CN1556137A - Preparation method of conductive polymer composite material possessing positive temperature coefficient characteristics - Google Patents
Preparation method of conductive polymer composite material possessing positive temperature coefficient characteristics Download PDFInfo
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- CN1556137A CN1556137A CNA2003101041852A CN200310104185A CN1556137A CN 1556137 A CN1556137 A CN 1556137A CN A2003101041852 A CNA2003101041852 A CN A2003101041852A CN 200310104185 A CN200310104185 A CN 200310104185A CN 1556137 A CN1556137 A CN 1556137A
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- carbon black
- conductive polymer
- polymer composite
- polyethylene
- temperature
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Abstract
An electrically conductive high-molecular composition with positive temp coefficient is prepared through treating the surface of carbon black by the epoxy modified aqueous emulsion of polyisoprene rubber, drying, high-temp plasticizing of polyethene, high-temp pugging of said carbon black and polyethene, and granulating. It has the improved electric property and toughness.
Description
One, technical field
The invention belongs to the manufacturing technology field of conductive polymer composite, be specifically related to a kind of preparation method with conductive polymer composite of positive temperature coefficient feature.
Two, background technology
Conductive polymer composite with positive temperature coefficient feature; present the heat-sensitive electric switch characteristic; can be used for making self-limiting heater temperature, over-current protecting element, little current switch and other temperature sensing device etc.; compare with the ceramic base PTC material; have the moulding of being easy to and processing continuously, flexible, in light weight, characteristics such as cost is low; in industries such as household electrical appliance, petrochemical complex, post and telecommunications, automotive industry, health care, agricultural herdings, application market is wide.
At present, the conductive polymer composite with positive temperature coefficient feature serves as main the acquisition to add conductive filler material all, as adding carbon black.Because black carbon surface contains a large amount of polarity oxy radicals, it disperses relatively poor in nonpolar macromolecular material such as polyethylene, makes the fragility of the conducing composite material that is obtained become big, mechanical property processibility variation, and electric property is also not satisfactory.In order to address these problems, people have carried out a large amount of research, as " Chinese plastics ", introduced in the polythene/carbon black system in 1999 13 (4), add macromolecular ethylene-vinyl acetate copolymer (EVA), can increase the toughness of conducing composite material, but make the positive temperature coefficient intensity of conducing composite material that certain decline be arranged.And for example " Journal of Applied Polymer Science " 1999 73 (489) etc. introduced the method for the conductive carbon black filler being carried out preparing after the chemical treatment positive-temperature-coefficient conductive polymer composite material.What this method was used is small molecules treatment agents such as nitric acid, titanic acid ester coupling molecule.The percolation threshold of the conducing composite material after the processing decreases, and electric property indexs such as positive temperature coefficient intensity make moderate progress, and when keeping the positive temperature coefficient intensity of material, can reduce the consumption of carbon black, but toughness can not improve.If reach then difficulty comparatively of purpose that mechanical properties such as the electric property that makes conducing composite material and toughness all have clear improvement, bring problems such as complicated operating process simultaneously.
Three, summary of the invention
The objective of the invention is to provide a kind of preparation method of conductive polymer composite newly with positive temperature coefficient feature at the deficiency of prior art.
Preparation method with conductive polymer composite of positive temperature coefficient feature provided by the invention, its technical process is black carbon surface processing → drying → poly high temperature plasticizing → polyethylene and carbon black high-temperature mixing → granulation, maybe with this pellet as masterbatch further with the polyethylene mixing granulator, it is characterized in that treatment agent that black carbon surface is handled for containing the epoxy modified aqueous emulsion of 20～40% polyisoprene rubbers, and the processing condition of each operation should be controlled to be:
(1) black carbon surface is handled the black carbon surface that at room temperature the epoxy modified aqueous emulsion spraying of polyisoprene rubber is distributed to high-speed stirring;
(2) dryly under 100 ℃ the temperature surface treated carbon black is dried to water content and is lower than 0.1% not being higher than;
(3) poly high temperature plasticizing is put into rubber and plastic Banbury mixer or two roller mill with polyethylene, under 145 ℃～220 ℃ of temperature, plastifies 3～5 minutes;
(4) high-temperature mixing of polyethylene and carbon black will be the surface-treated carbon black add in the high temperature plastifying polyethylene, 145 ℃～220 ℃ of temperature, mixing 5～15 minutes;
(5) after granulation is reduced to room temperature with the material that mixes, granulation can or with its as masterbatch further with the polyethylene mixing granulator.
