CN100519633C - Radiation crossliaking method of high polymer PTC material - Google Patents
Radiation crossliaking method of high polymer PTC material Download PDFInfo
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- CN100519633C CN100519633C CNB2004100156459A CN200410015645A CN100519633C CN 100519633 C CN100519633 C CN 100519633C CN B2004100156459 A CNB2004100156459 A CN B2004100156459A CN 200410015645 A CN200410015645 A CN 200410015645A CN 100519633 C CN100519633 C CN 100519633C
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- high molecular
- linking agent
- ptc material
- powder
- crosslinking
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Abstract
A process for preparing high-molecular PTCmaterial by radiation cross-linking method includes using electronic beam or gamma ray (Co60) to radiate the high-molecular polymer and electric conducting particles to make them be cross-linked to maximum, immersing to diffuse the cross-linking agent into the materials, and radiating again for cross-linking. The PTC material has high strength.
Description
Technical field
A kind of high molecular PTC material manufacturing method of the present invention relates to the manufacture method with radiation crosslinking processing high molecular PTC material, refers in particular to a kind of processing method that improves the crosslinked polymer degree.
Background technology
The positive temperature coefficient PTC of high molecular polymer--conducting particles composite conducting material (positivetemperature coefficient) characteristic after being found by Frydman in 1945, become the focus of research and development, so far, this class ptc material has been developed as Industrial products as the novel conductive functional materials.Just in certain temperature range, the resistivity of material self can increase with the rising of temperature so-called PTC phenomenon.These high molecular polymers comprise polyethylene, polypropylene, polyvinylidene difluoride (PVDF), voltalef, and their multipolymer.Conducting particles comprises carbon black, graphite, carbon fiber, metal-powder (as silver powder, copper powder, aluminium powder, nickel powder, Stainless Steel Powder).Have the thermistor that this class electrical conductor of ptc characteristics is made, be applied to the overcurrent protection setting of circuit; Also can make, be applied to be incubated the heating facility from the temperature control heating member.The high molecular PTC material has been widely applied in the various fields such as communication, computer, automobile, Industry Control, household electrical appliance, insulation heating.But the problem that present high molecular PTC material is faced is that uncrosslinked high molecular PTC material negative temperature coefficient (NTC) characteristic can occur after temperature surpasses transition temperature, influenced the practical application of this material.Just after surpassing certain temperature range, the resistivity of material self can reduce with the rising of temperature so-called NTC phenomenon.Radiation crosslinking can improve the NTC characteristic of high molecular PTC material, and along with the increase of radiation dose, the high molecular polymer degree of crosslinking improves, and the NTC phenomenon reduces gradually.Generally there is radiation crosslinking degree theoretical maximum in high molecular polymer, promptly reach this theoretical maximum after, improve radiation dose, degree of crosslinking no longer increases.The adding of linking agent can effectively improve cross-linking efficiency, but very little to the influence of degree of crosslinking, and reason is promptly to consume at the initial reaction stage linking agent.In order to address the above problem, the invention provides a kind of new technical scheme.
Summary of the invention
The object of the present invention is to provide a kind of manufacture method, improve high molecular polymer radiation crosslinking degree, eliminate the NTC phenomenon and improve PTC intensity with radiation crosslinking processing high molecular PTC material.
The object of the invention can be achieved through the following technical solutions: a kind of high molecular PTC material, and it is by high molecular polymer--and the conducting particles composite conducting material is formed, at first with electron beam or gamma-rays (Co
60) radiation crosslinking reaches maximum degree of crosslinking, with the mode of soaking, makes the linking agent scattering and permeating enter material matrix then, and then radiation crosslinking, further improves the high molecular polymer degree of crosslinking, improves PTC intensity thereby eliminate the NTC phenomenon.
The present invention has compared with prior art broken through the available degree of crosslinking maximum value of the common radiation crosslinking mode of high molecular polymer, further eliminates the NTC phenomenon and improves PTC intensity.
Description of drawings
Fig. 1, the usual method cross-linking radiation is to the influence curve figure of degree of crosslinking.
Fig. 2, the usual method cross-linking radiation is to the influence curve figure of polyethylene-carbon black matrix material ptc characteristics.
Fig. 3, the inventive method cross-linking radiation is to the influence curve figure of degree of crosslinking (pre-irradiation the 15Mrad pre-irradiation is crosslinked) for the second time.
Fig. 4, the inventive method cross-linking radiation is to the influence curve figure of polyethylene-carbon black composite conducting material ptc characteristics.
Embodiment
Table 1 unit: g
| Powdered conductive polymer composite | High density polyethylene(HDPE) | Carbon | Oxidation inhibitor | |
| 1 | 500 | 300 | 8 |
Annotate: high density polyethylene(HDPE): raise the sub-5000S of petro-chemical corporation
Carbon black: the XC-72 of Cabot Co.,Ltd
Oxidation inhibitor: the U.S. big lake chemical industry ANOX70 of company limited
Each component in the table 1 is mixing even in Banbury mixer under 190 ℃ of temperature, through cooling, being clipped in pad behind the pulverizing abrasive dust goes up in two steel plates of mylar, with the polythene strip of vulcanizing press compacting into about 0.5 mm thick, the compressing tablet temperature is controlled at 150～160 ℃, will guarantee as far as possible that compressing tablet is smooth, smooth, even, carry out cross-linking radiation with rumbatron, irradiation dose is 3Mrad to 30Mrad.Then crosslinked back sample is cut into suitable shape, adds in the linking agent tripropylene glycol double methacrylate, and they are placed in the glass dish, build lid.Constant temperature and timing then be it's time to expect sample taken out, and rinses in acetone, washes the linking agent on surface off, dries then, is placed in the loft drier and dries.The time of soaking linking agent is 48 hours; The temperature of soaking linking agent is 50 ℃.Carry out the radiation crosslinking second time then, irradiation dose is 3Mrad to 15Mrad.
