CN1363629A - Process for preparing electrically conductive high-molecular composite material by in-situ graft to modify electrically conductive filler - Google Patents
Process for preparing electrically conductive high-molecular composite material by in-situ graft to modify electrically conductive filler Download PDFInfo
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- CN1363629A CN1363629A CN 02114762 CN02114762A CN1363629A CN 1363629 A CN1363629 A CN 1363629A CN 02114762 CN02114762 CN 02114762 CN 02114762 A CN02114762 A CN 02114762A CN 1363629 A CN1363629 A CN 1363629A
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Abstract
An electrically conductive composite high-molecular material with positive temp coefficient (PTC) for heater with self limitation of temp and over-current protection element is prepared through pre-treating the electrically conductive filler by reactive treating agent and chemically graft reaction between said filler, treating agent and high-molecular base body. Its advantages include high adhesive to metallic electrode, high PTC and high stability.
Description
Technical field
The present invention relates to adopt the method modification conductive filler material filled high polymer of situ-formed graft or the conductive polymer composite that its blending resin matrix is constituted with positive temperature coefficient feature (PTC).
Background technology
The conductive polymer composite with positive temperature coefficient feature with the single macromolecule matrixes of filling such as unmodified electroconductive stuffing such as carbon black are constituted has conductivity adjustable in a big way, is easy to moulding, flexible, cost is low and PTC intensity height (〉=10
5) etc. characteristics (referring to US4,514,620; US4,732,701; US5,164,133; CN87102932; CN87102924).On this basis, PTC matrix material (the Chinese patent application: CN97108956) that adopts unmodified electroconductive stuffing filling blend macromolecule matrix to be constituted, the PTC effect stability of matrix material is improved, comprehensive mechanical performance, especially flexibility significantly improves.
But, since the interfacial interaction between matrix and unmodified conductive filler material such as the carbon black particle a little less than, and the carbon black particle that is dispersed in the matrix has stronger agglomeration power, so the dispersion of carbon black particle in matrix is thermodynamic instability.The PTC effect of PTC type matrix material depends primarily on degree of scatter and distribution and the result that with external conditions (effect of oxidative degradation and crosslinked, local superheating, electric field, light and mechanical stress) change thereof of carbon black in macromolecule matrix, no matter unmodified conductive filler material is single or the macromolecule matrix of blend if being filled, the PTC effect stability of gained matrix material is not very desirable.Before actual use, also need matrix material is carried out crosslinked, improve the playback of resistance temperature behavior, eliminate negative temperature coefficient of resistance (NTC) phenomenon.Common crosslinked method has chemically crosslinked, cross-linking radiation or crosslinked with silicane etc., though they have very great help to improving the material electrical property, but also exist some problems in the practical application: at first be crosslinked technology or equipment to be had higher requirement, for example, chemically crosslinked is very tight to the requirement of complete processing, is difficult to control in the course of processing, cross-linking radiation has then required the high-energy irradiation source, and this is that general factory is not available.In addition, crosslinked mechanical property to matrix material also has infringement.
Summary of the invention
The purpose of this invention is to provide a kind of polymer matrix PTC conducing composite material that adopts the method manufacturing of situ-formed graft; the interface interaction of its conductive filler material and macromolecule matrix is enhanced; has high PTC effect and playback thereof stability and processing characteristics stability; and improved cohesiveness between matrix and metal electrode; thereby overcome the existing above-mentioned deficiency of existing PTC matrix material, provide good base material for making self-limiting heater temperature and over-current protecting element etc.
Conducing composite material with positive temperature coefficient of the present invention contains crystalline polymer matrix A1, conductive filler material B and other auxiliary agent C, and getting macromolecule matrix A1 weight is 100%, each component with respect to the proportioning of matrix is in the matrix material:
A1： 100wt％(A1)
B： 5-40wt％(A1)
C： 1-15wt％(A1)
Wherein A1 is a degree of crystallinity greater than 15% thermal plastic high polymer, B is carbon black, graphite, metal or the metal oxide powder of median size 10-200nm, and C is one or more the mixture in lubricant, oxidation inhibitor, photostabilizer, copper ion inhibitor, thermo-stabilizer, fire retardant and the mineral filler; It is characterized in that said conductive filler material B is through following pretreated conductive filler material: unmodified conductive filler material is added in the reaction unit, under high-speed stirring, slowly add reactive treatment agent, the back discharging that stirs, air tight condition is transferred the usefulness of purchasing; Used reactive treatment agent is the mixture of vinylformic acid, methacrylic acid, acrylate and methyl acrylic ester or maleic anhydride monomer and superoxide, azo type free base initiator, amount of monomer is the 10-50wt% of filler weight, and the consumption of used radical initiator is the 0.1-5wt% of monomer consumption.
