CN1277220A - Preparation of composite conducting polymer material - Google Patents
Preparation of composite conducting polymer material Download PDFInfo
- Publication number
- CN1277220A CN1277220A CN 00119153 CN00119153A CN1277220A CN 1277220 A CN1277220 A CN 1277220A CN 00119153 CN00119153 CN 00119153 CN 00119153 A CN00119153 A CN 00119153A CN 1277220 A CN1277220 A CN 1277220A
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- Prior art keywords
- composite material
- preparation
- conductive composite
- carbon black
- polymer
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Links
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 title claims description 30
- 239000002322 conducting polymer Substances 0.000 title description 4
- 229920001940 conductive polymer Polymers 0.000 title description 4
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 239000011231 conductive filler Substances 0.000 claims abstract description 14
- 239000006229 carbon black Substances 0.000 claims description 44
- 229920001903 high density polyethylene Polymers 0.000 claims description 28
- 239000004700 high-density polyethylene Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 16
- 229920002943 EPDM rubber Polymers 0.000 claims description 11
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 7
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 claims description 7
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 2
- 239000005977 Ethylene Substances 0.000 claims 2
- 231100000987 absorbed dose Toxicity 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 238000010894 electron beam technology Methods 0.000 claims 1
- 239000000835 fiber Substances 0.000 claims 1
- 238000007670 refining Methods 0.000 claims 1
- 238000004227 thermal cracking Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 13
- 239000000203 mixture Substances 0.000 abstract description 5
- 229920001971 elastomer Polymers 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract 1
- 230000005855 radiation Effects 0.000 abstract 1
- 230000007704 transition Effects 0.000 abstract 1
- 235000019241 carbon black Nutrition 0.000 description 38
- 239000011159 matrix material Substances 0.000 description 8
- 229940063583 high-density polyethylene Drugs 0.000 description 6
- 229920001038 ethylene copolymer Polymers 0.000 description 5
- 239000005042 ethylene-ethyl acrylate Substances 0.000 description 5
- 241000872198 Serjania polyphylla Species 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Conductive Materials (AREA)
- Fuel Cell (AREA)
Abstract
本发明属于橡胶类聚合物导电复合材料的制备技术。本发明是将导电填料填充到非晶或结晶度很低的橡胶构成中,通过辐射交联,消除了原有的负温度系数效应,使之呈现出显著的PTC效应,并且其PTC转变温度可根据需要通过配比和加工条件调整。The invention belongs to the preparation technology of rubber polymer conductive composite material. The present invention fills the conductive filler into the amorphous or very low crystallinity rubber composition, eliminates the original negative temperature coefficient effect through radiation crosslinking, and makes it present a significant PTC effect, and its PTC transition temperature can be adjusted. Adjust the ratio and processing conditions as needed.
Description
The invention belongs to a kind of technology of preparing of composite conducting polymer material.
Composite conducting polymer material of the present invention has significant positive temperature coefficient effect.(positivetemperature coefficient, PTC) effect is meant the phenomenon that the resistivity of material raises and increases with temperature to positive temperature coefficient.As everyone knows, most polymers (as polyethylene, polypropylene etc.) is good isolator in its pure state.After sneaking into conductive filler material, especially after the concentration of conductive filler material surpassed a certain threshold value (being called the seepage flow threshold value), its resistivity significantly descended, and formed conduction or semiconduction matrix material.Some composite conducting material when the concentration of conductive filler material is near its threshold value, raises with temperature, and the hop of several magnitude can take place its resistivity, presents significant PTC effect.
In ptc polymer, polymer base material with the most use be high density polyethylene(HDPE) (high densitypolyethylene, HDPE), conductive filler material is the most frequently used be carbon black (carbon black, CB).At present, the ptc material that is made of high density polyethylene(HDPE) and carbon black exists the problem of two aspects: (1) is because polyethylene is the low surface energy material, poor with the interfacial interaction of carbon black, usually the required conductive filler material loading level of ptc material is bigger in addition, make the polythene/carbon black mixture exist poor mechanical property, carbon black is difficult for weakness such as dispersion.(2) when it uses as thermistors such as overcurrent protective devices, its room temperature resistivity remains further to be reduced.
The present invention adopts the base-material of the blend of high density polyethylene(HDPE) and other ethylene copolymer as ptc material, because ethylene copolymer is better than high density polyethylene(HDPE) to the affinity of carbon black, can strengthen the interfacial interaction of polymeric matrix and carbon black, improve the dispersion of carbon black in matrix, the PTC performance and the mechanical property of material are improved.
