CN101205327B - Polyolefin conductive polymer with middle-positive temperature coefficient - Google Patents
Polyolefin conductive polymer with middle-positive temperature coefficient Download PDFInfo
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- CN101205327B CN101205327B CN2007101905665A CN200710190566A CN101205327B CN 101205327 B CN101205327 B CN 101205327B CN 2007101905665 A CN2007101905665 A CN 2007101905665A CN 200710190566 A CN200710190566 A CN 200710190566A CN 101205327 B CN101205327 B CN 101205327B
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Abstract
The invention relates to a medium positive temperature coefficient polyolefin conductive polymer with more stable PCT property, and is characterized in that the polymer is composed of: 50-70 parts of high pressure polyethylene resin, 20-40 parts of polyisobutene, 20-30 parts of conductive carbon black, 1-3 parts of tribasic lead sulfate, 1-3 parts of calcium stearate, 4-7 parts of dipentaerythritol ester, 2-5 parts of chlorcosane, 3-6 parts of tetrapentaerythritol ester, and 3-5 parts of diisopropylbenzene peroxide. As for the obtained polyolefin conductive polymer, the PTC stability is largely increased, the PTC property fluctuation is small, and the durability is good. After about 1000 times of repeated power on / off tests, the deviation of temperature control ranges from minus 2-5 DEG. C to plus 2-5 DEG. C, which is largely smaller than the existing medium positive temperature coefficient polyolefin conducting polymer which has a deviation of temperature control ranging from minus 10 DEG. C to plus 10 DEG. C. The PTC effect is more evident, and the PTC property is very stable for long-term electrifying or power on / off circulation.
Description
Technical field
The present invention relates to the more stable middle temperature polyolefin conductive polymer with positive temperature coefficient of a kind of PCT characteristic, be used to make self-limiting heating cable.
Background technology
Positive temperature coefficient (PTC) conductive polymers, a kind of purposes is as self-limiting heating cable (cable) heating element, is mainly used in companion's heat of pipeline, valve and solar energy water heater pipes such as oil, chemical industry, heat power plant, ground heating, insulated cold wear, hand warmer heating, insulation.
PTC conductive polymer, because of the polymer kind with form differently, can form 65 ℃ of left and right sides low temperature modifications, about 105 ℃ middle warm types, greater than three temperature grade ptc materials of 110 ℃ of high temperature modifications.Warm PTC conductive polymer in the prior art, the relatively low Polyolefin and graphite of more employing price is base material, and the respective additive composition, a maximum deficiency is: the PCT character constancy is not ideal enough, repeats power on/off through long-time use and/or high reps, PTC stability is satisfied gradually decline, Curie temperature can take place than the large deviation change, and it is big to cause the PTC Curie-point temperature to disperse, and fluctuation range is at ± 10 ℃ usually, the temperature control instability is difficult to satisfy the hot temperature requirement of original design companion.
Chinese patent CN1135704 is disclosed from the polyethylene ptc material of limitting temperature at 110 ℃, consist of: high density polyethylene(HDPE) (HDPE) 60-80 part, graphitized carbon black or Shawinigan black 20-40 part, oxidation inhibitor, crosslinked through radiation crosslinking or the irradiation of rumbatron electron beam.Gained polyethylene ptc material, limitting temperature certainly is 110 ± 10 ℃.
The disclosed intelligent positive temperature coefficient self controlled heating cable of Chinese patent CN2525761, the automatic control heating element adopts by auxiliary agent mixing granulations such as polyvinylidene difluoride (PVDF) or polyethylene, conductive carbon black, lime carbonate, the positive temperature coefficient composite polymer material that obtains, report is not from the fluctuation of limit temperature.
The disclosed low temperature grade of Chinese patent CN1217353 (below 90 ℃), ptc characteristics stabilized resins composition, mainly by 10-70wt% linear low density polyethylene and adhesive resin, less than 10wt% vibrin or fluoro-resin, and 10-25wt% grafting or surface-treated acetylene carbon black composition, also can add fluoroelastomer and other processing aid.By the self controlled heating cable that said composition is made, the 6000hr that switches on continuously, temperature, power and resistance all do not have obvious downtrending, and 500 PTC stable performances of power on/off do not come from the warm fluctuation range of limit but give, and this PTC polymkeric substance belong to low temperature modification.
The disclosed heating temp of Chinese patent CN1699510 is 65 ℃ low temperature grade, a positive temperature coefficient fire-proof resin composition, linear low density polyethylene by 30～60% (LLDPE), 10～30% chlorinatedpolyethylene, 15～25% graphitized carbon black, 10～20% decabromodiphenyl oxide and ANTIMONY TRIOXIDE SB 203 99.8 PCT are also used fire retardant, and 5～10% processing aid composition, adopt electron irradiation crosslinked.The heating cables PTC intensity that this composition makes is more than 4, OI is greater than 26, room temperature resistivity is 102～105 Ω cm, energising is 6000 hours continuously, and power and resistance all do not have obvious downtrending, power on/off 500 times, ptc characteristics is stable, come from the warm fluctuation range of limit but give, this patent gained PTC is a low temperature modification equally, solution be fire-retardant problem.
