CN102604281A - Preparation method of crosslinking-free polymer-based high-temperature PTC (positive temperature coefficient) material - Google Patents
Preparation method of crosslinking-free polymer-based high-temperature PTC (positive temperature coefficient) material Download PDFInfo
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- CN102604281A CN102604281A CN2012100321268A CN201210032126A CN102604281A CN 102604281 A CN102604281 A CN 102604281A CN 2012100321268 A CN2012100321268 A CN 2012100321268A CN 201210032126 A CN201210032126 A CN 201210032126A CN 102604281 A CN102604281 A CN 102604281A
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Abstract
The invention relates to a preparation method of a crosslinking-free polymer-based high-temperature PTC (positive temperature coefficient) material. According to the preparation method provided by the invention, carbon black or nano titanium carbide is used as conducting filler, high-melting point (327 DEG C) crystalline polytetrafluoroethylene is used as a polymeric matrix, and a method similar to powder metallurgy is adopted to prepare the high-temperature polymer-based PTC material. The polymer-based PTC material and the preparation method of the polymer-based PTC material have the following characteristics: (1) because of the high-melting point polytetrafluoroethylene matrix, the material has a PTC transition temperature of higher than 300 DEG C; (2) the high molten viscosity of polytetrafluoroethylene limits the flocculation and rearrangement of conducting particles into a conductive paths at a high temperature, so as to eliminate a NTC (negative temperature coefficient) effect and carry out radiation crosslinking treatment with no need of additional steps and high cost; and (3) the preparation method has simple technological process and low processing cost, and has no use and discharge of toxic and harmful chemicals.
Description
Technical field
Technical field involved in the present invention is that a kind of PTC transition temperature surpasses high temperature polymer matrix PTC material of 300 ℃ and preparation method thereof, provides a kind of exempting to join the simple method of eliminating polymer matrix PTC material NTC effect simultaneously.
Background technology
Polymer-based positive temperature coefficient (positive temperature coefficient; PTC) conducing composite material (abbreviation polymer matrix PTC material) is one of relatively more popular intelligent macromolecule material of current research and development both at home and abroad; It is a matrix with the semicrystalline polymeric material usually; Add conductive filler materials such as carbon black, metal powder, MOX, the heterogeneous compound system that forms according to certain composite material preparation process.When temperature was elevated near the fusing point of polymeric matrix, the resistivity of polymer matrix PTC material can increase sharply near percolation threshold (can increase 1.5 ~ 8 one magnitude), produced the jump of several magnitude, and the transformation from (partly) conductor to isolator takes place.Utilize that this characteristic processes from the temperature control heating unit, after applying certain interchange or volts DS, can heat up rapidly, resistance also increases rapidly, and constant in preset temperature, thereby has temperature adjustment function and sensitive switching effect.Characteristics such as polymer matrix PTC material has conductivity adjustable in a big way, is easy to moulding, flexible, cost are low are widely used in preparation self-limiting heater temperature, overcurrent protection and TP etc.
Also there is following deficiency in present polymer matrix PTC material: the polymeric matrix that 1, generally adopts is Vilaterm, Vestolen PP 7052, this type of Injecatable EVA Copolymer crystalline polymer; Their fusing point is generally all below 150 ℃; Cause the PTC transition temperature of the polymer matrix PTC material that obtains lower (< 150 ℃), can not satisfy the application demand of high temperature occasion; 2, be raised to fusing point when above when temperature, uncrosslinked or crosslinkedly have the NTC phenomenon in the polymer matrix PTC material fully inadequately.The NTC phenomenon not only makes the electrical property of ptc material that irreversible variation takes place, and in the use of material, understands because of the too high deformation failure of material temperature, even catching fire.Usually the elimination NTC effect method that adopts is a radiation crosslinking, forms macromolecular network structure, the high temperature flocculation of restriction CB particle, and then eliminate the NTC phenomenon, this is to make ptc material reach the most important means of application request.But radiation crosslinking needs expensive cross-linking apparatus, has both increased the complicacy of material preparation process, has improved the production cost of material again.Therefore, the simple and easy method of inventing the polymer-based carbon high-temp PTC material of a kind of high PTC transition temperature (surpass 200 ℃ or higher) and eliminating NTC effect in the polymer matrix PTC material is all having great importance aspect the Application Areas of expansion polymer matrix PTC material and reduction cost of manufacture two.