On the other hand, the present invention adopts low structure carbon black to replace high structure carbon black as conductive filler material, and not only cost reduces, and the ptc material room temperature resistance that obtains is low, PTC intensity height.The generation of carbon black-filled polymer composites PTC effect is commonly considered as because temperature when raising, polymeric matrix molecular motion aggravation causes the depolymerization of carbon black agglomerate, and conductive channel destroys and produces.And the agglomeration again of carbon black recovers conductive channel, and resistivity reduces, and the generation negative temperature coefficient (negativetemperature coefficient, NTC) effect, thus offset the part positive temperature coefficient effect, make the PTC strength degradation.Low structure carbon black, the agglomeration ability, the NTC effect is little, so adopt low structure carbon black to replace high structure carbon black as conductive filler material, helps improving PTC intensity.On the other hand, the agglomeration ability makes the carbon black-filled polymer composites of low structure more approaching between the carbon black agglomerate, under the littler condition in gap, depolymerization still can take place produce the PTC effect, the little then resistivity in gap is corresponding less, so room temperature resistivity is lower.
The used ethylene copolymer of the present invention can be terpolymer EP rubber (EPDM) or ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA) etc.The proportioning of high density polyethylene(HDPE) and ethylene copolymer can be (95～5): (5～95), preferably (75～50): (25～50).
The used conductive filler material of the present invention can be a carbon black, carbon fiber, and metal or conductivity ceramics powder etc., wherein carbon black is preferably the oven process carbon black.The DBP value of carbon black is less than 300cm
3/ 100g is preferably less than 120cm
3/ 100g.
The proportioning of polymer base material and conductive filler material is (98～20) among the present invention: (2～80), preferably (85～40): (15～60).The blend of material can be adopted Banbury mixer, also can adopt mill, or both is used in combination.Melting temperature is 100～200 ℃, and mixing time is 5～10 minutes.After at first HDPE and ethylene copolymer being mixed, again with the carbon black blend.
The effect of high-energy ray irradiation is to suppress the NTC effect among the present invention, increases PTC effect intensity and stability.The high-energy ray irradiation that is adopted 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 scope 10～500KGy, preferably 50～300KGy.
Resistance test among the embodiment, high resistance area (＞10M Ω) adopt ZC36 type high resistant instrument, and low-resistance region (≤10M Ω) adopts digital multimeter.PTC intensity is used the electricalresistivity at resistivity and temperature relation curve upward peak place
pWith room temperature resistivity ρ
rThe ratio value representation.The structural parameter of used carbon black are listed in table 1.
The structural parameter of table 1 carbon black
Embodiment 1
| ??BP2000?????XC-72????CSF????FEF | |
| Particle diameter (nm) surface-area (m 2/ g) DBP value (cm 3/ 100g) volatility (%) | ????15?????????30?????50-70?40-48 ????1475???????254????230???41-50 ????330????????178????280???95-115 ????2.0????????1.5????1.0???- |
HDPE 30.75 grams, EPDM 10.25 grams behind 150 ℃ of following premixs, add 9 gram CSF carbon blacks in Banbury mixer, continued mixing 5 minutes, use 5 fens kinds of mill mixing again, use oil press at 140-150 ℃ of compressing tablet afterwards.Irradiation at room temperature carries out in the air, and absorption dose is 150KGy.The elongation at break 31.5% of resulting matrix material, tensile strength 27.4MPa.Embodiment 2
Implementation method is identical with embodiment 1, changes EPDM into the EVA of identical weight, the elongation at break 17.5%. tensile strength 27.1MPa of resulting matrix material.Embodiment 3
Implementation method is identical with embodiment 1, changes EPDM into the EEA of identical weight, the elongation at break 18.8%. tensile strength 26.0MPa of resulting matrix material.The comparative example 1
Implementation method is identical with embodiment 1, and the HDPE with EPDM changes identical weight into promptly uses HDPE to be base-material separately.The elongation at break 7.2% of resulting matrix material, tensile strength 34.5MPa.Embodiment 4-8
Implementation method is identical with embodiment 1, changes each set of dispense ratio, the results are shown in table 2.
