CN1317325C - Method for promoting high-density polyethylene /carbon ink composite material positive temperature coefficient property - Google Patents
Method for promoting high-density polyethylene /carbon ink composite material positive temperature coefficient property Download PDFInfo
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- CN1317325C CN1317325C CNB2005100214105A CN200510021410A CN1317325C CN 1317325 C CN1317325 C CN 1317325C CN B2005100214105 A CNB2005100214105 A CN B2005100214105A CN 200510021410 A CN200510021410 A CN 200510021410A CN 1317325 C CN1317325 C CN 1317325C
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Abstract
The present invention discloses a method for improving the positive temperature coefficient (PTC) performance of high-density polyethylene (HDPE) /carbon black (CB) composite materials. High-density polyethylene powder is radiated in air at a room temperature, the radiation dosage rate is from 0.1 to 1 kg/h, and the dosage is from 5 to 30kg. The carbon black is oxidized for 10 to 120 minutes by ozone under the conditions of the temperature of 60 to 95 DEG C and the ozone concentration of 11 to 55 mg/L. 100 parts by weight of the radiated high-density polyethylene, 25 to 60 parts by weight of the ozone-treated carbon black, and 0.1 to 0.5 part by weight of composite anti-oxidant are added to a blender mill to be melted and mixed for 10 to 15 minutes at the temperature of 140 to 160 DEG C to obtain the HDPE/CB composite materials compressed and molded into sheet materials with the thickness of 2mm by a compression molding machine at the molding temperature of 175 to 185 DEG C and under the molding pressure of 10Mpa; when the surfaces of the produced sheet materials are heated to 140 to 160 DEG C, copper electrode sheets are pressed into the sheet materials.
Description
One. technical field
The present invention relates to the method for a kind of raising high density polyethylene(HDPE) (HDPE)/carbon black (CB) composite material positive temperature coefficient (PTC) performance, belong to polymer processing field.
Two. background technology
Since 1945; Frydman has found since the PTC phenomenon of material in the new LDPE (film grade) (LDPE) of having filled carbon black (CB); the ptc material that with the polymkeric substance is matrix is all obtaining very big development aspect theory research and the engineering utilisation technology, utilize overflow protecting element that ptc polymer makes, Automatic Control Temperature Heater part, temperature sensor etc. to be widely used in fields such as electronics, automobile, medical treatment, chemical industry, food.The prosperous electric wire of the rattan company of the Raychem company of the external existing many companies such as the U.S. and Japan etc. can the quality of production resettable fuse and from the temperature control heating tape preferably, domestic owing to theoretical investigation is started late, add that offshore company holds in close confidence material preparation process, so the scale that domestic industry is produced is less, the kind scarcity of product, and second-rate.
The greatest problem of ptc polymer is exactly a PTC effect less stable in thermal cycling process repeatedly at present, and is difficult to obtain simultaneously lower room temperature resistivity and high PTC intensity.The cross-linking radiation of material can address the above problem to a certain extent, but cost is higher, to having relatively high expectations of ambiance, and relatively poor for the crosslinked homogeneity of thick sample.US5164133, US4514620, CN1343560, CN1188779, CN1363629 etc. disclose the method for improving the high molecular PTC material property, make the PTC intensity of material and the stability of PTC effect that raising to a certain degree arranged, but the manufacturing process of these methods is all comparatively complicated, and the material PTC intensity that obtains is not very high.
Three. summary of the invention
The objective of the invention is to provide the method for a kind of raising high density polyethylene(HDPE) (HDPE)/carbon black (CB) composite material positive temperature coefficient property at the deficiencies in the prior art, by irradiation HDPE and oxidizing carbon black through ozone, make that HDPE and carbon black biphase interface interaction strengthen greatly in the matrix material, control the sooty agglomeration well, and improved the sooty dispersion.
Purpose of the present invention is realized that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
Improve the method for high-density polyethylene/carbon ink composite material positive temperature coefficient performance:
(1) the high density polyethylene(HDPE) powder is at room temperature carried out irradiation in the air, radiation dose rate is 0.1-1kGy/h, and dosage is 5-30kGy;
(2) with carbon black at temperature 60-95 ℃, under the concentration 11-55mg/L condition of ozone gas, ozone oxidation 10-120min;
(3) with the carbon black 25-60 weight part after 100 weight parts of the high density polyethylene(HDPE) behind the above-mentioned irradiation and the ozonize, composite antioxidant 0.1-0.5 weight part, add melting mixing in the mill, melting temperature is 140-160 ℃, mixing time is 10-15min, obtain the high-density polyethylene/carbon ink mixture, this mixture is moulded the 2mm sheet material with the vulcanizing press compression molding, molding temperature is 175-185 ℃, molding pressure is 10-15MPa, and the sheet surface that makes is pressed into the copper electrode sheet when being heated to 140-160 ℃.
Wherein, carbon black is an oil oven method graphitized carbon black, and particle diameter is 20-100nm, and the sooty iodine absorption value is 40-150g/kg, and sooty dibutyl phthalate (DBP) absorption value is 120-300cm
3/ 100g.