Summary of the invention
The objective of the invention is to overcome the deficiency of existing polymer matrix PTC material and technology of preparing thereof, a kind of linked polymer base high-temp PTC preparation methods of exempting from is provided, concrete summary of the invention is:
The invention provides a kind of preparation method of high temperature polymer matrix PTC material, method steps is:
(1) described high temperature polymer matrix PTC material comprises following components in weight percentage: conductive filler material 1.0-15%; Tetrafluoroethylene 80 ~ 98%; Coupling agent 0.5 ~ 2.5%; Inhibitor 0.5 ~ 2.5%;
(2) described conductive filler material is to use through coupling agent modified back in advance, and modification procedure is: at room temperature make it in absolute ethyl alcohol, form suspension-s through ultra-sonic dispersion and stirring conductive filler material, continue stirring 10 ~ 30 minutes after adding coupling agent then; Add deionized water subsequently, at 40 ~ 60 ℃ of following ultra-sonic dispersion and stirred 15 ~ 60 minutes; The spinning powder, use absolute ethanol washing 1 ~ 3 time then after, 60 ~ 120 ℃ of following vacuum-dryings 2 ~ 5 hours, use after naturally cooling to room temperature;
(3) described polytetrafluorethylepowder powder is at 80 ~ 150 ℃ of following vacuum-drying 2 h, uses after naturally cooling to room temperature;
(4) mixing process: according to prescription with the conductive filler material of coupling agent treatment, polytetrafluorethylepowder powder, inhibitor ball mill high speed ball milling 0.5 ~ 2.5 hour;
(5) moulding process: adopt to be similar to the powder metallurgy method moulding; Mixed powder pressed down under the pressure of room temperature 50 ~ 100 MPa process diameter 1 ~ 3 cm; The disk shape sample of height 0.1-0.3 cm; Then at 340 ~ 380 ℃ of following hot pressed sinterings, obtain the high temperature polymer matrix PTC material after naturally cooling to room temperature.
Described conductive filler material is that in carbon black N550 or the nano titanium carbide one or more are composite; Described polytetrafluoroethylene (PTFE) fusing point is 327 ℃, and melt viscosity is 10
10Pas, median size is 25 μ m; Described coupling agent comprises a kind of in silane coupling agent γ-An Bingjisanyiyangjiguiwan, N-(2-aminoethyl)-3-aminopropyl triethoxysilane, γ-(methacryloxypropyl) propyl trimethoxy silicane, γ-glycidyl ether oxygen propyl trimethoxy silicane, the 3-mercaptopropyl trimethoxysilane; Described inhibitor can be a kind of in phenols or amine antioxidants such as antioxidant 1010, antioxidant 1076, oxidation inhibitor 168, oxidation inhibitor 1098, the antioxidant 2246.
Utilize the high melt viscosity of PTFE self (10
10Pas), temperature surpasses behind the fusing point can not the mobile characteristics, and the flocculation of restriction conductive filler material in the PTFE matrix forms new conductive path, exempts from the purpose that the NTC effect is eliminated in radiation thereby reach.
