CN1730530A - Method for improving high-density polyethylene /carbon ink composite material positive temperature coefficient property - Google Patents
Method for improving high-density polyethylene /carbon ink composite material positive temperature coefficient property Download PDFInfo
- Publication number
- CN1730530A CN1730530A CN 200510021411 CN200510021411A CN1730530A CN 1730530 A CN1730530 A CN 1730530A CN 200510021411 CN200510021411 CN 200510021411 CN 200510021411 A CN200510021411 A CN 200510021411A CN 1730530 A CN1730530 A CN 1730530A
- Authority
- CN
- China
- Prior art keywords
- density polyethylene
- carbon ink
- composite material
- carbon black
- hdpe
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a method for improving high-density polyethylene /carbon ink composite material positive temperature coefficient property, which comprises, (1) charging high density polyethylene 100 parts, carbon black 35-65 parts, polycaproamide 25-50 parts, maleic anhydride grafted polythene 0-45 parts, composite anti-oxidant 0.2-0.8 part into a rubber mill for milling, obtaining high-density polyethylene / carbon black composite, (2) molding the mixture into sheet material, heating the surface of the sheet material to 220 deg C, pressing into copper electrode sheets.
Description
One. technical field
The present invention relates to a kind of method of improving 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 provides a kind of method of improving high density polyethylene(HDPE) (HDPE)/carbon black (CB) composite material positive temperature coefficient (PTC) performance at the deficiencies in the prior art, in the blend of HDPE and CB, add the HDPE (MAH-HDPE) of polycaprolactam (PA6) and maleic anhydride graft, the matrix material that makes has less room temperature resistivity, the very high PTC intensity and the stability of PTC effect preferably, and do not have negative temperature coefficient (NTC) effect.
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, it is characterized in that this composite-material formula component is:
100 parts of high density polyethylene(HDPE)s
Carbon black 35-65 part
Polycaprolactam 25-55 part
Maleic anhydride grafted polyethylene 0-45 part
Composite antioxidant 0.2-0.8 part
This matrix material prepares as follows:
(1) with 100 parts of high density polyethylene(HDPE), carbon black 35-65 part, polycaprolactam 25-50 part, maleic anhydride grafted polyethylene 0-45 part, composite antioxidant 0.2-0.8 part adds in the mill mixing, melting temperature is 225-245 ℃, and mixing time is 10-15min, obtains the high-density polyethylene/carbon ink mixture.
(2) above-mentioned mixture is moulded the 2mm thick sheet to the mixture compression molding with vulcanizing press, molding temperature is 230-240 ℃, and molding pressure is 10-15MPa, is pressed into the copper electrode sheet when sheet surface that makes is heated to 220 ℃.
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 the sooty dibutyl phthalate absorption is 120-300cm
3/ 100g.Composite antioxidant be 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) in 1: 4-4: 1 ratio is composite.
The PTC test performance of material is shown in table 1 and Fig. 1,2, the result shows that the HDPE/CB matrix material that adds PA6 and MAH-HDPE is when guaranteeing lower room temperature resistivity, have very high PTC intensity, can eliminate the NTC effect, the PTC stability in thermal cycling repeatedly is also fine.
The present invention has following advantage:
(1) by the PA6 that adds to the solid phase stabilization of HDPE/CB mixture and MAH-HDPE interface constraint effect to the HDPE/CB mixture, suppressed agglomeration and the position skew of carbon black in matrix effectively, can improve PTC intensity, eliminate the NTC effect, improve repeatedly the stability of PTC effect in the heating cycle.
(2) technology is simple, environmentally safe, and cost is lower.
Four. description of drawings
Fig. 1 HDPE/CB, HDPE/PA6/CB and HDPE/MAH-HDPE/PA6/CB matrix material ptc characteristics curve comparison diagram
Fig. 2 does not add the stability of PTC effect in the matrix material heating cycle of PA6 and MAH-HDPE.
Fig. 3 adds the stability of PTC effect in the matrix material heating cycle of PA6 and MAH-HDPE.
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 high density polyethylene(HDPE) 100g, carbon black 40g, polycaprolactam 25g, antioxidant 1010 and oxidation inhibitor 168 is 0.3g altogether, join carry out in the mill mixing, melting temperature 225-235 ℃, mixing time is 10min, and the mixture of acquisition is moulded the 2mm thick sheet with the vulcanizing press compression molding, and molding temperature is 230-240 ℃, molding pressure is 10-15MPa, is pressed into the copper electrode sheet when again the sheet surface that makes being heated to 230 ℃.