Table 2
Embodiment HDPE (%) EPDM (%) CB (%) PTC intensity (ρ
p/ ρ
r)
4????????56.0????????28.0?????????16???????????3×10
6
5????????54.7????????27.3?????????18???????????3×10
9
6????????53.3????????26.7?????????20???????????3×10
9
7????????52.0????????26.0?????????22???????????2×10
8
8 50.7 25.3 24 3 * 10
5Comparative example 2-6
Implementation method is identical with embodiment 1, uses HDPE to be base-material separately, the results are shown in table 3.
Table 3
Comparative example HDPE (%) CB (%) PTC intensity (ρ
p/ ρ
r)
2??????????85.5?????????14.5???????????1×10
3
3??????????85.0?????????15.0???????????2×10
9
4??????????84.0?????????16.0???????????3×10
8
5??????????82.0?????????18.0???????????1×10
4
6 80.0 20.0 1 * 10
4Embodiment 9-13
Implementation method is identical with embodiment 1, with FEF carbon black replaced C SF carbon black, and changes proportioning, and the result is as shown in table 4.
Table 4
Embodiment HDPE EPDM CB room temperature resistivity PTC intensity
(％)????(％)????(％)????(Ω·cm)???(ρ
p/ρ
r)
9???????56.3????18.7?????25?????2×10
7?????2×10
7
10??????52.5????17.5?????30?????2×10
4?????2×10
9
11??????48.7????16.3?????35?????2×10
3?????5×10
9
12??????45.0????15.0?????40?????2×10
3?????4×10
8
13 41.3 13.7 45 1 * 10
32 * 10
4Comparative example 7-13
Implementation method is same as embodiment 9-13, replaces the FEF carbon black with BP2000 carbon black and XC-72 carbon black respectively, the results are shown in table 5.
Table 5 embodiment HDPE EPDM BP2000 XC-72 room temperature resistivity PTC intensity
(％)????(％)?????(％)?????(％)?????(Ω·cm)????(ρ
p/ρ
r)
7?????????71.3????23.7??????5?????????????????3×10
13???????-
8?????????69.0????23.0??????8?????????????????2×10
8??????1×10
6
9?????????67.5????22.5??????10????????????????5×10
6??????2×10
3
10????????63.7????21.3??????15????????????????1×10
5??????1×10
2
11????????63.7????21.3??????????????15????????3×10
9??????3×10
5
12????????61.5????20.5??????????????18????????1×10
6??????2×10
8
13 60.0 20.0 20 2 * 10
45 * 10
2Embodiment 14-17
Implementation method replaces EPDM with sub-embodiment 9-13 with EEA, and changes proportioning, the results are shown in table 6.
Table 6 embodiment HDPE EEA CB room temperature resistivity PTC intensity
(％)???(％)???(％)????(Ω·cm)?????(ρ
p/ρ
r)
14??????56.3???18.7????25?????3×10
3???????2×10
10
15??????52.5???17.5????30?????1×10
3???????3×10
10
16??????48.7???16.3????35?????6×10
2???????3×10
6
17 45.0 15.0 40 2 * 10
23 * 10
4Comparative example 14-19
Implementation method is same as embodiment 14-17, replaces the FEF carbon black with BP2000 carbon black and XC-72 carbon black respectively, the results are shown in table 7.
Table 7 embodiment HDPE EEA BP2000 XC-72 room temperature resistivity PTC intensity
(％)????(％)????(％)??????(％)?????(Ω·cm)?????(ρ
p/ρ
r)
14??????69.0????23.0?????8??????????????????1×10
7??????2×10
2
15??????67.5????22.5?????10?????????????????1×10
6???????40
16??????63.7????21.3?????15?????????????????5×10
5???????4
17??????63.7????21.3??????????????15????????2×10
6??????6×10
7
18??????61.5????20.5??????????????18????????8×10
4??????6×10
3
19 58.5 19.5 22 1 * 10
45 * 10
2Embodiment 18-22
Implementation method is same as embodiment 9-13, replaces EPDM with EVA, and changes proportioning, the results are shown in table 8.
Table 8
Embodiment HDPE EVA FEF room temperature resistivity PTC intensity
(％)????(％)???(％)????(Ω·cm)????(ρ
p/ρ
r)
18??????56.3????18.7????25??????8×10
3?????3×10
10
19??????52.5????17.5????30??????8×10
2?????4×10
10
20??????48.7????16.3????35??????4×10
2?????3×10
10
21??????45.0????15.0????40??????3×10
2?????2×10
6
22 41.3 13.7 45 2 * 10
21 * 10
4Comparative example 20-26
Implementation method is same as embodiment 18-22, replaces the FEF carbon black with BP2000 carbon black and XC-72 carbon black respectively, the results are shown in table 9.