The disclosed high temperature grade of Chinese patent CN1218067 (greater than 110 ℃) has the resin combination of ptc characteristics, mainly form, also can add a small amount of oildag, crosslinking sensitizer, fluoroelastomer processing aid and CaCO by 35～80wt% fluoro-resin, the extraordinary viton of 5～50wt%, 2～10wt% vibrin and 5～12wt% Shawinigan black
3, TiO
2Deng.The heating cables that said composition is made, power and temperature do not descend in the circulation of energising and power on/off continuously, and be safe in utilization, (OI is greater than 50 for the flame-retarding characteristic height, can put out certainly), not only equally give and come from the warm fluctuation range of limit, and base materials employed be the higher relatively fluoro-resin of price, viton.
Summary of the invention
The object of the invention is to overcome above-mentioned prior art deficiency, and the middle temperature polyolefin conductive polymer with positive temperature coefficient that a kind of ptc characteristics is stable, fluctuation is little, persistence is good is provided.
The object of the invention realizes that main the improvement is to adopt high-pressure polyethylene and polyisobutene composite base-material; And employing pentaerythritol tetrathioglycollate oxidation inhibitor, bis(pentaerythritolester) and clorafin softening agent, tribasic lead sulfate and calcium stearate one package stabilizer (K-1330), dicumyl peroxide (DCP) linking agent, thereby make warm polyolefin conductive polymer with positive temperature coefficient in the gained, have the ptc characteristics more stable than prior art.Specifically, warm polyolefin conductive polymer with positive temperature coefficient among the present invention, it is characterized in that forming and comprise: high pressure polyethylene resin 50-70 part, polyisobutene 20-40 part, conductive carbon black 20-30 part, tribasic lead sulfate 1-3 part, calcium stearate 1-3 part, bis(pentaerythritolester) 4-7 part, clorafin 2-5 part, pentaerythritol tetrathioglycollate 3-6 part, dicumyl peroxide 3-5 part.
Among the present invention
Polyolefin polymer adopts high pressure polyethylene resin and polyisobutene composite base-material, more helps the ptc characteristics stabilized presentation, and the PTC Curie temperature is concentrated stable more.
Pentaerythritol tetrathioglycollate oxidation inhibitor, heatproof oxidation performance can be excellent, and be difficult for decomposing, and good with the polyolefin base material intermiscibility, and it is stable also to help ptc characteristics.
Bis(pentaerythritolester) and clorafin softening agent: very approaching with polyolefine material dielectric coefficient ε and solubility exponent δ, intermiscibility is good, and it is stable also to help ptc characteristics; And itself and base-material and conductive carbon black flowability match, and can improve shaping characteristic.Wherein, the ratio of bis(pentaerythritolester) and clorafin weight, a kind of 2-2.5 that is preferably: 1-1.5.
Tribasic lead sulfate and calcium stearate stablizer: heat-resisting, photostabilization good, very easily mixes with polyolefine material, it is stable also to help ptc characteristics, and has good processing properties.Both mix and use better weight ratio to be 1.5-2.0: 1.5-2.0.
Dicumyl peroxide (DCP) linking agent, non-volatile, the thermotolerance height, chemical stability is good, can make that the PTC performance after crosslinked is more stable.
In addition, can also add normally used various functional agent among the present invention, realize corresponding function.For example UV light absorber is 1 part, lubricant 3-5 part, and 1 part of weighting agent, fire retardant or the like adds kind and has no special requirements, and can be normally used.
Warm polyolefin conductive polymer with positive temperature coefficient preparation among the present invention, to prepare PTC conductive polymer suitable with common chemically crosslinked, has no special requirements.
Warm polyolefin conductive polymer with positive temperature coefficient among the present invention, owing to adopt high pressure polyethylene resin and polyisobutene composite base-material, and the specific adjuvant acting in conjunction of selecting, make the gained polyolefin conductive polymer, PTC stability greatly improves, the ptc characteristics fluctuation is little, persistence is good, through power on/off repeatedly about 1000 times, the temperature control deviation has only ± 2-5 ℃ (temperature controlling range 105 ± 2-5 ℃), be significantly smaller than existing in warm polyolefin conductive polymer with positive temperature coefficient, temperature control deviation ± 10 ℃ great fluctuation process scope, PTC effect are obviously outstanding more, and energising or power on/off cycle P TC characteristic are very stable for a long time.Make self-limiting heating cable (self controlled heating cable) with this, have autocontrol temperature precision height, use the temperature control deviation little repeatedly, improved temperature-controlled precision greatly.