Embodiment 2: with high density polyethylene(HDPE) 100g, carbon black 45g, polycaprolactam 43g, antioxidant 1010 and oxidation inhibitor 168 is 0.8g altogether, join carry out in the mill mixing, melting temperature 225-235 ℃, mixing time is 10min, and the mixture of acquisition is moulded the 2mm thick sheet with the vulcanizing press compression molding, and molding temperature is 230-240 ℃, molding pressure is 10-15MPa, is pressed into the copper electrode sheet when again the sheet surface that makes being heated to 230 ℃.
Embodiment 3: with high density polyethylene(HDPE) 100g, and carbon black 65g, polycaprolactam 53g, maleic anhydride grafted polyethylene 25g, antioxidant 1010 and oxidation inhibitor 168 is 0.2g altogether, join to carry out mixingly in the mill, and melting temperature 235-245 ℃, mixing time is 10min.The mixture that obtains is moulded the 2mm thick sheet with the vulcanizing press compression molding, and molding temperature is 230-240 ℃, and molding pressure is 10-15MPa, is pressed into the copper electrode sheet when again the sheet surface that makes being heated to 230 ℃.
Embodiment 4: with high density polyethylene(HDPE) 100g, and carbon black 65g, polycaprolactam 35g, maleic anhydride grafted polyethylene 43g, antioxidant 1010 and oxidation inhibitor 168 is 0.5g altogether, join to carry out mixingly in the mill, and melting temperature 225-235 ℃, mixing time is 10min.The mixture that obtains is moulded the 2mm thick sheet with the vulcanizing press compression molding, and molding temperature is 230-240 ℃, and molding pressure is 10-15MPa, is pressed into the copper electrode sheet when again the sheet surface that makes being heated to 230 ℃.
Comparison example: with high density polyethylene(HDPE) 100g, carbon black 28g, antioxidant 1010 and oxidation inhibitor 168 is 0.5g altogether, join mill and carry out mixingly, and melting temperature 225-235 ℃, mixing time is 10min.The mixture that obtains is moulded the 2mm thick sheet with the vulcanizing press compression molding, and molding temperature is 230-240 ℃, and molding pressure is 10-15MPa, is pressed into the copper electrode sheet when again the sheet surface that makes being heated to 230 ℃.
Table 1 adds the ptc characteristics of the HDPE/CB matrix material of PA6 and MAH-HDPE
| 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 | 68.39 42.36 44.13 33.50 29.99 | 1.12×10 6 1.80×10 9 9.75×10 8 2.63×10 10 1.18×10 11 | 4.21 7.63 7.34 8.89 9.59 | 9.91×10 2 4.18×10 8 5.36×10 8 2.20×10 10 1.80×10 11 |
Claims (5)
1. method of improving the high-density polyethylene/carbon ink composite material positive temperature coefficient performance is characterized in that this composite-material formula component is by weight:
100 parts of high density polyethylene(HDPE)s
Carbon black 35-65 part
Polycaprolactam 25-55 part
Maleic anhydride grafted polyethylene 0-45 part
Composite antioxidant 0.2-0.8 part
This matrix material prepares as follows:
(1) with 100 parts of high density polyethylene(HDPE), carbon black 35-65 part, polycaprolactam 25-50 part, maleic anhydride grafted polyethylene 0-45 part, composite antioxidant 0.2-0.8 part adds in the mill mixing, melting temperature is 225-245 ℃, and mixing time is 10-15min, obtains the high-density polyethylene/carbon ink mixture.
(2) above-mentioned mixture is moulded the 2mm thick sheet to the mixture compression molding with vulcanizing press, molding temperature is 230-240 ℃, and molding pressure is 10-15MPa, is pressed into the copper electrode sheet when sheet surface that makes is heated to 220 ℃.
2. the method for improving the high-density polyethylene/carbon ink composite material positive temperature coefficient performance as claimed in 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 method for improving the high-density polyethylene/carbon ink composite material positive temperature coefficient performance as claimed in claim 1, it is characterized in that composite antioxidant is four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and tricresyl phosphite (2, the 4-di-tert-butyl) ester be in 1: 4-4: 1 ratio is composite.
4. the high-density polyethylene/carbon ink composite material for preparing of method according to claim 1.