The invention has the advantages that: adopt the matrix of high temperature resistant dystectic tetrafluoroethylene as preparation high temperature polymer matrix PTC material; Make the PTC transition temperature of matrix material near the fusing point of tetrafluoroethylene; Up to more than 320 ℃, can satisfy the application under the high temperature polymer matrix PTC material high temperature occasion; The preparation process of material is not used and poisoned element or poisonous organic solvent, and is harmless, free from environmental pollution; Utilize the high melt viscosity of PTFE self (10
10Pas), temperature surpasses behind the fusing point can not the mobile characteristics, and the motion of restriction conductive filler material in the PTFE matrix prevents that effectively its flocculation from forming new conductive path, joins the purpose of eliminating the NTC effect thereby reach to exempt from, and effectively reduces the cost of manufacture of ptc material.
Description of drawings
The sooty transmission electron micrograph of Fig. 1 for using among the present invention;
Fig. 2 is the transmission electron micrograph of the nano titanium carbide that uses among the present invention;
Fig. 3 is the molecular structural formula of the silane coupling agent that uses among the present invention;
Fig. 4 is the molecular structural formula of the oxidation inhibitor that uses among the present invention;
Fig. 5 prepares the process flow sheet of high temperature polymer matrix PTC material for the present invention;
Fig. 6 is the resistivity-temperature characteristics figure of ptc polymer in the specific embodiment 1;
Fig. 7 is the resistivity-temperature characteristics figure of ptc polymer in the specific embodiment 2;
Fig. 8 is the resistivity-temperature characteristics figure of ptc polymer in the specific embodiment 3;
Fig. 9 is the resistivity-temperature characteristics figure of ptc polymer in the specific embodiment 4;
Figure 10 is the resistivity-temperature characteristics figure of ptc polymer in the specific embodiment 5.
Embodiment
Below through combining specific embodiment that the present invention is done further detailed description, like Fig. 1,2,3,4, shown in 5:
Adopt following components in weight percentage in the present embodiment: carbon black: 0.2158 g (8%), tetrafluoroethylene: 2.4547 g (91%), silane coupling agent γ-An Bingjisanyiyangjiguiwan: 0.0135 g (0.5%), antioxidant 1010: 0.0135 g (0.5%).
Carbon black N550 uses after the modification of silane coupling agent γ-An Bingjisanyiyangjiguiwan in advance; Modification procedure is: at room temperature make it in absolute ethyl alcohol, form suspension-s through ultra-sonic dispersion and stirring carbon black N550, add then and continue behind the γ-An Bingjisanyiyangjiguiwan to stir 10 minutes; Add deionized water subsequently, at 50 ℃ of following ultra-sonic dispersion and stirred 15 minutes; The spinning powder, use absolute ethanol washing 3 times then after, 80 ℃ of following vacuum-dryings 2 hours, use after naturally cooling to room temperature;
Polytetrafluorethylepowder powder is at 80 ℃ of following vacuum-drying 2 h, uses after naturally cooling to room temperature.
The preparation method of high temperature polymer matrix PTC material may further comprise the steps:
(1) mixing process: the carbon black N550 powder that γ-An Bingjisanyiyangjiguiwan is handled, the polytetrafluorethylepowder powder of drying treatment and antioxidant 1010 were ball mill high speed ball milling 2 hours;
(2) moulding process: mixed powder pressed down under the pressure of room temperature 100 MPa process diameter 2 cm, the disk shape sample of height 0.2 cm then at 380 ℃ of following hot pressed sinterings, obtains the high temperature polymer matrix PTC material after naturally cooling to room temperature.With measuring its resistance-temperature performance behind the polymer matrix PTC material sample surfaces coated with conductive elargol of this prescription, its performance is seen accompanying drawing 6.
Adopt following components in weight percentage in the present embodiment: carbon black: 0.1843 g (5%), tetrafluoroethylene: 3.4648 g (94%), silane coupling agent γ-An Bingjisanyiyangjiguiwan: 0.0184 g (0.5%), antioxidant 1010: 0.0184 g (0.5%).
Except prescription changed, identical among other operating process and the embodiment 1, the resistance-temperature performance that obtains the high temperature polymer matrix PTC material according to technical process shown in Figure 5 was seen accompanying drawing 7.
