CN1137185C - Preparation of Composite conducting rubber polymer material - Google Patents
Preparation of Composite conducting rubber polymer material Download PDFInfo
- Publication number
- CN1137185C CN1137185C CNB001191551A CN00119155A CN1137185C CN 1137185 C CN1137185 C CN 1137185C CN B001191551 A CNB001191551 A CN B001191551A CN 00119155 A CN00119155 A CN 00119155A CN 1137185 C CN1137185 C CN 1137185C
- Authority
- CN
- China
- Prior art keywords
- rubber
- preparation
- composite conducting
- conducting polymer
- polymer material
- 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.)
- Expired - Fee Related
Links
Abstract
The present invention belongs to a preparing technique of a polymer conducting composite material. The present invention improves the PTC performance and the mechanical performance of the conducting composite material through the combination of high-density polyethylene and an ethylene type copolymer and the selection of carbon black variety.
Description
The invention belongs to the technology of preparing of composite conducting rubber polymer material.
Conducing composite material of the present invention is distributed to conductive filler material and constitutes in the rubber polymer, and this mixture presents significant positive temperature coefficient (positive temperature coefficient, PTC) effect.The PTC effect is meant the phenomenon that the resistivity of material raises and increases with temperature.
The PTC effect is at first being found in adulterated barium titanate ceramics, and is being used widely.The PTC transformation of barium titanate ceramics occurs near the crystalline curie transition temperature (130 ℃).When replacing barium, its transition temperature is reduced with strontium; And when replacing barium, transition temperature is raise with lead.This makes the transition temperature (100～420 ℃) in very wide temperature range of ceramic ptc material regulate, and under ceramic ptc material long term high temperature environment and the electric Circulation, presents extraordinary stability.But effects limit such as its complete processing complexity, cost height, room temperature resistance height its application in some aspects.
On the contrary, ptc polymer, low just because of cost, be easy to processing, the advantage of aspect such as geomery is unrestricted and more and more coming into one's own, and from siding temperaturing heating belt, overcurrent protective device, aspects such as restrictor obtain to use.At present ptc polymer mainly is to be base-material with crystalline polymkeric substance, by obtaining with the conductive filler material blend, it is to occur near the polymer crystallization fusing point that its PTC changes, and this makes and wants to change the polymer base material that the PTC transition temperature must select to have different melting points.Yet be not that any crystalline polymer can both present significant PTC effect, in fact only find polyethylene at present, the relatively more suitable ptc material of doing of several polymkeric substance that polyvinylidene difluoride (PVDF) etc. are few in number.Therefore the adjustment of ptc polymer transition temperature exists some difficulties.
Conducing composite material of the present invention is to be the ptc material of polymeric matrix with amorphous or the very low rubber of degree of crystallinity.Carbon black mixture that it is generally acknowledged amorphous polymer does not have PTC effect or PTC effect very low, does not have practical value.The present invention utilizes high-energy ray irradiation, suppress or eliminated negative temperature coefficient (the negative temperaturecoefficient of rubber conducing composite material, NTC) effect, the PTC performance of amorphous electrically conductive composite is significantly improved, its PTC intensity (on resistivity-temperature curve, the ratio of peak resistance rate and room temperature resistivity) can be up to 10
7The order of magnitude.On the other hand, electrically conductive composite of the present invention, its PTC transition temperature be with the difference of conductive filler material kind and concentration, and the difference of absorption dose and changing, and the PTC transition temperature of mixture just can be regulated within the specific limits like this.Another characteristics are that its resistivity-temperature curve is gradual change rather than hop, makes it be better than the crystalline polymer ptc material as application facet such as temperature sensors.
The used rubber of the present invention is preferably the rubber clone that is easy to radiation crosslinking under the room temperature, as ethylene-propylene-diene monomer (EPDM), cis-1,4-polybutadiene rubber (BR), paracril (NBR), silicon rubber (SiR) etc., can be single variety rubber, also can be the blend of two or more rubber.
The used conductive filler material of the present invention can be carbon black, carbon fiber, metal or conductivity ceramics powder etc., wherein carbon black oven process carbon black preferably.
The proportioning of rubber and conductive filler material is (98～10) among the present invention: (2～90), preferably (85～35): (15～65).
The blend of rubber and conductive filler material can be adopted Banbury mixer among the present invention, also can adopt mill, or both is used in combination.Melting temperature is 100～200 ℃, and mixing time is 5～10 minutes, and mixing time begins to clock after all being added by conductive filler material.
