CN103396599B - Self-limiting heating cable polymer matrix PTC matrix material and preparation method thereof - Google Patents
Self-limiting heating cable polymer matrix PTC matrix material and preparation method thereof Download PDFInfo
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Abstract
A kind of self-limiting heating cable polymer matrix PTC matrix material, it is characterized in that: it is made up of the raw material of following mass percent, Low Density Polyethylene 55-65%, ethylene-vinyl acetate copolymer 20-25%, carbon black 10-15%, barium titanate 2-5%, neopentyl glycol 5-10%, trimethylolethane 5-10%, tetramethylolmethane 5-10%, Tutofusin tris 5-10%, benzophenone 2-3%; Wherein, the Low Density Polyethylene trade mark is 18D, and melting index is 2.0g/min; In ethylene-vinyl acetate copolymer, vinyl acetate mass percent is 14% and 51%.The invention has the beneficial effects as follows: in conventional formulation, add the phase-change heat-storage materials such as neopentyl glycol, tetramethylolmethane, Tutofusin tris as NTC effect inhibitor energy temporarily absorbing environmental heat, delay the generation of NTC effect, prevent the local superheating that material internal defect and impurity or externalities cause, avoid system " thermal runaway " and accelerated deterioration, improve high-temperature stability and the work-ing life of material.Adopt barium titanate inorganic particulate not only can the heating power of micro-controlled material, improve the stability of matrix material.
Description
technical field:
The present invention relates to accompanying-heat cable technical field, refer in particular to a kind of self-limiting heating cable polymer matrix PTC matrix material and preparation method thereof.
background technology:
Polymer matrix PTC material is using polymkeric substance as matrix, the conducting particless such as carbon black, graphite, carbon fiber, metal as filler by the blended matrix material with PTC effect be prepared from.Have cheap, machine-shaping easily, electric property and mechanical property advantages of higher, be widely used in fields such as companion heat, insulation, current limliting, sensings, especially polyvinyl PTC temp auto-controlled cable is all on the actual application in the field of thermal insulation of domatic and culvert, the oil pipeline etc. of building, airport, road and bridge.
It is obvious to there is NTC effect in polyvinyl PTC temp auto-controlled cable, and NTC is the important factor affecting ptc material repeatability and work-ing life.Current ptc material ubiquity repeatability is poor, and the problems such as work-ing life is short seriously hinder its application.
summary of the invention:
The object of the invention is to there is NTC effect defect for current polyvinyl PTC temp auto-controlled cable, provide one can effectively suppress NTC effect, there is good repeatability, long service life, the PTC composite material had good stability; Another object of the present invention is to provide the preparation method of this kind of PTC composite material.
The object of the invention is to realize as follows: a kind of self-limiting heating cable polymer matrix PTC matrix material, it is made up of the raw material of following mass percent, Low Density Polyethylene 55-65%, ethylene-vinyl acetate copolymer 20-25%, carbon black 10-15%, barium titanate 2-5%, neopentyl glycol 5-10%, trimethylolethane 5-10%, tetramethylolmethane 5-10%, Tutofusin tris 5-10%, benzophenone 2-3%; Wherein, the Low Density Polyethylene trade mark is 18D, and melting index is 2.0g/min; In ethylene-vinyl acetate copolymer, vinyl acetate mass percent is 14% and 51%.
The self-limiting heating cable preparation method of polymer matrix PTC matrix material, comprises the following steps:
Step 1, take following raw material composition:
Low Density Polyethylene mass percent 55-65%, ethylene-vinyl acetate copolymer mass percent 20-25%, carbon black mass percentage ratio 10-15%, barium titanate mass percent 2-5%, neopentyl glycol mass percent 5-10%, trimethylolethane mass percent 5-10%, tetramethylolmethane mass percent 5-10%, Tutofusin tris mass percent 5-10%, benzophenone mass percent 1-3%;
Step 2, Low Density Polyethylene step 1 taken, ethylene-vinyl acetate copolymer are divided into 6:4 to be divided into two parts in mass ratio, and portion is added torque rheometer, and under the condition of rheometer temperature 140 DEG C, rotating speed 40r/min, banburying 3 minutes, makes its melting;
Step 3, in the melt of step 2 gained, add the organic phase change materials such as carbon black, barium titanate, benzophenone, neopentyl glycol after, add the first mixed thing of another part of Low Density Polyethylene in step 2, ethylene-vinyl acetate copolymer again, under the condition of rheometer temperature 140 DEG C, rotating speed 40r/min, banburying discharging in 10 minutes;
Step 4, make heating tape, step 3 gained pellet is coated on two copper conductors parallel to each other by screw extrusion press, then adopts
60after Co gamma-rays carries out cross-linking radiation, to its coated polyethylene layer, then carry out constant temperature normalized; Treatment temp 80 degrees Celsius, 2 hours treatment times.