Table 9 embodiment HDPE EVA BP2000 XC-72 room temperature resistivity PTC intensity
(％)????(％)????(％)?????(％)?????(Ω·cm)????(ρ
p/ρ
r)
20??????70.5????23.5?????6?????????????????4×10
13???????4
21??????69.0????23.0?????8?????????????????4×10
6??????1×10
2
22??????67.5????22.5?????10????????????????2×10
6????????8
23??????63.7????21.3?????15????????????????2×10
5????????5
24??????63.7????21.3?????????????15????????1×10
6??????8×10
7
25??????61.5????20.5?????????????18????????4×10
4??????6×10
4
26??????58.5????19.5?????????????22????????3×10
4??????6×10
2
Claims (14)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001191535A CN1137184C (en) | 2000-06-23 | 2000-06-23 | Preparation of composite conducting polymer material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001191535A CN1137184C (en) | 2000-06-23 | 2000-06-23 | Preparation of composite conducting polymer material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1277220A true CN1277220A (en) | 2000-12-20 |
| CN1137184C CN1137184C (en) | 2004-02-04 |
Family
ID=4587525
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001191535A Expired - Fee Related CN1137184C (en) | 2000-06-23 | 2000-06-23 | Preparation of composite conducting polymer material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1137184C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100343925C (en) * | 2002-03-19 | 2007-10-17 | 热力蒂思科有限公司 | PTC conductive composition containing a low molecular weight polyethylene processing aid |
| CN101928422A (en) * | 2010-04-26 | 2010-12-29 | 大连理工大学 | Preparation method of a polymer-based conductive heating composite film material |
| CN102751530A (en) * | 2011-06-02 | 2012-10-24 | 张潘毅 | High capacity lithium ion battery containing metal conductive substances |
| CN104861273A (en) * | 2015-06-11 | 2015-08-26 | 郑州轻工业学院 | Composite material for thermistor and preparation method and application of composite material |
| CN105017608A (en) * | 2015-06-25 | 2015-11-04 | 广东顺德鲁华光电新材料实业有限公司 | Conductive polymer material and preparation method thereof |
| EP3545035A1 (en) * | 2016-11-23 | 2019-10-02 | Union Carbide Chemicals & Plastics Technology LLC | Multiphase conductive polymer composite compositions |
| CN116462899A (en) * | 2023-04-26 | 2023-07-21 | 芜湖佳宏新材料股份有限公司 | A kind of low resistance PPTC material and preparation method |
-
2000
- 2000-06-23 CN CNB001191535A patent/CN1137184C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100343925C (en) * | 2002-03-19 | 2007-10-17 | 热力蒂思科有限公司 | PTC conductive composition containing a low molecular weight polyethylene processing aid |
| CN101928422A (en) * | 2010-04-26 | 2010-12-29 | 大连理工大学 | Preparation method of a polymer-based conductive heating composite film material |
| CN102751530A (en) * | 2011-06-02 | 2012-10-24 | 张潘毅 | High capacity lithium ion battery containing metal conductive substances |
| CN102751530B (en) * | 2011-06-02 | 2014-12-03 | 张潘毅 | High capacity lithium ion battery containing metal conductive substances |
| CN104861273A (en) * | 2015-06-11 | 2015-08-26 | 郑州轻工业学院 | Composite material for thermistor and preparation method and application of composite material |
| CN104861273B (en) * | 2015-06-11 | 2016-05-25 | 郑州轻工业学院 | Be used for composite of thermistor and its preparation method and application |
| CN105017608A (en) * | 2015-06-25 | 2015-11-04 | 广东顺德鲁华光电新材料实业有限公司 | Conductive polymer material and preparation method thereof |
| EP3545035A1 (en) * | 2016-11-23 | 2019-10-02 | Union Carbide Chemicals & Plastics Technology LLC | Multiphase conductive polymer composite compositions |
| EP3545035B1 (en) * | 2016-11-23 | 2025-06-25 | Union Carbide Corporation | Multiphase conductive polymer composite compositions |
| CN116462899A (en) * | 2023-04-26 | 2023-07-21 | 芜湖佳宏新材料股份有限公司 | A kind of low resistance PPTC material and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1137184C (en) | 2004-02-04 |
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