Because the black carbon surface treatment agent that the present invention uses is the epoxy modified aqueous emulsion of polyisoprene rubber, and contains reactive both sexes macromole in this emulsion, and the nonpolar segment similar to polyethylene arranged, and is good with poly consistency; And having again to have than strong interaction with carbon black hydroxyl isopolarity group, chemically combined epoxy group(ing) can take place, thereby the carbon black after handling with the epoxy modified aqueous emulsion of polyisoprene rubber and the conductive polymer composite with positive temperature coefficient feature of the mixing acquisition of polyethylene, mechanical properties such as its electric property and toughness all have clear improvement simultaneously, and operating process is very simple.
The epoxy modified aqueous emulsion of used in the present invention polyisoprene rubber is in wherein contained dry rubber substance, with the ratio of carbon black be 2～20: 100, preferred 10～20: 100; The epoxidation level of the used epoxy modified aqueous emulsion of polyisoprene rubber is 15～50%; Surface treatment carbon black and poly mixing ratio are 15～40: 100.
The present invention has following advantage:
1, handle the conducing composite material that makes after the modification through the epoxy modified aqueous emulsion of polyisoprene rubber, its positive temperature coefficient intensity can improve about two orders of magnitude, and its toughness and modulus can improve respectively more than 20% and 15% simultaneously.
2, owing to having with consumption, the epoxy modified aqueous emulsion treatment agent of selecting for use of polyisoprene rubber increases, the characteristics that move to carbon black high filler loading capacity direction in the diafiltration zone of system, so just can control percolation threshold and the diafiltration zone that matrix material forms conductive network effectively by the consumption of the epoxy modified aqueous emulsion of control polyisoprene rubber according to the requirement of preparing product.
3, owing to also having with consumption, the epoxy modified aqueous emulsion treatment agent of selecting for use of polyisoprene rubber increases, the switch temperature of material, be the characteristics that resistance increases in a leap on the positive temperature coefficient curve temperature increases to some extent, thereby adjust the consumption of the epoxy modified aqueous emulsion of polyisoprene rubber, can also change the switch temperature of matrix material effectively.
4, handle black carbon surface with the epoxy modified aqueous emulsion of polyisoprene rubber, consumption is few, and operating process is easy, and dispersing and mixing is even.
5, the epoxy modified aqueous emulsion treatment agent of the polyisoprene rubber of selecting for use directly is taken from industrialization product, and raw material is easy to get, low price.
6, the epoxy modified aqueous emulsion treatment agent of the polyisoprene rubber of selecting for use is not because water-base emulsion produces pollution and destruction to operating process and environment.
Four, embodiment
Provide embodiment below so that the present invention is specifically described; be necessary to be pointed out that at this following examples can only be 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 of this area makes some nonessential improvement and adjusts according to the content of the invention described above and still belongs to protection scope of the present invention.
Embodiment 1
(1) processing of conductive carbon black at room temperature with the epoxy modified aqueous emulsion of polyisoprene rubber in wherein contained dry rubber substance, in the ratio with carbon black is 4: 100, and epoxidation level is the black carbon surface that the epoxy modified aqueous emulsion spraying of 50% polyisoprene rubber is distributed to high-speed stirring, after treating that its blending dispersion evenly, under 100 ℃ the temperature surface treated carbon black is dried to water content and is lower than 0.1% not being higher than;
(2) the conducing composite material preparation is put into the rubber and plastic Banbury mixer with polyethylene pellet, at rotating speed is 25～35 rev/mins, temperature is under 170 ℃, plastify after 4 minutes, weight ratio by polyethylene and conductive carbon black is 100: 15, will be the surface-treated carbon black add in the high temperature plastifying polyethylene, continued mixing 6 minutes; After taking-up is cooled to room temperature, make conductive polymer composite pellet with plastic breaker with positive temperature coefficient feature.The goods that the gained pellet is available compacting, extrude, the injecting method preparation has the conductive polymer composite of positive temperature coefficient effect.