The invention has the beneficial effects as follows: in conventional formulation, add the phase-change heat-storage materials such as neopentyl glycol, tetramethylolmethane, Tutofusin tris as NTC effect inhibitor energy temporarily absorbing environmental heat, delay the generation of NTC effect, prevent the local superheating that material internal defect and impurity or externalities cause, avoid system " thermal runaway " and accelerated deterioration, improve high-temperature stability and the work-ing life of material; Low Density Polyethylene and ethylene-vinyl acetate copolymer is adopted to be that body material has remarkable effect to the PTC strength and stability improving material; If single employing base polyethylene, because it is non-polar polymer, as the polar particle carbon black of filler and barium titanate, distribution content is lower wherein, make the room temperature resistance of material higher, thus its PTC intensity is lower; And adopt Low Density Polyethylene and ethylene-vinyl acetate copolymer to be body material, because ethylene-vinyl acetate copolymer is polar copolymer, it embodies good pardon to polar filler carbon black, barium titanate particles, thus make the distribution content increase in the base of carbon black and barium titanate, the corresponding reduction of room temperature resistance of material, thus the PTC intensity of material increases, and stability strengthens; In addition ethylene-vinyl acetate copolymer has very excellent resistance to deterioration and ozone resistance, thus improves the work-ing life of matrix material; Adopt barium titanate inorganic particulate not only can the heating power of micro-controlled material, do not affect the electroconductibility of compound system, and due to the obstruction of barium titanate particles and its electropositive sucking action in temperature-rise period, inhibit the nodulizing of conducting particles, thus improve the stability of matrix material; Adopt Multistep feeding method, filler is joined in the body material of melting, filler grain is disperseed fully; Avoid in disposable feeding in raw material because blapharoplast is heated uneven, carbon black and barium titanate are wrapped in wherein by the particle first melted, have impact on the motion of filler grain, and then continued parcel by the blapharoplast in succession melted and produce a large amount of agglomerations of filler grain.
embodiment:
Self-limiting heating cable polymer matrix PTC matrix material of the present invention is made up of the raw material of following mass percent: Low Density Polyethylene 55-65%, ethylene-vinyl acetate copolymer 20-25%, carbon black 10-15%, barium titanate 2-5%, neopentyl glycol 5-10%, trimethylolethane 5-10%, Tutofusin tris 5-10%, benzophenone 2-3%.
Wherein, the Low Density Polyethylene trade mark is 18D, and melting index is 2.0g/min; In ethylene-vinyl acetate copolymer, vinyl acetate mass percent is 14% and 51%.
The preparation method of self-limiting heating cable polymer matrix PTC matrix material of the present invention, comprises the following steps:
Step 1, by mass percent take raw material composition:
Low Density Polyethylene 55-65%, ethylene-vinyl acetate copolymer 20-25%, carbon black 10-15%, barium titanate 2-5%, neopentyl glycol 5-10%, trimethylolethane 5-10%, tetramethylolmethane 5-10%, Tutofusin tris 5-10%, benzophenone 2-3%;
Step 2, Low Density Polyethylene step 1 taken, ethylene-vinyl acetate copolymer are divided into 6:4 to be divided into two parts in mass ratio; by mass ratio be 6 portion add torque rheometer; rheometer temperature 140 DEG C, under the condition of rotating speed 40r/min, banburying 3 minutes, makes its melting;
Step 3, in the melt of step 2 gained, add the organic phase change materials such as carbon black, barium titanate, benzophenone, neopentyl glycol after, add Low Density Polyethylene, ethylene-vinyl acetate copolymer that weight ratio in step 2 is 4 again, rheometer temperature 140 DEG C, banburying discharging in 10 minutes under the condition of rotating speed 40r/min.
Step 4, making heating tape.Step 3 gained pellet is coated on two copper conductors parallel to each other by screw extrusion press, then adopts
60after Co gamma-rays carries out cross-linking radiation, to its coated polyethylene layer, then carry out constant temperature normalized.Treatment temp: 80 degrees Celsius, 2 hours treatment times.
The present invention is further illustrated below in conjunction with example.
Example 1
Step 1, take raw material composition:
30.0g Low Density Polyethylene, 7.5g vinyl acetate content are ethylene-vinyl acetate copolymer, 3.0g neopentyl glycol, 7.0g carbon black, 1.25g barium titanate, the 1.25g benzophenone of 14%;
Step 2, by 30g Low Density Polyethylene and 7.5g ethylene-vinyl acetate copolymer tentatively blended after be divided into A, B two parts, A part 22.5g, B part 15.0g.Preliminary for A part blend is added torque rheometer, and rheometer temperature 140 DEG C, under the condition of rotating speed 40r/min, banburying 3 minutes, makes its melting.
Step 3, in the melt of step 2 gained, add step 3.0g neopentyl glycol, 7.0g carbon black, 1.25g barium titanate, 1.25g benzophenone after, add 15.0g Low Density Polyethylene, ethylene-vinyl acetate copolymer again, rheometer temperature 140 DEG C, banburying discharging in 10 minutes under the condition of rotating speed 40r/min.
