD by cable) and ZC-36 type high resistant instrument (Shanghai precision instrumentation company limited) to carry out electrical testing, result is shown in Fig. 2.Can be seen that the excess effusion value of Graphene/PA6/UHMWPE composite is 0.29wt.%, there is good electric property；Network factors t=2.37, according to t value between 1.1-1.3, conductive network is two-dimentional；If t value is between 1.6-2.0, conductive network is close to three-dimensional, it can be determined that the Graphene going out the present invention defines in the composite close to three-dimensional conductive network.
Temperature-sensing property: in order to investigate the temperature-sensing property of Graphene/PA6/UHMWPE composite, adopt TH2683 Insulation Resistance Tester that the temperature-resistance behavior in program control heating and cooling of the embodiment 3 gained composite has been studied, wherein, the speed of program control heating and cooling is 2 DEG C/min, cycle-index is 4, and deduction graph is as shown in Figure 4；Fig. 5 is the temperature-resistance rate behavior in the first circulation temperature-rise period, it can be seen that along with the rising of temperature, the resistivity of composite is gradually reduced, and presents typical NTC feature.Being found by repeatedly heating and cooling circulating research, this NTC feature has good repeatability, as shown in Figure 6.Additionally, find in experimentation, in the present invention, when Graphene content is lower than 0.1%, composite material resistance is too high, and beyond testing range, the NTC effect of material cannot be carried out test；When Graphene content is more than 1.5%, system conductive network is very perfect, and its NTC effect in test process is also less obvious.
Four kinds of component: PA6, MAH-g-PE, UHMWPE, Graphenes are included by the composite prepared by the inventive method；PA6 is as the carrier of conductive filler Graphene and the interparticle binding agent of polymer UHMWPE；Low-molecular-weight MAH-g-PE can strengthen the compatibility between PA6 and UHMWPE；UHMWPE, as main matrix material, effectively limits the volumetric expansion destruction to conductive network of PA6；Selective graphene is distributed in PA6 phase, at utmost reduces UHMWPE and expands the destruction of graphene conductive network in PA6 phase, thus preparing target product.
The present invention has been prepared by the unique design of the following aspects has CPCs: the first of NTC feature, the selection of conductive filler；Relative to conventional conductive filler (such as CB, CNTs), Graphene has numerous superiority: specific surface area is big, and chemical stability is good, and thermal conductivity and electrical conductivity are high；Additionally, Graphene is prone to assemble, bend in composite preparation process, therefore in theory, the expansion of a degree of macromolecule matrix can make the Graphene tendency of bending stretch, and reduces Graphene spacing, makes composite material resistance rate decline.Second, the selective distribution of conductive filler, so can at utmost reduce UHMWPE and expand the destruction of graphene conductive network in PA6 phase.3rd, the selection of macromolecule matrix, two kinds of incompatible macromolecule respectively UHMWPE and PA6, and the thermal coefficient of expansion of PA6 (is about 8.30 × 10-4Mm/ DEG C) thermal coefficient of expansion that is significantly greater than UHMWPE (is about 1.50 × 10-4Mm/ DEG C), this can make UHMWPE that the volumetric expansion of PA6 is played a definite limitation effect, thus avoiding PA6 volume sharply expansion damage conductive network.
The each proportioning raw materials of table 1 embodiment 1-5
Comparative example 1-7
The present invention also adopts CNTs as conductive filler, and concrete raw material and proportioning are as shown in table 2, and preparation method is with embodiment 1.
Performance test:
Fig. 1 b is the polarizing microscope figure of comparative example 3 gained composite, wherein the region of white is UHMWPE phase, black region is CNTs/PA6 phase, as shown in Figure 1, PA6 is scattered carrier and the interparticle binding agent of polymer UHMWPE of conductive filler CNTs, has identical microstructure characteristic with embodiment 3.
Electric property: method is with embodiment 3, and result is shown in Fig. 2.Can be seen that the excess effusion value of CNTs/PA6/UHMWPE composite is 0.14wt.%, there is good electric property；Network factors t=2.10, it can be determined that go out CNTs and define in the composite close to three-dimensional conductive network.Compared with embodiment, CNTs/PA6/UHMWPE has better electric property.This is probably Graphene and there occurs curling in composite preparation process.
Temperature-sensing property: method is with embodiment 3, and result is shown in Fig. 5.It can be seen that along with the rising of temperature, the resistivity of composite is held essentially constant at first, near PA6 fusing point, presenting more weak PTC effect subsequently.These are different from the result of embodiment 3, are mainly due to the 1 dimension microstructure characteristic of CNTs.
Experiment finds, when adopting CNT as conductive filler, it is impossible to produce NTC effect.
The each proportioning raw materials of table 2 comparative example 1-7
Comparative example 8-14
The present invention also adopts white carbon black (CB) as conductive filler, and concrete raw material and proportioning are as shown in table 3, and preparation method is with embodiment 1.
Performance test:
Fig. 1 c is the polarizing microscope figure of comparative example 11 gained composite, wherein the region of white is UHMWPE phase, black region is CB/PA6 phase, as shown in Figure 1, PA6 is scattered carrier and the interparticle binding agent of polymer UHMWPE of conductive filler CB, has identical microstructure characteristic with embodiment 3.