High-energy ray irradiation of the present invention can be Co
60Gamma-radiation also can be a high energy electron ray, and irradiation is at room temperature in the vacuum or carry out in the air.Absorption dose depends on the needs, and increases absorption dose and can reduce the PTC transition temperature, makes resistivity-temperature curve steepening.Absorption dose is preferably lower than 5MGy.
(carbon black CB) is the CSF carbon black, particle diameter 50-70nm, specific surface area 230m to used carbon black in the embodiments of the invention
2/ g, the DBP value is 280m
2/ mg.Resistance test, high resistance area (＞10M Ω) adopt ZC36 type high resistant instrument, and low-resistance region (≤10M Ω) adopts digital multimeter.The PTC transition temperature is defined as the intersection point that resistance increases the extended line of the extended line of resistance-temperature curve in district and cold zone resistance-temperature curve fast.PTC intensity is with the electricalresistivity at peak value place
pWith room temperature resistivity ρ
rCompare value representation.
Embodiment 1
The blend 5 minutes in Banbury mixer of 150 ℃ of 35 gram EPDM rubber and 15 gram CSF carbon blacks is used the oil press compressing tablet, irradiation 0.15MGy in the air under the room temperature, the PTC transition temperature of mixture, 77 ℃, PTC intensity, 2 * 10 100 ℃ times
7
Embodiment 2-4
Implementation method is same as embodiment 1, changes material proportion in the mixture, and gained the results are shown in table 1.
Table 1
Embodiment E PDM CB transition temperature PTC intensity
(gram) (gram) (℃) (ρ
p/ ρ
r)
2 34 16 82 8×10
6
3 36 14 55 3×10
6
4 37 13 42 2 * 10
5Embodiment 5-8
Implementation method is same as embodiment 1, changes the gamma-radiation absorption dose, and gained the results are shown in table 2.
Table 2
Embodiment absorption dose transition temperature PTC intensity
(MGy) (℃) (ρ
p/ρ
r)
5 0.05 105 4×10
5
6 0.10 72 3×10
6
7 0.70 42 3×10
8
8 2.50 38 1 * 10
7Comparative example 1-5
Implementation method is same as embodiment 1, but does not carry out gamma-radiation irradiation, the results are shown in table 3.
Table 3
Comparative example EPDM CB room temperature resistivity PTC intensity
(gram) (gram) (Ω Lu m) (ρ
p/ ρ
r)
1 37 13 3E9 NTC
2 35 15 6E7 NTC
3 34 16 3E6 NTC
4 32 18 2E5 4
5 30 20 7E3 50
Embodiment 9
33 gram NBR rubber and 190 ℃ of blend in Banbury mixer of 17 gram carbon blacks are used the oil press compressing tablet down for 180 ℃, irradiation 0.15MGy in the air under the room temperature, and resulting mixture PTC transition temperature is 56 ℃, PTC intensity, 40.The comparative example 6
Implementation method is same as embodiment 9, but does not carry out gamma-radiation irradiation, and resulting mixture presents the NTC effect.
Claims (8)
1, a kind of preparation method of composite conducting rubber polymer material, it is characterized in that the elastomeric material that this material is filled by conductive filler material constitutes, Banbury mixer is adopted in the blend of material, or employing mill, or both are used in combination, melting temperature is 100～200 ℃, and mixing time is 5～10 minutes, obtains ptc material through high-energy ray irradiation afterwards.
2, the preparation method of composite conducting polymer material as claimed in claim 1 is characterized in that rubber is single variety rubber in terpolymer EP rubber or cis-1,4-polybutadiene rubber, paracril, the silicon rubber, or the blend of two or more rubber wherein.
3, the preparation method of composite conducting polymer material as claimed in claim 1 is characterized in that conductive filler material is carbon black or carbon fiber, metal, conductivity ceramics powder.
4, as the preparation method of claim 1 or 2 or 3 described composite conducting polymer materials, the weight proportion that it is characterized in that rubber and conductive filler material is 98～10: 2～90.
5, the preparation method of composite conducting polymer material as claimed in claim 4, the weight proportion that it is characterized in that rubber and conductive filler material is 85～35: 15～65.
6, the preparation method of composite conducting polymer material as claimed in claim 1 is characterized in that the high-energy ray irradiation process adopts Co
60Gamma-radiation or high energy electron ray.
7, the preparation method of composite conducting polymer material as claimed in claim 6, the irradiation that it is characterized in that conducing composite material at room temperature carries out in vacuum or the air.