Step 4, making heating tape.Step 3 gained pellet is coated on two copper conductors parallel to each other by screw extrusion press, then adopts
60after Co gamma-rays carries out cross-linking radiation, to its coated polyethylene layer, then carry out constant temperature normalized.Treatment temp 80 degrees Celsius, 2 hours treatment times.
Example 2,
Employing vinyl acetate content is the vinyl acetate content in the ethylene-vinyl acetate copolymer replacement example 1 of 51% is the ethylene-vinyl acetate copolymer of 14%, and all the other step conditions are as example 1.
Example 3,
Adopt the neopentyl glycol in trimethylolethane replacement example 1, all the other step conditions are as example 1.
Example 4, the neopentyl glycol adopted in Tutofusin tris replacement example 1, all the other step conditions are as example 1.
Claims (2)
1. a self-limiting heating cable polymer matrix PTC matrix material, it is characterized in that: it is made up of the raw material of following mass percent, Low Density Polyethylene 55-65%, ethylene-vinyl acetate copolymer 20-25%, carbon black 10-15%, barium titanate 2-5%, neopentyl glycol 5-10%, trimethylolethane 5-10%, tetramethylolmethane 5-10%, Tutofusin tris 5-10%, benzophenone 2-3%; Wherein, the Low Density Polyethylene trade mark is 18D, and melting index is 2.0g/min; In ethylene-vinyl acetate copolymer, vinyl acetate mass percent is 14% and 51%.
2. self-limiting heating cable polymer matrix PTC matrix material according to claim 1, it is characterized in that, preparation method comprises the following steps:
Step 1, take following raw material composition:
Low Density Polyethylene mass percent 55-65%, ethylene-vinyl acetate copolymer mass percent 20-25%, carbon black mass percentage ratio 10-15%, barium titanate mass percent 2-5%, neopentyl glycol mass percent 5-10%, trimethylolethane mass percent 5-10%, tetramethylolmethane mass percent 5-10%, Tutofusin tris mass percent 5-10%, benzophenone mass percent 1-3%;
Step 2, Low Density Polyethylene step 1 taken, ethylene-vinyl acetate copolymer are divided into 6:4 to be divided into two parts in mass ratio, and portion is added torque rheometer, and under the condition of rheometer temperature 140 DEG C, rotating speed 40r/min, banburying 3 minutes, makes its melting;
Step 3, in the melt of step 2 gained, add carbon black, barium titanate, benzophenone, neopentyl glycol, trimethylolethane, tetramethylolmethane and Tutofusin tris organic phase change material after, add the first mixed thing of another part of Low Density Polyethylene in step 2, ethylene-vinyl acetate copolymer again, under the condition of rheometer temperature 140 DEG C, rotating speed 40r/min, banburying discharging in 10 minutes.
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| CN103745772B (en) * | 2013-12-29 | 2016-05-18 | 湖南华菱线缆股份有限公司 | Phase transformation temp auto-controlled shielded cable |
| CN104036866A (en) * | 2014-06-27 | 2014-09-10 | 国家电网公司 | Phase-change temperature-control type high-voltage cable |
| CN104403177A (en) * | 2014-12-17 | 2015-03-11 | 大连联合高分子材料有限公司 | Wear-resistant heat-shrinkable sleeve for aluminum pipeline of automobile air conditioner as well as preparation method and application of wear-resistant heat-shrinkable sleeve |
| CN105061848B (en) * | 2015-06-11 | 2019-02-01 | 上海大学 | 36V self limiting temperature adds-accompanying-heat cable core ribbon material and preparation method thereof |
| CN104961966B (en) * | 2015-07-17 | 2018-06-08 | 广东环威电线电缆股份有限公司 | Heat the preparation method of cable, semi-conductive high polymer material and semi-conductive high polymer material |
| CN109836823A (en) * | 2019-02-25 | 2019-06-04 | 清华大学 | A kind of regulation method of insulation material material temperature resistance characteristic |
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| CN1546425A (en) * | 2003-12-02 | 2004-11-17 | 天津大学 | Graphite, phenolic resin, (Ba1-x-y, Srx, Pby) TiO3 based PTC thermistor and method for preparing the same |
| CN102408606A (en) * | 2011-09-02 | 2012-04-11 | 西安盖沃热能科技有限公司 | Flame-retardant PTC (positive temperature coefficient) polymer electroconductive material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1546425A (en) * | 2003-12-02 | 2004-11-17 | 天津大学 | Graphite, phenolic resin, (Ba1-x-y, Srx, Pby) TiO3 based PTC thermistor and method for preparing the same |
| CN102408606A (en) * | 2011-09-02 | 2012-04-11 | 西安盖沃热能科技有限公司 | Flame-retardant PTC (positive temperature coefficient) polymer electroconductive material and preparation method thereof |
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