Matrix material of the present invention also can contain the second macromolecule matrix A2, and A2 and A1 constitute the blend matrix; A2 is and A1 compatible crystallinity or the amorphous thermoplastic polymer of part perhaps mutually; Getting macromolecule matrix (A1+A2) is 100, and the proportioning of the relative matrix of each component is in the matrix material:
A1： 50-95wt％(A1+A2)
A2： 5-50wt％(A1+A2)
B： 5-40wt％(A1+A2)
C： 1-15wt％(A1+A2)
The used conductive filler material B of above-mentioned matrix material of the present invention is generally the graphitized carbon black (being preferably oil oven method granulation graphitized carbon black) of median size 15-100nm.
Working method with situ-formed graft that conducing composite material adopted of positive temperature coefficient of the present invention, be by before processing, conductive filler material being carried out pre-treatment with reactive component (double bond containing compound and radical polymerization initiator), carrying out realizing in the mixing process grafting modification is carried out on the conductive filler material surface with macromolecular material then.For example use vinylformic acid (AA) and dicumyl peroxide (DCP), by a certain percentage carbon black is handled, to be added to mixing facilities mixing with ratio and macromolecule matrix in certain sequence with it then, DCP decomposes the chemical graft reaction of initiation AA to carbon blacksurface in this process, realize the chemical bonding effect between while and polymeric matrix, AA has played function served as bridge between conductive filler material and polymeric matrix, with conductive filler material to receive on the polymeric matrix with chemical bond-linking, thereby regulate conductive filler material and conductive filler material, interfacial interaction equilibrium of forces between conductive filler material and the macromolecule matrix, to reduce carbon black ionic motor capacity, limit its moving region, from control in essence conductive filler material degree of scatter and distribution, and make it reply circulation ratio to improve.
The present invention does not have particular restriction to crystalline polymer A1, all degree of crystallinity all can be used greater than 15% thermal plastic high polymer, as: high density polyethylene(HDPE) (HDPE), new LDPE (film grade) (LDPE), LLDPE (LLDPE), polyvinylidene difluoride (PVDF) (PVDF), isotatic polypropylene (IPP), ethene-propylene copolymer (EPM), ethylene-vinyl acetate ester copolymer (EVA), ethene-ethyl acrylate copolymer (EEA), polyamide (PA), polycarbonate (PC), polysulfones (PSF) and thermoplastic polyester.The second polymer A2 is and crystalline polymer (A1) compatible crystallinity or the amorphous thermoplastic polymer of part perhaps mutually; Look the difference of crystalline polymer, the second polymer A2 preferably contains the thermoplastic elastomer of polarity segment or functional group, have than crystalline polymer better toughness, anti-deflecting and anti-stress cracking, as: ethylene-vinyl acetate ester copolymer (EVA), ethene-ethyl acrylate copolymer (EEA), ethene-maleic anhydride copolymer (EMA), chlorinatedpolyethylene (CPE) etc., and various rubber, as: natural rubber (NR), butadiene-acrylonitrile rubber (NBR) etc.; Amorphous resin can be polymethylmethacrylate (PMMA), polystyrene (PS), polycarbonate (PC) and polysulfones etc.
Electroconductive stuffing generally is Powdered, as: carbon black, graphite, metal or metal oxide powder.Above-mentioned electroconductive stuffing can use separately, but also different sorts, different-grain diameter mix use.The particle diameter of conductive powder has median size 10-200nm usually.Before processing, need conductive filler material is carried out pre-treatment.