Composite antioxidant is that four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters (1010) and tricresyl phosphite (2, the 4-di-tert-butyl) ester (168) press 1: 4-4: 1 part by weight is composite.
The PTC test performance of material is shown in table 1 and Fig. 1,2, the result shows by γ-HDPE and o-CB compound ptc material when guaranteeing lower room temperature resistivity, has very high PTC intensity, can basically eliminate negative temperature coefficient (NTC) effect, the PTC stability in heating cycle repeatedly is fine.
High-density polyethylene/carbon ink composite material can be used to make overflow protecting element and from temperature control heating tape aspect.
The present invention has following advantage:
(1) by irradiation HDPE, oxidizing carbon black through ozone has significantly improved the interface combination of HDPE/CB biphase, can effectively suppress agglomeration and the position skew of carbon black in matrix, so can improve PTC intensity, eliminate the NTC effect, improve the stability of PTC effect in the thermal cycling repeatedly.
(2) technology is simple, environmentally safe, and cost is lower.
Four. description of drawings
The ptc characteristics curve of Fig. 1 irradiation HDPE and ozonize carbon black CB matrix material
The stability of the matrix material of Fig. 2 comparison example PTC effect in heating cycle
The stability of the matrix material of Fig. 3 embodiment 1 PTC effect in heating cycle
The stability of the matrix material of Fig. 4 embodiment 4 PTC effect in heating cycle
Five. specific implementation method
Below by embodiment the present invention is specifically described; be necessary to be pointed out that at this following examples only are used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to the content of the invention described above.
Embodiment 1: with the HDPE powder through the 1kGy/h dose rate, 5kGy dosage irradiation, obtain γ-HDPE, get γ-HDPE 100g then, CB 36g is untreated, antioxidant 1010 and oxidation inhibitor 168 is 0.3g altogether, join carry out in the mill mixing, melting temperature 150-160 ℃, mixing time is 10-15min, and the mixture of acquisition is moulded the 2mm thick sheet with the vulcanizing press compression molding, and molding temperature is 175-185 ℃, molding pressure is 10-15MPa, is pressed into the copper electrode sheet when again the sheet surface that makes being heated to 140-160 ℃.
Embodiment 2: with HDPE through the 0.1kGy/h dose rate, 10kGy dosage irradiation, obtain γ-HDPE, get γ-HDPE 100g then, CB 40g is untreated, antioxidant 1010 and oxidation inhibitor 168 altogether 0.5g join carry out in the mill mixing, melting temperature 150-160 ℃, mixing time is 10-15min, the mixture that obtains is moulded the 2mm thick sheet with the vulcanizing press compression molding, molding temperature is 175-185 ℃, and molding pressure is 10-15MPa, again with the sheet material table that makes and be pressed into the copper electrode sheet when being heated to 140-160 ℃.
Embodiment 3: with the HDPE powder through the 1kGy/h dose rate, 5kGy dosage irradiation, obtain γ-HDPE, carbon black is inserted in the ozone reactor at 60 ℃, handle 30min under the ozone concn 11mg/L condition, obtain o-CB, get γ-HDPE 100g then, o-CB 42g, antioxidant 1010 and oxidation inhibitor 168 is 0.5g altogether, join and carry out mixingly in the mill, melting temperature 150-160 ℃, mixing time is 10-15min, the mixture that obtains is moulded the 2mm thick sheet with the vulcanizing press compression molding, molding temperature is 175-185 ℃, and molding pressure is 10-15MPa, is pressed into the copper electrode sheet when again the sheet surface that makes being heated to 140-160 ℃.
Embodiment 4: with HDPE through the 0.1kGy/h dose rate, 10kGy dosage irradiation, obtain γ-HDPE, carbon black is inserted in the ozone reactor at 80 ℃, ozone concn 55mg/L handles 90min down, obtain o-CB, get γ-HDPE100g then, o-CB 49g, antioxidant 1010 and oxidation inhibitor 168 is 0.1g altogether, join and carry out mixingly in the mill, melting temperature 160-170 ℃, mixing time is 10-15min, the mixture that obtains is moulded the 2mm thick sheet with the vulcanizing press compression molding, molding temperature is 175-185 ℃, and molding pressure is 10-15MPa, is pressed into the copper electrode sheet when again the sheet surface that makes being heated to 140-160 ℃.
Embodiment 5: with HDPE through the 0.1kGy/h dose rate, 30kGy dosage irradiation, obtain γ-HDPE, carbon black is inserted in the ozone reactor at 95 ℃, ozone concn 33mg/L handles 90min down, obtain o-CB, get γ-HDPE100g then, o-CB 55g, antioxidant 1010 and oxidation inhibitor 168 is 0.5g altogether, join and carry out mixingly in the mill, melting temperature 160-170 ℃, mixing time is 10-15min, the mixture that obtains is moulded the 2mm thick sheet with the vulcanizing press compression molding, molding temperature is 175-185 ℃, and molding pressure is 10-15MPa, is pressed into the copper electrode sheet when again the sheet surface that makes being heated to 140-160 ℃.