Adopt following components in weight percentage in the present embodiment: carbon black: 0.1843 g (15%), tetrafluoroethylene: 1.0321 g (84%), silane coupling agent γ-An Bingjisanyiyangjiguiwan: 0.0117 g (0.5%), antioxidant 1010: 0.0117 g (0.5%).
Except prescription changed, identical among other operating process and the embodiment 1, the resistance-temperature performance that obtains the high temperature polymer matrix PTC material according to technical process shown in Figure 5 was seen accompanying drawing 8.
Embodiment 4
Adopt following components in weight percentage in the present embodiment: titanium carbide: 0.2147 g (9%), tetrafluoroethylene: 2.1470 g (90%), silane coupling agent N-(2-aminoethyl)-3-aminopropyl triethoxysilane: 0.0119 g (0.5%), oxidation inhibitor 1098:0.0119 g (0.5%).
Except prescription changed, identical among other operating process and the embodiment 1, the resistance-temperature performance that obtains the high temperature polymer matrix PTC material according to technical process shown in Figure 5 was seen accompanying drawing 9.
Adopt following components in weight percentage in the present embodiment: carbon black N550:0.1548 g (4%), titanium carbide: 0.1548 g (4%), tetrafluoroethylene: 3.4830 g (90%), silane coupling agent N-(2-aminoethyl)-3-aminopropyl triethoxysilane: 0.0387 g (1.0%), antioxidant 1076: 0.0387 g (1.0%).
Except prescription changed, identical among other operating process and the embodiment 1, the resistance-temperature performance that obtains the high temperature polymer matrix PTC material according to technical process shown in Figure 5 was seen accompanying drawing 10.
Claims (3)
1. exempt from linked polymer base high-temp PTC preparation methods for one kind, it is characterized in that method steps is:
(1) described high temperature polymer matrix PTC material comprises following components in weight percentage: conductive filler material 1.0-15%; Tetrafluoroethylene 80 ~ 98%; Coupling agent 0.5 ~ 2.5%; Inhibitor 0.5 ~ 2.5%;
(2) described conductive filler material is to use through coupling agent modified back in advance, and modification procedure is: at room temperature make it in absolute ethyl alcohol, form suspension-s through ultra-sonic dispersion and stirring conductive filler material, continue stirring 10 ~ 30 minutes after adding coupling agent then; Add deionized water subsequently, at 40 ~ 60 ℃ of following ultra-sonic dispersion and stirred 15 ~ 60 minutes; The spinning powder, use absolute ethanol washing 1 ~ 3 time then after, 60 ~ 120 ℃ of following vacuum-dryings 2 ~ 5 hours, use after naturally cooling to room temperature;
(3) described polytetrafluorethylepowder powder is at 80 ~ 150 ℃ of following vacuum-drying 2 h, uses after naturally cooling to room temperature;
(4) mixing process: according to prescription with the conductive filler material of coupling agent treatment, polytetrafluorethylepowder powder, inhibitor ball mill high speed ball milling 0.5 ~ 2.5 hour;
(5) moulding process: adopt to be similar to the powder metallurgy method moulding; Mixed powder pressed down under the pressure of room temperature 50 ~ 100 MPa process diameter 1 ~ 3 cm; The disk shape sample of height 0.1-0.3 cm; Then at 340 ~ 380 ℃ of following hot pressed sinterings, obtain the high temperature polymer matrix PTC material after naturally cooling to room temperature.
2. a kind of linked polymer base high-temp PTC preparation methods of exempting from according to claim 1 is characterized in that described conductive filler material is that in carbon black N550 or the nano titanium carbide one or more are composite; Described polytetrafluoroethylene (PTFE) fusing point is 327 ℃, and melt viscosity is 10
10Pas, median size is 25 μ m; Described coupling agent comprises a kind of in silane coupling agent γ-An Bingjisanyiyangjiguiwan, N-(2-aminoethyl)-3-aminopropyl triethoxysilane, γ-(methacryloxypropyl) propyl trimethoxy silicane, γ-glycidyl ether oxygen propyl trimethoxy silicane, the 3-mercaptopropyl trimethoxysilane; Described inhibitor can be a kind of in phenols or amine antioxidants such as antioxidant 1010, antioxidant 1076, oxidation inhibitor 168, oxidation inhibitor 1098, the antioxidant 2246.