Embodiment 2
(1) processing of conductive carbon black at room temperature with the epoxy modified aqueous emulsion of polyisoprene rubber in wherein contained dry rubber substance, in the ratio with carbon black is 20: 100, and epoxidation level is the black carbon surface that the epoxy modified aqueous emulsion spraying of 25% polyisoprene rubber is distributed to high-speed stirring, after treating that its blending dispersion evenly, under 100 ℃ the temperature surface treated carbon black is dried to water content and is lower than 0.1% not being higher than;
(2) the conducing composite material preparation is put into the rubber and plastic Banbury mixer with polyethylene pellet, at rotating speed is 25～35 rev/mins, temperature is under 220 ℃, plastify after 3 minutes, weight ratio by polyethylene and conductive carbon black is 100: 40, will be the surface-treated carbon black add in the high temperature plastifying polyethylene, continued mixing 10 minutes; After taking-up is cooled to room temperature, make conductive polymer composite pellet with plastic breaker with positive temperature coefficient feature.The goods that the gained pellet is available compacting, extrude, the injecting method preparation has the conductive polymer composite of positive temperature coefficient effect.
Embodiment 3
(1) processing of conductive carbon black at room temperature with the epoxy modified aqueous emulsion of polyisoprene rubber in wherein contained dry rubber substance, in the ratio with carbon black is 15: 100, and epoxidation level is the black carbon surface that the epoxy modified aqueous emulsion spraying of 15% polyisoprene rubber is distributed to high-speed stirring, after treating that its blending dispersion evenly, under 100 ℃ the temperature surface treated carbon black is dried to water content and is lower than 0.1% not being higher than;
(2) the conducing composite material preparation is put into the rubber and plastic Banbury mixer with polyethylene pellet, at rotating speed is 25～35 rev/mins, temperature is under 190 ℃, plastify after 3 minutes, weight ratio by polyethylene and conductive carbon black is 100: 30, will be the surface-treated carbon black add in the high temperature plastifying polyethylene, continued mixing 15 minutes; After taking-up is cooled to room temperature, make conductive polymer composite pellet with plastic breaker with positive temperature coefficient feature.The goods that the gained pellet is available compacting, extrude, the injecting method preparation has the conductive polymer composite of positive temperature coefficient effect.
Embodiment 4
(1) processing of conductive carbon black at room temperature with the epoxy modified aqueous emulsion of polyisoprene rubber in wherein contained dry rubber substance, in the ratio with carbon black is 10: 100, and epoxidation level is the black carbon surface that the epoxy modified aqueous emulsion spraying of 30% polyisoprene rubber is distributed to high-speed stirring, after treating that its blending dispersion evenly, under 100 ℃ the temperature surface treated carbon black is dried to water content and is lower than 0.1% not being higher than;
(2) polyethylene pellet is put into temperature is after roller is wrapped in plasticizing in two roller mills of 160 ℃ for conducing composite material preparation, weight ratio by polyethylene and conductive carbon black is 100: 20, will be the surface-treated carbon black add in the high temperature plastifying polyethylene, continued mixing 10 minutes; After taking-up is cooled to room temperature, make conductive polymer composite pellet with plastic breaker with positive temperature coefficient feature.The goods that the gained pellet is available compacting, extrude, the injecting method preparation has the conductive polymer composite of positive temperature coefficient effect.
Embodiment 5
(1) processing of conductive carbon black at room temperature with the epoxy modified aqueous emulsion of polyisoprene rubber in wherein contained dry rubber substance, in the ratio with carbon black is 15: 100, and epoxidation level is the black carbon surface that the epoxy modified aqueous emulsion spraying of 40% polyisoprene rubber is distributed to high-speed stirring, after treating that its blending dispersion evenly, under 100 ℃ the temperature surface treated carbon black is dried to water content and is lower than 0.1% not being higher than;
(2) the conducing composite material preparation is put into the rubber and plastic Banbury mixer with polyethylene pellet, at rotating speed is 25～35 rev/mins, temperature is under 180 ℃, plastify after 4 minutes, weight ratio by polyethylene and conductive carbon black is 100: 50, will be the surface-treated carbon black add in the high temperature plastifying polyethylene, continued mixing 8 minutes; After taking-up is cooled to room temperature, make masterbatch with plastic breaker.With this masterbatch and the pure material of polyethylene is that 1: 1 ratio is made into mixture by weight, is under 170～210 ℃ at plasticating temperature, extrudes bar with forcing machine after mixing, makes the pellet of the conductive polymer composite with positive temperature coefficient feature with dicing machine.The goods that the gained pellet is available compacting, extrude, the injecting method preparation has the conductive polymer composite of positive temperature coefficient effect.