Comparison example: incite somebody to action the not HDPE powder 100g of radiation treatment, untreated CB 30g, antioxidant 1010 and oxidation inhibitor 168 altogether 0.3g join carry out in the mill mixing, melting temperature 150-160 ℃, mixing time is 10-15min, and the mixture of acquisition is moulded the 2mm thick sheet with the vulcanizing press compression molding, and molding temperature is 175-185 ℃, molding pressure is 10-15MPa, is pressed into the copper electrode sheet when again the sheet surface that makes being heated to 140-160 ℃.
The ptc characteristics of table 1 irradiation HDPE and ozonize CB matrix material
| Matrix material | Room temperature resistivity ρ r (Ω cm) | 140 ℃ of electricalresistivity max (Ω cm) | PTC intensity lg (ρ max/ ρ r) | 150 ℃ of resistivity (Ω cm) |
| Comparison example embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 | 22.18 10.83 22.41 23.93 24.24 20.04 | 1.12×10 4 7.24×10 4 1.25×10 11 2.51×10 11 8.81×10 10 1.12×10 9 | 2.71 3.83 9.75 10.0 9.56 7.75 | 6.60×10 2 1.96×10 4 1.07×10 11 6.02×10 10 8.81×10 10 4.27×10 9 |
Claims (4)
1. improve the method for high-density polyethylene/carbon ink composite material positive temperature coefficient performance, it is characterized in that:
(1) the high density polyethylene(HDPE) powder is at room temperature carried out irradiation in the air, radiation dose rate is 0.1-1kGy/h, and dosage is 5-30kGy;
(2) with carbon black at temperature 60-95 ℃, under the concentration 11-55mg/L condition of ozone gas, ozone oxidation 10-120min;
(3) with the carbon black 25-60 weight part after 100 weight parts of the high density polyethylene(HDPE) behind the above-mentioned irradiation and the ozonize, composite antioxidant 0.1-0.5 weight part, add melting mixing in the mill, melting temperature is 140-160 ℃, mixing time is 10-15min, obtain the high-density polyethylene/carbon ink mixture, this mixture is moulded the 2mm sheet material with the vulcanizing press compression molding, molding temperature is 175-185 ℃, molding pressure is 10-15MPa, and the sheet surface that makes is pressed into the copper electrode sheet when being heated to 140-160 ℃;
Wherein, composite antioxidant is that four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and tricresyl phosphite (2, the 4-di-tert-butyl) ester press 1: 4-4: 1 part by weight is composite.
2. improve the method for high-density polyethylene/carbon ink composite material positive temperature coefficient performance according to claim 1, it is characterized in that carbon black is an oil oven method graphitized carbon black, particle diameter is 20-100nm, and the sooty iodine absorption value is 40-150g/kg, and the sooty dibutyl phthalate absorption is 120-300cm
3/ 100g.
3. the high-density polyethylene/carbon ink composite material for preparing of method according to claim 1.
4. as the purposes of high-density polyethylene/carbon ink composite material as described in the claim 3, it is characterized in that this matrix material can be used to make overflow protecting element and from temperature control heating tape aspect.
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| CNB2005100214105A CN1317325C (en) | 2005-08-04 | 2005-08-04 | Method for promoting high-density polyethylene /carbon ink composite material positive temperature coefficient property |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101357552B (en) * | 2007-07-30 | 2011-06-15 | 比亚迪股份有限公司 | Printing method for light solidifying coating surface |
| CN101638521B (en) * | 2008-07-30 | 2011-10-12 | 比亚迪股份有限公司 | Material with positive temperature coefficients |
| CN101697648B (en) * | 2009-11-05 | 2013-12-25 | 安徽安邦控制系统有限公司 | Self-regulating polymer heating tape |
| CN101697649B (en) * | 2009-11-05 | 2013-12-25 | 安徽安邦控制系统有限公司 | Explosion proof type macromolecular self-regulating heating tape |
| KR102597360B1 (en) * | 2016-12-12 | 2023-11-03 | 오씨아이 주식회사 | Manufactuing apparatus of carbon black and method of manufacturing the same |
| CN112111093A (en) * | 2020-09-23 | 2020-12-22 | 芜湖科阳新材料股份有限公司 | PTC conductive composite material for heat tracing band and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20050023133A (en) * | 2003-08-27 | 2005-03-09 | 한국화학연구원 | Conductive polymer composition containing ozone-treated carbon black and ptc device prepared therefrom |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20050023133A (en) * | 2003-08-27 | 2005-03-09 | 한국화학연구원 | Conductive polymer composition containing ozone-treated carbon black and ptc device prepared therefrom |
Non-Patent Citations (1)
| Title |
|---|
| 聚乙烯/炭黑导电复合材料PTC特性的研究(II) 何慧，塑料工业，第31卷第9期 2003 * |
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