3. the removing method of the described high temperature polymer matrix PTC material of claim 1 a NTC effect is characterized in that: utilize the high melt viscosity of PTFE self (10
10Pas), temperature surpasses behind the fusing point can not the mobile characteristics, and the flocculation of restriction conductive filler material in the PTFE matrix forms new conductive path, exempts from the purpose that the NTC effect is eliminated in radiation thereby reach.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104788818A (en) * | 2015-04-09 | 2015-07-22 | 郑州大学 | PTC (positive temperature coefficient) polymer-matrix conductive composite with adjustable PTC strength and preparation method of composite |
| CN108084614A (en) * | 2017-11-25 | 2018-05-29 | 芜湖市恒鑫电缆有限责任公司 | A kind of PTC high-molecular conductive material for self limiting temperature accompanying-heat cable |
| CN110359035A (en) * | 2019-06-05 | 2019-10-22 | 山东青洁能环保有限公司 | Evaporative condenser heat exchanging pipe supermolecule film covering method |
| WO2019205546A1 (en) * | 2018-04-25 | 2019-10-31 | 华南理工大学 | Functionalized two-dimensional layered transition metal carbide material f-mxene and preparation method therefor and use thereof in rubber |
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| CN101560325A (en) * | 2009-05-26 | 2009-10-21 | 上海科特高分子材料有限公司 | High-temperature resistant PTC electroconductive composition, high-temperature resistant PTC device containing composition and manufacturing method thereof |
| CN101724214A (en) * | 2009-11-05 | 2010-06-09 | 南通华兴化学工程建设有限公司 | Antistatic polytetrafluoroethylene piping component |
| CN101851383A (en) * | 2010-06-09 | 2010-10-06 | 深圳市东维丰电子科技股份有限公司 | Conductive polymer composite material and preparation method thereof |
| CN201648280U (en) * | 2009-11-05 | 2010-11-24 | 南通华兴化学工程建设有限公司 | Antistatic polytetrafluoroethylene piping component |
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Patent Citations (4)
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| CN101560325A (en) * | 2009-05-26 | 2009-10-21 | 上海科特高分子材料有限公司 | High-temperature resistant PTC electroconductive composition, high-temperature resistant PTC device containing composition and manufacturing method thereof |
| CN101724214A (en) * | 2009-11-05 | 2010-06-09 | 南通华兴化学工程建设有限公司 | Antistatic polytetrafluoroethylene piping component |
| CN201648280U (en) * | 2009-11-05 | 2010-11-24 | 南通华兴化学工程建设有限公司 | Antistatic polytetrafluoroethylene piping component |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104788818A (en) * | 2015-04-09 | 2015-07-22 | 郑州大学 | PTC (positive temperature coefficient) polymer-matrix conductive composite with adjustable PTC strength and preparation method of composite |
| 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 |
| CN108084614A (en) * | 2017-11-25 | 2018-05-29 | 芜湖市恒鑫电缆有限责任公司 | A kind of PTC high-molecular conductive material for self limiting temperature accompanying-heat cable |
| WO2019205546A1 (en) * | 2018-04-25 | 2019-10-31 | 华南理工大学 | Functionalized two-dimensional layered transition metal carbide material f-mxene and preparation method therefor and use thereof in rubber |
| CN110359035A (en) * | 2019-06-05 | 2019-10-22 | 山东青洁能环保有限公司 | Evaporative condenser heat exchanging pipe supermolecule film covering method |
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Application publication date: 20120725 |