Claims (6)
1, a kind of preparation method with conductive polymer composite of positive temperature coefficient feature, its technical process is black carbon surface processing → drying → poly high temperature plasticizing → polyethylene and carbon black high-temperature mixing → granulation, maybe with this pellet as masterbatch further with the polyethylene mixing granulator, it is characterized in that treatment agent that black carbon surface is handled for containing the epoxy modified aqueous emulsion of 20～40% polyisoprene rubbers, and the processing condition of each operation should be controlled to be:
(1) black carbon surface is handled the black carbon surface that at room temperature the epoxy modified aqueous emulsion spraying of polyisoprene rubber is distributed to high-speed stirring;
(2) dryly under 100 ℃ the temperature surface treated carbon black is dried to water content and is lower than 0.1% not being higher than;
(3) poly high temperature plasticizing is put into rubber and plastic Banbury mixer or two roller mill with polyethylene, under 145 ℃～220 ℃ of temperature, plastifies 3～5 minutes;
(4) high-temperature mixing of polyethylene and carbon black will be the surface-treated carbon black add in the high temperature plastifying polyethylene, 145 ℃～220 ℃ of temperature, mixing 5～15 minutes;
(5) after granulation is reduced to room temperature with the material that mixes, pelletizing can or with its as masterbatch further with the polyethylene mixing granulator.
2, the preparation method with conductive polymer composite of positive temperature coefficient feature according to claim 1, it is characterized in that the epoxy modified aqueous emulsion of used polyisoprene rubber in wherein contained dry rubber substance, with the weight ratio of carbon black be 2～20: 100.
3, the preparation method with conductive polymer composite of positive temperature coefficient feature according to claim 2, it is characterized in that the epoxy modified aqueous emulsion of used polyisoprene rubber in wherein contained dry rubber substance, with the weight ratio of carbon black be 10～20: 100.
4, according to claim 1 or 2 or 3 described preparation methods with conductive polymer composite of positive temperature coefficient feature, the epoxidation level that it is characterized in that the used epoxy modified aqueous emulsion of polyisoprene rubber is 15～50%.
5,, it is characterized in that surface treatment carbon black and poly mixing weight ratio are 1540: 100 according to claim 1 or 2 or 3 described preparation methods with conductive polymer composite of positive temperature coefficient feature.
6, the preparation method with conductive polymer composite of positive temperature coefficient feature according to claim 4 is characterized in that surface treatment carbon black and poly mixing weight ratio are 15～40: 100.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200310104185 CN1246376C (en) | 2003-12-31 | 2003-12-31 | Preparation method of conductive polymer composite material possessing positive temperature coefficient characteristics |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100381493C (en) * | 2006-05-19 | 2008-04-16 | 浙江大学 | Method for preparing conductive polymer composite material from metal granule modified carbon black |
| CN102061028A (en) * | 2010-12-13 | 2011-05-18 | 四川大学 | Preparation method of conductive polymer composite with low percolation value |
| CN105647017A (en) * | 2016-04-05 | 2016-06-08 | 四川大学 | Conducting polymer composite with continuous isolation structure and preparation method thereof |
| CN111253663A (en) * | 2020-03-12 | 2020-06-09 | 华南理工大学 | Self-temperature-control flexible polymer PTC material and preparation method thereof |
-
2003
- 2003-12-31 CN CN 200310104185 patent/CN1246376C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100381493C (en) * | 2006-05-19 | 2008-04-16 | 浙江大学 | Method for preparing conductive polymer composite material from metal granule modified carbon black |
| CN102061028A (en) * | 2010-12-13 | 2011-05-18 | 四川大学 | Preparation method of conductive polymer composite with low percolation value |
| CN105647017A (en) * | 2016-04-05 | 2016-06-08 | 四川大学 | Conducting polymer composite with continuous isolation structure and preparation method thereof |
| CN111253663A (en) * | 2020-03-12 | 2020-06-09 | 华南理工大学 | Self-temperature-control flexible polymer PTC material and preparation method thereof |
| CN111253663B (en) * | 2020-03-12 | 2022-04-22 | 华南理工大学 | Self-temperature-control flexible polymer PTC material and preparation method thereof |
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| CN1246376C (en) | 2006-03-22 |
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Granted publication date: 20060322 Termination date: 20111231 |