Electric property: method is with embodiment 3, and result is shown in Fig. 2.Can be seen that the excess effusion value of CB/PA6/UHMWPE composite is 1.17wt.%, there is good electric property；Network factors t=2.65, it can be determined that go out CB and define the conductive network of approximate three-dimensional in the composite.Compared with embodiment, CB/PA6/UHMWPE electric property is poor, and this electric conductivity being mainly due to Graphene is substantially excellent in CB, and Graphene has bigger radius-thickness ratio.
Temperature-sensing property: method is with embodiment 3, and result is shown in Fig. 5.It can be seen that along with the rising of temperature, the resistivity of composite gradually rises, near UHMWPE and PA6 fusing point, present obvious rising trend, namely double PTC characteristics.These are different from the result of embodiment 3, are mainly due to the 0 dimension microstructure characteristic of CB.
Experiment finds, when adopting CB as conductive filler, it is impossible to produce NTC effect.Additionally, experiment also compares the flocculation figure of the embodiment of the present invention 3 and comparative example 3, comparative example 13, three all presents good flocculating effect, illustrates that the present invention is easily operated.
The each proportioning raw materials of table 3 comparative example 8-14
Claims (9)
1. there is the polymer-matrix thermo-sensitive resistor material of negative temperature coefficient effect, it is characterised in that its raw material and weight content thereof be:
288.5～96.9 parts of polymer 1+ polymer
Conductive filler 0.1～1.5 part
Compatilizer 3～10 parts；
Further, in described polymer-matrix thermo-sensitive resistor material, conductive filler is distributed in polymer 2 phase；
Wherein, the melt index≤7g/10min of described polymer 1, the melt index >=12g/10min of polymer 2, melt index measures according to GB/T3682-2000；The thermal coefficient of expansion of polymer 2 is more than the thermal coefficient of expansion of polymer 1, and conductive filler is two dimension conductive filler；The quality proportioning of polymer 1 and polymer 2 is (3 7)～(7 3)；
The described polymer 1 at least one in ultra-high molecular weight polyethylene, polymethyl methacrylate, Merlon or polystyrene；
The described polymer 2 at least one in nylon 6, nylon66 fiber, nylon 1010, NYLON610, nylon 1212, polyformaldehyde or polyethylene terephthalate；
Described compatilizer at least one in maleic anhydride grafted polyethylene or maleic anhydride inoculated polypropylene；
Described conductive filler at least one in Graphene, graphite or nano graphite flakes.
2. there is the polymer-matrix thermo-sensitive resistor material of negative temperature coefficient effect according to claim 1, it is characterized in that, polymer 1+ polymer 2 is 95.5 parts, and the weight proportion of polymer 1 and polymer 2 is 73, the parts by weight of compatilizer are 3 parts, and the parts by weight of conductive filler are 1.5 parts.
3. the polymer-matrix thermo-sensitive resistor material with negative temperature coefficient effect according to claim 1 or claim 2, it is characterized in that, described polymer 1 is ultra-high molecular weight polyethylene, and polymer 2 is nylon 6, conductive filler is Graphene, and compatilizer is maleic anhydride grafted polyethylene.
4. having the polymer-matrix thermo-sensitive resistor material of negative temperature coefficient effect according to claim 3, it is characterised in that the weight average molecular weight of described ultra-high molecular weight polyethylene is 100～8,000,000, particle diameter is 5～200 μm；The weight average molecular weight of nylon 6 is 2～50,000；The thickness of Graphene is 0.55～3.74nm, and specific surface area is 400～1000m2/ g, length is 0.5～3 μm；The percent grafting of maleic anhydride grafted polyethylene is 0.5～2%.
5. the preparation method described in any one of Claims 1 to 4 with the polymer-matrix thermo-sensitive resistor material of negative temperature coefficient effect, it is characterized in that, first by polymer 2 and conductive filler stirring and evenly mixing in formic acid, sequentially add compatilizer powder and polymer 2 is mixed to get composite through solution, after flocculation, formic acid is volatilized, then by gained composite through the hot-forming polymer-matrix thermo-sensitive resistor material that can obtain there is negative temperature coefficient effect.
6. the preparation method according to claim 5 with the polymer-matrix thermo-sensitive resistor material of negative temperature coefficient effect, it is characterized in that, described polymer 1 is ultra-high molecular weight polyethylene, and polymer 2 is nylon 6, conductive filler is Graphene, when compatilizer is maleic anhydride grafted polyethylene；The preparation method of described maleic anhydride grafted polyethylene powder is: mixed with dimethylbenzene by maleic anhydride grafted polyethylene pellet, temperature be 120～140 DEG C, rotating speed be 180～230r/min when, mechanical agitation 0.5～2 hour, makes maleic anhydride grafted polyethylene be completely dissolved in dimethylbenzene；Then by maleic anhydride grafted polyethylene/xylene solution natural air drying 80-120 hour until being completely dried；Finally dried material block is crushed to Powdered, obtains maleic anhydride grafted polyethylene powder；Wherein, maleic anhydride grafted polyethylene pellet is that every 100ml dimethylbenzene adds 5～15g maleic anhydride grafted polyethylene pellet with the ratio of dimethylbenzene.