Below in conjunction with several embodiments, further specify the present invention.
Embodiment
Embodiment: press embodiment proportioning table,, fully stir mixed with the proportioning mixing of materials, under 100-130 ℃, carry out on the twin-screw extruder mixing, compression molding in 140-175 ℃ of extruding pelletization, gets PTC conductive polymer of the present invention through single screw extrusion machine.
This conductive polymers extruded extrude into the core band on conductor, crosslinked back extruded insulation layer, screen layer, squeeze jacket promptly get Curie point and are the middle temperature self-limiting heating cable about 105 ℃.
Embodiment proportioning table (weight part)
In addition, omit UV light absorber, lubricant, weighting agent, ptc characteristics is not had influence substantially.
Claims (4)
1. middle temperature polyolefin conductive polymer with positive temperature coefficient, it is characterized in that the weight composition comprises: high pressure polyethylene resin 50-70 part, polyisobutene 20-40 part, conductive carbon black 20-30 part, tribasic lead sulfate 1-3 part, calcium stearate 1-3 part, bis(pentaerythritolester) 4-7 part, clorafin 2-5 part, pentaerythritol tetrathioglycollate 3-6 part, dicumyl peroxide 3-5 part.
According to claim 1 described in warm polyolefin conductive polymer with positive temperature coefficient, it is characterized in that also being added with 1 part of UV light absorber, lubricant 3-5 part, 1 part of weighting agent.
According to claim 1 or 2 described in warm polyolefin conductive polymer with positive temperature coefficient, it is characterized in that tribasic lead sulfate and calcium stearate weight ratio are 1.5-2.0: 1.5-2.0.
According to claim 1 or 2 described in warm polyolefin conductive polymer with positive temperature coefficient, it is characterized in that the bis(pentaerythritolester) and the ratio of clorafin weight are 2-2.5: 1-1.5.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2007101905665A CN101205327B (en) | 2007-12-01 | 2007-12-01 | Polyolefin conductive polymer with middle-positive temperature coefficient |
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| CN2007101905665A CN101205327B (en) | 2007-12-01 | 2007-12-01 | Polyolefin conductive polymer with middle-positive temperature coefficient |
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| CN101205327A CN101205327A (en) | 2008-06-25 |
| CN101205327B true CN101205327B (en) | 2010-11-03 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101602870B (en) * | 2009-07-08 | 2011-10-19 | 江苏中兴电缆有限公司 | Soft cross-linked polyethylene insulating material |
| CN101885872B (en) * | 2010-07-27 | 2012-09-05 | 芜湖市旭辉电工新材料有限责任公司 | PTC high molecular heating material special for self-temperature limiting electric tracing band of 95 DEG C |
| CN103333400B (en) * | 2013-05-29 | 2016-05-04 | 安徽荣玖光纤通信科技有限公司 | A kind of LLDPE is PTC macromolecule conducting material of major ingredient and preparation method thereof |
| CN103554619A (en) * | 2013-10-31 | 2014-02-05 | 合肥得润电子器件有限公司 | Modified low-density polyethylene insulation material for automobile wire harness |
| CN103554615A (en) * | 2013-10-31 | 2014-02-05 | 合肥得润电子器件有限公司 | Weather-proof and damp-proof polyethylene insulating material for wire harnesses of communication equipment |
| CN104817753A (en) * | 2015-05-21 | 2015-08-05 | 广东威林工程塑料有限公司 | PE material for high-adsorbability PIB treating powder and preparation method of PE material |
| CN105482217A (en) * | 2015-12-04 | 2016-04-13 | 南京理工大学常熟研究院有限公司 | Preparation method of LDPE electromagnetic shielding material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6620343B1 (en) * | 2002-03-19 | 2003-09-16 | Therm-O-Disc Incorporated | PTC conductive composition containing a low molecular weight polyethylene processing aid |
| CN1704447A (en) * | 2004-05-26 | 2005-12-07 | 中国科学院金属研究所 | Conductive composite materials with positive temperature coefficient effect and process for making same |
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2007
- 2007-12-01 CN CN2007101905665A patent/CN101205327B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6620343B1 (en) * | 2002-03-19 | 2003-09-16 | Therm-O-Disc Incorporated | PTC conductive composition containing a low molecular weight polyethylene processing aid |
| CN1704447A (en) * | 2004-05-26 | 2005-12-07 | 中国科学院金属研究所 | Conductive composite materials with positive temperature coefficient effect and process for making same |
Non-Patent Citations (1)
| Title |
|---|
| JP特开平5-314814A 1993.11.26 |
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