Pre-treatment step and processing condition to conductive filler material are as follows: unmodified conductive filler material added in the reaction unit, under high-speed stirring, slowly add reactive treatment agent, and the back discharging that stirs, air tight condition is transferred the usefulness of purchasing.Used reactive treatment agent is vinylformic acid (AA), methacrylic acid, ethyl propenoate (EA), butyl acrylate (BA), Isooctyl acrylate monomer (2-EHA), and methyl acrylic ester or maleic anhydride (MA) wait and the mixture of superoxide, azo type free base initiator, amount of monomer is the 10-50wt% of carbon black weight, and the amount of used radical initiator is the 0.1-5wt% (being preferably 0.2-2wt%) of monomer consumption.
In addition, can also add other an amount of auxiliary agents, as: lubricant, oxidation inhibitor, photostabilizer, copper ion inhibitor, thermo-stabilizer, fire retardant, mineral filler wait the over-all properties of regulating ptc material.
Matrix material of the present invention is with macromolecule matrix A1 or A1+A2, and pretreated conductive filler material B and other auxiliary agents C form through step manufacturings such as mixing, granulation/fragmentation, moulding, thermal treatments, and concrete steps and processing condition are as follows:
1. mixing: each component raw material is joined in the mixing facilities by a certain percentage, and at the mixing 5-60 of the melting temperature of fusing point that is not less than matrix or softening temperature minute, the cylinder of mixing facilities or screw speed were 20-80rpm;
2. granulation/fragmentation: with the said mixture material with tablets press or pulverizer fragmentation after, obtain the matrix material pellet;
3. moulding: according to shape of product needs with above-mentioned pellet by mold pressing, extrude or technology moulding such as injection molding;
4. thermal treatment: the PTC matrix material after the moulding was handled 5-15 hour being lower than under polymer-based bulk melting point 25-30 ℃ the temperature, obtained the product matrix material.
The present invention is according to the ptc conductive polymer matrix material of above-mentioned material compositing formula and manufacturing process preparation, and room temperature resistivity is 10
3-10
6Ω .cm, PTC intensity＞10
3, and can suppress the NTC effect effectively, the temperature of composite material resistance rate generation transition can be regulated in 50-160 ℃ of scope.Owing to adopt the method for situ-formed graft conductive filler material and matrix resin have been carried out modification simultaneously, regulated the interfacial interaction power of conductive filler material and macromolecule matrix, make the selectivity of conductive filler material generation microcosmic disperse, add the synergy of the lubrication etc. of properties-correcting agent, cause PTC intensity, the PTC effect repetition stability of matrix material to significantly improve, the scope of resistivity transition narrows down.
Ptc material of the present invention can be used as the exothermic material of electricradiator, has good heat conductivity, the joule heating that produces is evenly distributed, and limits warm control characteristic good certainly, non-stop run and discontinuous operation life-span (energising heating outage refrigeration cycle repeatedly) length (＞5000h).
Description of drawings
Fig. 1 is the room temperature resistivity ρ of embodiment 2, embodiment 3 and comparative example 1 matrix material
25Relation curve with the variation of times of thermal cycle.
The relation curve that the electricalresistivity that Fig. 2 is comparative example 1 matrix material under thermal cycle conditions repeatedly changes with temperature T.
The relation curve that the electricalresistivity that Fig. 3 is embodiment 3 matrix materials under thermal cycle conditions repeatedly changes with temperature T.
Embodiment
The present invention is further illustrated to reach accompanying drawing by the following examples.
Embodiment 1-11 makes the PTC conducing composite material by aforementioned each concrete steps and processing condition, comparative example 1-4 except that conductive filler material is unprocessed, all same embodiment of other steps and processing condition.Following table 1, table 2 are the character of each component raw material of using in embodiment and the comparative example, and table 3 is the charging capacity (by weight) of component raw material in each embodiment and the comparative example, and table 4 is the product performance of composites of each embodiment and comparative example.