5. as the purposes of high-density polyethylene/carbon ink composite material as described in the claim 4, it is characterized in that this matrix material can be used to make overflow protecting element and from temperature control heating tape aspect.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510021411XA CN100484991C (en) | 2005-08-04 | 2005-08-04 | Method for improving high-density polyethylene /carbon ink composite material positive temperature coefficient property |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510021411XA CN100484991C (en) | 2005-08-04 | 2005-08-04 | Method for improving high-density polyethylene /carbon ink composite material positive temperature coefficient property |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1730530A true CN1730530A (en) | 2006-02-08 |
| CN100484991C CN100484991C (en) | 2009-05-06 |
Family
ID=35962954
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200510021411XA Expired - Fee Related CN100484991C (en) | 2005-08-04 | 2005-08-04 | Method for improving high-density polyethylene /carbon ink composite material positive temperature coefficient property |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100484991C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102598162A (en) * | 2009-10-30 | 2012-07-18 | 沙伯基础创新塑料知识产权有限公司 | Positive temperature coefficient materials with reduced negative temperature coefficient effect |
| CN103319765A (en) * | 2012-03-22 | 2013-09-25 | 金发科技股份有限公司 | Conductive barrier polyethylene composition, its preparation method and application |
| CN107141778A (en) * | 2017-05-08 | 2017-09-08 | 句容市博远电子有限公司 | A kind of semistor and preparation method thereof |
-
2005
- 2005-08-04 CN CNB200510021411XA patent/CN100484991C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102598162A (en) * | 2009-10-30 | 2012-07-18 | 沙伯基础创新塑料知识产权有限公司 | Positive temperature coefficient materials with reduced negative temperature coefficient effect |
| CN103319765A (en) * | 2012-03-22 | 2013-09-25 | 金发科技股份有限公司 | Conductive barrier polyethylene composition, its preparation method and application |
| CN103319765B (en) * | 2012-03-22 | 2015-12-16 | 金发科技股份有限公司 | A kind of conduction, barrier polyethylene composition and its preparation method and application |
| CN107141778A (en) * | 2017-05-08 | 2017-09-08 | 句容市博远电子有限公司 | A kind of semistor and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100484991C (en) | 2009-05-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107459642B (en) | High-content graphene modified nylon 6 master batch and preparation method and application thereof | |
| CN101754599B (en) | Application of injection molding wood plastic composite in producing electric appliance housing | |
| CN104861297B (en) | A kind of hexagonal boron nitride/polypropylene polymer composite and preparation method | |
| CN1317325C (en) | Method for promoting high-density polyethylene /carbon ink composite material positive temperature coefficient property | |
| CN103862589B (en) | A kind of melt blending prepares the method for polyamide-based heat-conductive composite material | |
| CN106633338B (en) | A kind of conductive polymer material and preparation method thereof | |
| CN102604358A (en) | Thermal-conductive antistatic PC/ABS (polycarbonate/acrylonitrile butadiene styrene) material and preparation method thereof | |
| CN109096572A (en) | A kind of olefin polymerization nanometer composite insulating material and preparation method thereof of high dc breakdown intensity | |
| CN106633303B (en) | The nano combined crosslinked polyethylene insulation material and preparation method thereof of high dc breakdown field strength | |
| CN107523049B (en) | Graphene polymer composite heat-conducting plastic and preparation method thereof | |
| CN103804743A (en) | Low-resistance PTC (positive temperature coefficient) composite material | |
| CN1730530A (en) | Method for improving high-density polyethylene /carbon ink composite material positive temperature coefficient property | |
| CN109575528A (en) | Low dielectric high tenacity enhancing PBT/PPO composition and preparation method thereof | |
| CN113736167A (en) | Weather-resistant silane crosslinked polyethylene overhead insulating material and preparation method thereof | |
| CN105034186B (en) | The preparation method of photovoltaic cable jacket layer material | |
| CN1704447A (en) | Conductive composite materials with positive temperature coefficient effect and process for making same | |
| CN1528817A (en) | Polyolefin/carbon black PTC conductive composite material and preparing method thereof | |
| CN108997718B (en) | High-thermal-conductivity halogen-free flame-retardant TPEE elastomer composition | |
| CN1263801C (en) | Process for preparing electrically conductive high-molecular composite material by in-situ graft to modify electrically conductive filler | |
| CN112521675B (en) | Insulating cold-resistant cable material and preparation method and application thereof | |
| CN106589766A (en) | PA-ABS alloy and preparation method of same | |
| CN108192207A (en) | A kind of high-performance conductive PP composite material and preparation method | |
| CN112724666B (en) | graphene/PA 10T nanocomposite and preparation method thereof | |
| CN112898700A (en) | Heat-resistant environment-friendly cable insulation material and preparation method thereof | |
| CN1068357C (en) | Positive temp coefficient high molecular material compsns. and prepn. process thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090506 Termination date: 20120804 |