The mensuration of cross-linking radiation degree: accurately take by weighing about 0.2 gram of sample, be placed in the stainless steel string bag, put into fatty extractor extracting again, solvent is a dimethylbenzene.Extracting is put into baking oven and is dried to constant weight (temperature is controlled at 60～70 ℃), and calculate its gel content after finishing.
The mensuration of PTC intensity: the sample two sides that cross-linking radiation is good as electrode, is cut into the small pieces of 10*10mm size with the vulcanizing press composite copper foil, with rt test instrument test resistance-temperature curve.
Sample cross-linking radiation degree and PTC intensity such as Fig. 1 of adopting usual method to obtain, the usual method cross-linking radiation to the influence curve figure of degree of crosslinking and Fig. 2 usual method cross-linking radiation to shown in the influence of polyethylene-carbon black composite conducting material ptc characteristics, along with the increase degree of crosslinking of irradiation dose no longer increases after reaching maximum value.
Adopt sample cross-linking radiation degree that the inventive method obtains and PTC intensity as Fig. 3 the inventive method cross-linking radiation to the influence of degree of crosslinking (second time pre-irradiation the 15Mrad pre-irradiation is crosslinked) and Fig. 4 the inventive method cross-linking radiation to shown in the influence curve figure of polyethylene-carbon black composite conducting material ptc characteristics, adopt the inventive method can further improve the high molecular polymer degree of crosslinking, improve PTC intensity thereby eliminate the NTC phenomenon.
Claims (3)
1. high molecular PTC material radiation crosslinking method, the high molecular PTC material is by high molecular polymer--and conducting particles is compound to be formed, and it is characterized in that: at first, with electron beam or gamma-rays Co
60The radiation crosslinking macromolecule conducting material reaches maximum degree of crosslinking, and then, the macromolecule conducting material that will reach maximum degree of crosslinking is immersed in the linking agent, and the linking agent scattering and permeating is entered in the material matrix; Again, once more with electron beam or gamma-rays Co
60Radiation crosslinking, obtain to eliminate the high molecular PTC material that the NTC phenomenon improves PTC intensity, wherein, described high molecular polymer is polyethylene, polypropylene, polyvinylidene difluoride (PVDF), voltalef, and their multipolymer, described conducting particles is carbon black, graphite, carbon fiber, metal-powder, and metal-powder is silver powder, copper powder, aluminium powder, nickel powder, Stainless Steel Powder.
2. according to the described a kind of high molecular PTC material radiation crosslinking method of claim 1, it is characterized in that: will process high molecular PTC material that the method for high molecular PTC material makes once more with the mode of soaking linking agent with radiation crosslinking, make the linking agent scattering and permeating enter material matrix, and then with electron beam or gamma-rays Co
60Radiation crosslinking.
3. according to claim 1 or 2 described a kind of high molecular PTC material radiation crosslinking methods, it is characterized in that: described linking agent is the tripropylene glycol double methacrylate, and the time of soaking linking agent is 48 hours; The temperature of soaking linking agent is 50 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100156459A CN100519633C (en) | 2004-01-06 | 2004-01-06 | Radiation crossliaking method of high polymer PTC material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100156459A CN100519633C (en) | 2004-01-06 | 2004-01-06 | Radiation crossliaking method of high polymer PTC material |
Publications (2)
| Publication Number | Publication Date |
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| CN1556133A CN1556133A (en) | 2004-12-22 |
| CN100519633C true CN100519633C (en) | 2009-07-29 |
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| CNB2004100156459A Expired - Fee Related CN100519633C (en) | 2004-01-06 | 2004-01-06 | Radiation crossliaking method of high polymer PTC material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304874B (en) * | 2013-05-24 | 2016-03-02 | 安邦电气集团有限公司 | Flame retardant type PTC polymer heating material and preparation method thereof |
| CN107115795B (en) * | 2017-03-24 | 2021-01-19 | 浙江师范大学 | Separation membrane with pH-dependent flux under acidic condition and preparation method thereof |
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Owner name: SHANGHAI CHANGYUAN WAYON CIRCUIT PROTECTION CO., L Free format text: FORMER NAME: SHANGHAI CHANGYUAN WEIAN ELECTRONIC LINE PROTECTION CO., LTD. |
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Address after: 200092, Siping Road, Shanghai, No. 710, 715-Z Patentee after: Shanghai Changyuan Wayon Circuit Protection Co., Ltd. Address before: 200092, Siping Road, Shanghai, No. 710, 715-Z Patentee before: Shanghai Changyuan Wayon Circuit Protection Co., Ltd. |
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