The polymer-based volume property kind of table 1 name of an article melt index fusing point density production producer
(g/10min) (℃) (g/cm
3) the HDPE 0.2-0.8 130-140 0.920-0.945 of crystalline polymer LDPE 0.3-0.7 100-115 0.910-0.925 Beijing Yanshan Petrochemical Company (A1)
PVDF 0.1-0.5 180-195 second polymer EVA 2.0-15.0 80-95 0.930-0.980 Mitsubishi oiling company (A2) (the VAC content
10-40％)
(AN contains Lanzhou chemical industrial company to NBR
Amount 15-50%)
Table 2 conductive filler material character (carbon black) median size specific surface area DBP absorption value true density surface-element content is than (the m of manufacturer (nm)
2/ g) (ml/100mg) (g/cm
3) rubber group Zi Gong among [O]/[C] the 15-70 150-300 120-125 1.90 0.0277
Carbon black research institute
Table 3 ptc material is formed proportioning
A1/A2 B C treatment agent embodiment 1 LDPE 25 3.2 AA
100 2.5 embodiment, 2 LDPE, 25 3.2 AA
100 5 embodiment, 3 LDPE, 25 3.2 AA
100 7.5 embodiment, 4 LDPE/EVA, 25 3.2 AA
80,/20 7.5 embodiment, 5 LDPE, 25 3.2 AA
100 12.5 embodiment, 6 HDPE/NBR, 30 3.2 AA
80,/20 9 embodiment, 7 PVDF, 30 3.2 AA
100 9 embodiment, 8 LDPE, 25 3.2 BA
100 7.5 embodiment, 9 LDPE/EVA, 25 3.2 BA
80,/20 7.5 embodiment, 10 HDPE/NBR, 30 3.2 BA
80,/20 9 embodiment, 11 PVDF, 30 3.2 BA
100 9 comparative examples, 1 LDPE 25 3.2 0
100 comparative examples, 2 LDPE/EVA 25 3.2 0
80/20 comparative example, 3 HDPE/NBR 30 3.2 0
80/20 comparative example, 4 PVDF 30 3.2 0
100
Table 4 ptc material performance relatively
Room temperature resistivity PTC intensity T
10T
100T
100-T
10
(Ω.cm) (℃) (℃) (℃)
Embodiment 11 345 2.8 * 10
3164 180 16
Comparative example 1 900 1.12 * 10
272 90 18
Comparative example 2 860 0.97 * 10
268 87 19
Comparative example 3 430 8.0 * 10
2107 125 18
Comparative example 4 320 7.5 * 10
2165 182 17
* be the PTC effect or resistivity (ρ)-temperature (T) curvilinear characteristic of exosyndrome material, with resistivity transition peak value ρ on this relation curve
MaxWith room temperature (25 ℃) electricalresistivity
25Ratio ρ
Max/ ρ
25Be defined as PTC intensity; Resistivity is increased to ρ
25Pairing temperature is designated as T in the time of ten times
10Resistivity is increased to ρ
25100 times the time pairing temperature be designated as T
100ρ
Max/ ρ
25Be worth greatly more, then the PTC intensity of matrix material is high more; T
10And T
100Difference T
100-T
10More little, then the temperature range of composite material resistance rate generation transition is narrow more, and transition is more precipitous.
Claims (3)
1. the conducing composite material with positive temperature coefficient contains crystalline polymer matrix A1, conductive filler material B and other auxiliary agent C, and getting macromolecule matrix A1 weight is 100%, each component with respect to the proportioning of matrix is in the matrix material:
A1： 100wt％(A1)
B： 5-40wt％(A1)
C： 1-15wt％(A1)
Wherein A1 is a degree of crystallinity greater than 15% thermal plastic high polymer, B is carbon black, graphite, metal or the metal oxide powder of median size 10-200nm, and C is one or more the mixture in lubricant, oxidation inhibitor, photostabilizer, copper ion inhibitor, thermo-stabilizer, fire retardant and the mineral filler; It is characterized in that said conductive filler material B is through following pretreated conductive filler material: unmodified conductive filler material is added in the reaction unit, under high-speed stirring, slowly add reactive treatment agent, the back discharging that stirs, air tight condition is transferred the usefulness of purchasing; Used reactive treatment agent is the mixture of vinylformic acid, methacrylic acid, acrylate and methyl acrylic ester or maleic anhydride monomer and superoxide, azo type free base initiator, amount of monomer is the 10-50wt% of filler weight, and the consumption of used radical initiator is the 0.1-5% of monomer consumption.
2. matrix material according to claim 1 is characterized in that this matrix material also contains the second macromolecule matrix A2, and A2 is and A1 compatible crystallinity or the amorphous thermoplastic polymer of part perhaps mutually; Getting macromolecule matrix (A1+A2) is 100, and the proportioning of the relative matrix of each component is in the matrix material:
A1： 50-95wt％(A1+A2)
A2： 5-50wt％(A1+A2)
B： 5-40wt％(A1+A2)
C： 1-15wt％(A1+A2)
3. a matrix material as claimed in claim 1 or 2 is characterized in that said conductive filler material B is the graphitized carbon black of median size 15-100nm.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02114762 CN1263801C (en) | 2002-01-21 | 2002-01-21 | Process for preparing electrically conductive high-molecular composite material by in-situ graft to modify electrically conductive filler |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02114762 CN1263801C (en) | 2002-01-21 | 2002-01-21 | Process for preparing electrically conductive high-molecular composite material by in-situ graft to modify electrically conductive filler |
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| Publication Number | Publication Date |
|---|---|
| CN1363629A true CN1363629A (en) | 2002-08-14 |
| CN1263801C CN1263801C (en) | 2006-07-12 |
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|---|---|---|---|
| CN 02114762 Expired - Fee Related CN1263801C (en) | 2002-01-21 | 2002-01-21 | Process for preparing electrically conductive high-molecular composite material by in-situ graft to modify electrically conductive filler |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100429268C (en) * | 2005-08-02 | 2008-10-29 | 中国石油天然气股份有限公司 | Polymer composition with positive temperature coefficient of resistance and preparation method thereof |
| CN103073686A (en) * | 2013-01-07 | 2013-05-01 | 安邦电气集团有限公司 | High thermal stability polymer matrix conductive composite and method for preparing self-regulating heating cable by adopting high thermal stability polymer matrix conductive composite |
| WO2014029068A1 (en) * | 2012-08-20 | 2014-02-27 | Feng Lin | Conductive engineering plastic and preparation method thereof |
| CN105694412A (en) * | 2012-08-20 | 2016-06-22 | 冯林 | Conducting engineering plastic |
| CN105981114A (en) * | 2014-02-06 | 2016-09-28 | 国立研究开发法人科学技术振兴机构 | Resin composition for temperature sensor, element for temperature sensor, and method for producing element for temperature sensor |
| CN106833026A (en) * | 2017-02-08 | 2017-06-13 | 广西华纳新材料科技有限公司 | A kind of surface treatment method of PVC powdered whitings |
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2002
- 2002-01-21 CN CN 02114762 patent/CN1263801C/en not_active Expired - Fee Related
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| CN100429268C (en) * | 2005-08-02 | 2008-10-29 | 中国石油天然气股份有限公司 | Polymer composition with positive temperature coefficient of resistance and preparation method thereof |
| WO2014029068A1 (en) * | 2012-08-20 | 2014-02-27 | Feng Lin | Conductive engineering plastic and preparation method thereof |
| CN103814077A (en) * | 2012-08-20 | 2014-05-21 | 冯林 | Conductive engineering plastic and preparation method thereof |
| CN103814077B (en) * | 2012-08-20 | 2016-03-30 | 深圳市捷创新材料有限公司 | A kind of method preparing conductive engineering plastics |
| CN105694412A (en) * | 2012-08-20 | 2016-06-22 | 冯林 | Conducting engineering plastic |
| CN103073686A (en) * | 2013-01-07 | 2013-05-01 | 安邦电气集团有限公司 | High thermal stability polymer matrix conductive composite and method for preparing self-regulating heating cable by adopting high thermal stability polymer matrix conductive composite |
| CN105981114A (en) * | 2014-02-06 | 2016-09-28 | 国立研究开发法人科学技术振兴机构 | Resin composition for temperature sensor, element for temperature sensor, and method for producing element for temperature sensor |
| CN105981114B (en) * | 2014-02-06 | 2018-05-04 | 国立研究开发法人科学技术振兴机构 | Resin composition for temperature sensor, element for temperature sensor, and method for producing element for temperature sensor |
| US10302506B2 (en) | 2014-02-06 | 2019-05-28 | Japan Science And Technology Agency | Resin composition for temperature sensor, element for temperature sensor, temperature sensor, and method for producing element for temperature sensor |
| CN106833026A (en) * | 2017-02-08 | 2017-06-13 | 广西华纳新材料科技有限公司 | A kind of surface treatment method of PVC powdered whitings |
| CN111944594A (en) * | 2020-08-26 | 2020-11-17 | 惠州市阿特斯润滑技术有限公司 | Guide rod conductive grease |
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|---|---|
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