7. the preparation method according to claim 6 with the polymer-matrix thermo-sensitive resistor material of negative temperature coefficient effect, it is characterized in that, the preparation method of described composite is: is first dissolved in by nylon 6 in the formic acid of 50～80 DEG C and obtains nylon 6/ formic acid solution, is placed in formic acid by Graphene and ultrasonic disperse obtains uniform graphene dispersing solution；After graphene dispersing solution poured into stirring and evenly mixing in nylon 6/ formic acid solution of cooling；Sequentially adding maleic anhydride grafted polyethylene powder and ultra-high molecular weight polyethylene, stir 20～50min, supersound process 20～50min obtains mixed liquor；Afterwards gained mixed liquor is added dropwise in dehydrated alcohol or methanol, stirs the mixture that flocculates；Finally by vacuum filtration, dry obtain composite.
8. the preparation method according to claim 5 with the polymer-matrix thermo-sensitive resistor material of negative temperature coefficient effect, it is characterized in that, hot-forming process conditions are: preheat 5～30min below the above decomposition temperature of melt temperature of polymer 1, polymer 2, then hot pressing 5～20min under 5～15MPa pressure, finally colds pressing to room temperature under 5～15MPa pressure.
9. the preparation method according to claim 6 or 7 with the polymer-matrix thermo-sensitive resistor material of negative temperature coefficient effect, it is characterized in that, hot-forming process conditions are: preheating 8min at 240 DEG C, then hot pressing 5min under 14MPa pressure, finally colds pressing to room temperature under 14MPa pressure.
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| SG11201706905QA (en) * | 2015-03-12 | 2017-09-28 | Total Res & Technology Feluy | Thermal switch based on polymer compound |
| CN104788818B (en) * | 2015-04-09 | 2017-05-31 | 郑州大学 | Regulatable PTC polymer base conductive composite materials of PTC intensity and preparation method thereof |
| CN104927791B (en) * | 2015-06-15 | 2018-06-15 | 西北工业大学 | Graphene oxide and NTC Semiconductor Powder hybrid solar heat-absorbing materials and preparation method |
| 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 |
| CN106947233B (en) * | 2017-04-18 | 2019-03-29 | 杭州高烯科技有限公司 | A kind of PC/PA6/ graphene composite material and preparation method thereof |
| CN108002746A (en) * | 2017-11-23 | 2018-05-08 | 苏州南尔材料科技有限公司 | A kind of preparation method of NTC thermistor material |
| CN108515713B (en) * | 2018-03-12 | 2019-07-19 | 西北工业大学 | A kind of NTC powder and graphene composite plane thermosensitive film preparation method |
| CN108693218B (en) * | 2018-03-23 | 2023-11-03 | 天津大学 | Intelligent aggregate capable of sensing water content information inside hydraulic building |
| CN111454500B (en) * | 2020-04-13 | 2021-11-16 | 四川大学 | 3D conductive network structure polymer antistatic material, preparation method thereof and application of ultralow molecular weight polyethylene |
| CN114249979B (en) * | 2020-09-21 | 2022-08-30 | 金发科技股份有限公司 | Polyamide composition with NTC effect and preparation method thereof |
| CN113174097B (en) * | 2021-02-25 | 2024-01-30 | 嘉兴市振明包装材料有限公司 | Self-temperature-limiting heating element, manufacturing method thereof and self-temperature-limiting heating sheet |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1431984A1 (en) * | 2002-12-17 | 2004-06-23 | E. I. du Pont de Nemours and Company | Polymer resistor composition having a substantially neutral temperature coefficient of resistance and methods and compositions relating thereto |
| CN101654530A (en) * | 2009-09-18 | 2010-02-24 | 清华大学 | Negative temperature coefficient polymer composite material for temperature sensing cable and preparation method |
| CN102532669A (en) * | 2012-01-12 | 2012-07-04 | 上海交通大学 | High polymer-based graphene composite material with positive resistance temperature coefficient and preparation method |
| CN103554680A (en) * | 2013-10-12 | 2014-02-05 | 青岛科技大学 | Preparation method of NTC material based on thermoplastic vulcanizate |
-
2014
- 2014-12-11 CN CN201410759145.XA patent/CN104497394B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1431984A1 (en) * | 2002-12-17 | 2004-06-23 | E. I. du Pont de Nemours and Company | Polymer resistor composition having a substantially neutral temperature coefficient of resistance and methods and compositions relating thereto |
| CN101654530A (en) * | 2009-09-18 | 2010-02-24 | 清华大学 | Negative temperature coefficient polymer composite material for temperature sensing cable and preparation method |
| CN102532669A (en) * | 2012-01-12 | 2012-07-04 | 上海交通大学 | High polymer-based graphene composite material with positive resistance temperature coefficient and preparation method |
| CN103554680A (en) * | 2013-10-12 | 2014-02-05 | 青岛科技大学 | Preparation method of NTC material based on thermoplastic vulcanizate |
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