8,, it is characterized in that irradiation dose is lower than 5MGy as the preparation method of claim 6 or 7 described composite conducting polymer materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001191551A CN1137185C (en) | 2000-06-23 | 2000-06-23 | Preparation of Composite conducting rubber polymer material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001191551A CN1137185C (en) | 2000-06-23 | 2000-06-23 | Preparation of Composite conducting rubber polymer material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1277221A CN1277221A (en) | 2000-12-20 |
| CN1137185C true CN1137185C (en) | 2004-02-04 |
Family
ID=4587527
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001191551A Expired - Fee Related CN1137185C (en) | 2000-06-23 | 2000-06-23 | Preparation of Composite conducting rubber polymer material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1137185C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8367986B2 (en) | 2006-10-17 | 2013-02-05 | Conflux Ab | Heating element |
| US10982082B1 (en) | 2020-08-17 | 2021-04-20 | King Abdulaziz University | Conductive nanocomposite having a dual temperature coefficient of resistance and a method of preparing |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103289416A (en) * | 2013-05-22 | 2013-09-11 | 吴江市德佐日用化学品有限公司 | Environment-friendly flame-retardant silicone rubber and butadiene rubber blending material |
| CN103588983B (en) * | 2013-11-28 | 2015-04-08 | 青岛科技大学 | Preparation method for flexible high-molecular PTC material |
| CN103709524A (en) * | 2013-12-16 | 2014-04-09 | 芜湖万润机械有限责任公司 | Antibacterial rubber apron |
| CN105199244B (en) * | 2015-10-10 | 2017-10-03 | 中国工程物理研究院核物理与化学研究所 | A kind of ternary ethlene propyene rubbercompound material and preparation method thereof |
| CN105670297A (en) * | 2016-01-28 | 2016-06-15 | 深圳市慧瑞电子材料有限公司 | Conductive rubber material for flexible sensors as well as preparation method and application of conductive rubber material |
-
2000
- 2000-06-23 CN CNB001191551A patent/CN1137185C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8367986B2 (en) | 2006-10-17 | 2013-02-05 | Conflux Ab | Heating element |
| CN101523975B (en) * | 2006-10-17 | 2013-11-06 | 整合公司 | Heating element |
| US10982082B1 (en) | 2020-08-17 | 2021-04-20 | King Abdulaziz University | Conductive nanocomposite having a dual temperature coefficient of resistance and a method of preparing |
| US11203684B1 (en) | 2020-08-17 | 2021-12-21 | King Abdulaziz University | Method for making an elastomeric conductive nanocomposite |
| US11214671B1 (en) | 2020-08-17 | 2022-01-04 | King Abdulaziz University | Elastomeric iron/graphene nanocomposite |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1277221A (en) | 2000-12-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7618550B2 (en) | Polymer compound with nonlinear current-voltage characteristic and process for producing a polymer compound | |
| US5705555A (en) | Conductive polymer compositions | |
| Zhang et al. | Percolation threshold and morphology of composites of conducting carbon black/polypropylene/EVA | |
| US5747147A (en) | Conductive polymer composition and device | |
| US4237441A (en) | Low resistivity PTC compositions | |
| US7651636B2 (en) | Nonlinear electrical material for high and medium voltage applications | |
| EP0197781B1 (en) | Melt-shapeable fluoropolymer compositions | |
| GB1561355A (en) | Voltage stable positive temperature coefficient of resistance compositions | |
| WO2001009905A2 (en) | Electrically conductive polymer composition | |
| CN1625785A (en) | PTC conductive composition containing a low molecular weight polyethylene processing aid | |
| CN1137185C (en) | Preparation of Composite conducting rubber polymer material | |
| EP0912631A1 (en) | Ptc conductive polymer compositions containing high molecular weight polymer materials | |
| CA1104808A (en) | Conductive polymer compositions | |
| Huang et al. | Effect of processing on the positive temperature coefficient of resistivity in lead metaplumbate/polyethylene composites | |
| US6114433A (en) | PTC conductive polymer composition | |
| JPH0416500B2 (en) | ||
| EP0371059A1 (en) | Conductive polymer composition | |
| JP2004522299A (en) | PTC conductive polymer composition | |
| CN1137184C (en) | Preparation of composite conducting polymer material | |
| KR0153409B1 (en) | Polymer composition having positive temperature coefficient characteristics | |
| JPS63146402A (en) | Positive resistance-temperature coefficient resistor | |
| JPH0737703A (en) | Positive temperature characteristic resin composition | |
| CA2067721C (en) | Conductive polymer compositions | |
| CN112210176A (en) | Polyvinylidene fluoride-based conductive composite material and PTC element | |
| Zhang et al. | Study on the positive and negative temperature coefficient effects of composite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |