CN104817695A - Polyaniline composite conductive adhesive powder and preparation method thereof - Google Patents
Polyaniline composite conductive adhesive powder and preparation method thereof Download PDFInfo
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- CN104817695A CN104817695A CN201510246266.9A CN201510246266A CN104817695A CN 104817695 A CN104817695 A CN 104817695A CN 201510246266 A CN201510246266 A CN 201510246266A CN 104817695 A CN104817695 A CN 104817695A
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Abstract
The invention relates to a polyaniline composite conductive adhesive powder and a preparation method thereof. The preparation method comprises the following steps: (1) carrying out surface pretreatment on the rubber powder; (2) carrying out surface activation treatment on the rubber powder by using a silicon coupling agent; and (3) carrying out aniline polymerization graft modification. The invention also relates to the preparation method of the polyaniline composite conductive adhesive powder. The preparation method has the advantages of wide raw material sources, simple technical process and lower production cost, can easily implement industrialization, can recycle junked tires, widens the application range of the rubber powder, is beneficial to solving the problem of the black pollution caused by the junked tires, and provides a new green utilization way for comprehensive utilization and recycling of junked tires. The composite powder has the advantages of favorable conductivity, favorable electromagnetic shielding property and the like, and is applicable to the fields of electromagnetic wave shielding products, antistatic paints and the like.
Description
Technical field
The present invention relates to a kind of composite conducting rubber powder and preparation method thereof, be specifically related to a kind of preparation method of polyaniline composite conducting rubber powder.
Background technology
In recent years, the contradiction between the continuous sharp increase of China's damaged tire and the scarcity of rubber sources is increasingly sharpened.2014, China's damaged tire reached 3.13 hundred million (being roughly equal to 9,600,000 tons), exceedes the U.S. and leaps to the first in the world.The damaged tire of bulk deposition is not only not easily degenerated, and easy initiation fire, breed bacteria, mosquito; Meanwhile, junked tire, as the resource misplacing position, more and more causes the attention of countries in the world.Since becoming rubber powder development after junked tire is pulverized, pulverized rubber industry is flourish, represents the developing direction of junked tire recycle, has wide market outlook.But because pulverized rubber industry is relative in China's starting, manufacturing enterprise is few, enterprise disperses its production capacity not enough, waste-tyre rubber-powder is penetrated modified being applied to mainly through mechanical-chemical modification, regenerative sulfur binding modification, grafting or interpenetrating polymer modification, gas modification, core-shell structure copolymer modification, physics good fortune and is prepared rubber powder modified road bitumen or for the production of reclaimed rubber, the application of these two aspects all belongs to low value-added simple utilization; And obviously delayed with developed country in the super-refinement, Functionalization research and development etc. of waste-tyre rubber-powder, thus limit the range of application of rubber powder, junked tire digestion amount is lower.Therefore, realize rubber powder super-refinement, functionalization, and then expand rubber powder range of application, seek the effective way of green digestion junked tire in enormous quantities, seem particularly urgent.
At present, conductive powder comprises carbon filler (graphite, carbon black, carbon fiber), metallic stuffing (silver, nickel, copper, aluminium, zinc, tin, stainless steel etc.) and metallic compound (stannic oxide, oxidation, iron sulphide etc.), cladded type matrix material (mica, polymer surfaces metal refining etc. of stannic oxide parcel) and static inhibitor etc.And composite conductive powder mainly utilizes the inorganic material powders such as metal or metal oxide or organic materials by preparations such as the precipitator method, solid phase method, so-gel, alkoxide decomposition, microemulsion method, hydrothermal methods, there is the shortcomings such as production cost is higher, processing condition are harsh, consumed resource is larger.Meanwhile, also not by adopting chemistry directly modified modified to rubber powder, giving the electroconductibility function that rubber powder is new, preparing the report of composite conducting rubber powder.
Summary of the invention
Technical problem to be solved by this invention is, provides a kind of polyaniline composite conducting rubber powder with good electroconductibility, electromagnet shield effect, low cost.
The further technical problem to be solved of the present invention is, provides that a kind of production cost is low, technique is simple, make full use of waste-tyre rubber-powder, have good electroconductibility, the preparation method of the composite conducting rubber powder of electromagnet shield effect.
The technical scheme that the present invention solves the employing of its technical problem is that a kind of polyaniline composite conducting rubber powder, can be prepared by following step: (1) vulcanized rubber powder pre-treatment; (2) adopt silicone couplet to vulcanized rubber powder activation treatment; (3) aniline polymerization graft modification is carried out at 0 ~ 10 DEG C.
Further, described silicone couplet is γ-aminopropyl triethoxysilane, and also referred to as 3-aminopropyl triethoxysilane, chemical structural formula is NH
2cH
2cH
2cH
2si (OC
2h
5)
3, such as commodity are called silicone couplet KH-560, adopt silicone couplet KH-560 to carry out preliminary modification, can form reactive, hydrophilic group at vulcanized rubber powder.
The technical scheme that the present invention solves the employing of its technical problem is further that a kind of preparation method of composite conducting rubber powder, comprises the following steps:
(1) vulcanized rubber powder pre-treatment: get 30 ~ 50g, 100 ~ 200 object tire glue powders are placed in 600 ~ 1000ml, mass concentration is the alkali lye of 8 ~ 12%, stir lower immersion treatment 5 ~ 10h, suction filtration, washing, drying;
(2) vulcanized rubber powder activation treatment: the rubber powder after step (1) surface preparation is placed in 400 ~ 600ml, methanol-water solution, wherein, the volume ratio of methyl alcohol and water is 5: 1 ~ 10: 1, and drip the silane coupling agent of 30 ~ 40ml, slowly stir lower ultrasonic disperse 20 ~ 30min;
(3) aniline polymerization graft modification: hydrophilically modified rubber powder activated in step (2) is placed in 400 ~ 600ml, mass concentration is the acid solution of 8 ~ 12%, drip the aniline of 0.10 ~ 0.15mol, continue supersound process 10 ~ 20min, slow dropping 50ml, 0.1mol/L ammonium persulfate aqueous solution, stirring reaction 8 ~ 12h at 0 ~ 10 DEG C, through suction filtration, washing, drying, obtain polyaniline composite conducting rubber powder.
Further, in step (1), described alkali lye is sodium hydroxide solution.
Further, in step (2), described acid solution is hydrochloric acid soln.
The present invention selects waste-tyre rubber-powder to be raw material, and raw material sources is extensive, adopts polyaniline grafting modification, prepares composite conductive powder, and technical process is simple, and production cost is lower, is easy to industrialization; And junked tire recycling can be realized, expand rubber powder range of application, contribute to solving waste tire " black pollution " problem, and provide new green utilization approach for junked tire comprehensive utilization of resources; The present invention is by grafting modification, and give the performance that rubber powder is new, the modification composite conductive powder of preparation has good electroconductibility, electromagnet shield effect etc., can be applicable in the industrial circle such as electromagnetic wave shielding, Antistatic Paint and product.Facts have proved, the specific conductivity of the polyaniline composite conducting rubber powder of the present invention is 5.384 ~ 5.657S/cm; In 30-1500MHz, its electromagnet shield effect is 75 ~ 79dB.
Embodiment
Below in conjunction with embodiment, the present invention is illustrated further.
Embodiment 1
(1) vulcanized rubber powder pre-treatment: get 30g, 100 object tire glue powders are placed in the sodium hydroxide solution that 600ml mass concentration is 10%, stirs lower immersion treatment 5h, suction filtration, washing, drying;
(2) vulcanized rubber powder activation treatment: the rubber powder after step (1) surface preparation is placed in 400ml methanol-water solution (volume ratio of methyl alcohol and water is 8: 1), and add the silane coupling agent of 30ml, slowly stir lower ultrasonic disperse 20min.
(3) graft modification: hydrophilically modified rubber powder activated in step (2) is placed in 500ml, mass concentration is the acid solution of 10%, drip the aniline of 0.10mol, after continuing supersound process 10min, the slow ammonium persulfate aqueous solution dripping 50ml, 0.1mol/L, stirring reaction 8h at 0 DEG C, through suction filtration, washing, drying, obtain polyaniline composite conducting rubber powder.
The specific conductivity of polyaniline composite conducting rubber powder that after measured prepared by embodiment is 5.384S/cm; In 30-1500MHz, its electromagnet shield effect is 75dB.
Embodiment 2
(1) vulcanized rubber powder pre-treatment: get 50g, 200 object tire glue powders are placed in the sodium hydroxide solution that 1000ml mass concentration is 10%, stirs lower immersion treatment 10h, suction filtration, washing, drying;
(2) vulcanized rubber powder activation treatment: the rubber powder after step (1) surface preparation is placed in 500ml methanol-water solution (volume ratio of methyl alcohol and water is 8: 1), and add the silane coupling agent of 40ml, slowly stir lower ultrasonic disperse 30min.
(3) graft modification: hydrophilically modified rubber powder activated in step (2) is placed in 500ml, mass concentration is the acid solution of 10%, drip the aniline of 0.15mol, after continuing supersound process 20min, the slow ammonium persulfate aqueous solution dripping 50ml, 0.1mol/L, stirring reaction 12h at 10 DEG C, through suction filtration, washing, drying, obtain polyaniline composite conducting rubber powder.
The specific conductivity of the polyaniline composite conducting rubber powder of embodiment 2 preparation is 5.657S/cm after measured; In 30-1500MHz, its electromagnet shield effect is 79dB.
Embodiment 3
(1) vulcanized rubber powder pre-treatment: get 40g, 150 object tire glue powders are placed in the sodium hydroxide solution that 800ml mass concentration is 10%, stirs lower immersion treatment 8h, suction filtration, washing, drying;
(2) vulcanized rubber powder activation treatment: the rubber powder after step (1) surface preparation is placed in 500ml methanol-water solution (volume ratio of methyl alcohol and water is 8: 1), and add the silane coupling agent of 35ml, slowly stir lower ultrasonic disperse 25min.
(3) graft modification: hydrophilically modified rubber powder activated in step (2) is placed in 500ml, mass concentration is the acid solution of 10%, drip the aniline of 0.12mol, after continuing supersound process 15min, the slow ammonium persulfate aqueous solution dripping 50ml, 0.1mol/L, stirring reaction 10h at 5 DEG C, through suction filtration, washing, drying, obtain polyaniline composite conducting rubber powder.
The specific conductivity of the polyaniline composite conducting rubber powder of embodiment 3 preparation is 5.462S/cm after measured; In 30-1500MHz, its electromagnet shield effect is 76dB.
Claims (5)
1. a polyaniline composite conducting rubber powder, is characterized in that, can be prepared by following step: (1) vulcanized rubber powder pre-treatment; (2) adopt silicone couplet to vulcanized rubber powder activation treatment; (3) aniline polymerization graft modification is carried out at 0 ~ 10 DEG C.
2. polyaniline composite conducting rubber powder according to claim 1, is characterized in that, described silicone couplet is γ-aminopropyl triethoxysilane.
3. a preparation method for polyaniline composite conducting rubber powder as claimed in claim 1 or 2, is characterized in that, comprise the following steps:
(1) vulcanized rubber powder pre-treatment: get 30 ~ 50g, 100 ~ 200 object tire glue powders are placed in 600 ~ 1000ml, mass concentration is the alkali lye of 8 ~ 12%, stir lower immersion treatment 5 ~ 10h, suction filtration, washing, drying;
(2) vulcanized rubber powder activation treatment: the rubber powder after step (1) surface preparation is placed in 400 ~ 600ml, methanol-water solution, wherein, the volume ratio of methyl alcohol and water is 5: 1 ~ 10: 1, and drip the silane coupling agent of 30 ~ 40ml, slowly stir lower ultrasonic disperse 20 ~ 30min;
(3) aniline polymerization graft modification: hydrophilically modified rubber powder activated in step (2) is placed in 400 ~ 600ml, mass concentration is the acid solution of 8 ~ 12%, drip the aniline of 0.10 ~ 0.15mol, continue supersound process 10 ~ 20min, slow dropping 50ml, 0.1mol/L ammonium persulfate aqueous solution, stirring reaction 8 ~ 12h at 0 ~ 10 DEG C, through suction filtration, washing, drying, obtain polyaniline composite conducting rubber powder.
4. the preparation method of polyaniline composite conducting rubber powder according to claim 3, is characterized in that, in step (1), described alkali lye is sodium hydroxide solution.
5. the preparation method of the polyaniline composite conducting rubber powder according to claim 3 or 4, is characterized in that, in step (2), described acid solution is hydrochloric acid soln.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1995128A (en) * | 2006-12-19 | 2007-07-11 | 江门市科恒实业有限责任公司 | Conductive plastic material and its preparation method and application |
CN102732155A (en) * | 2012-07-20 | 2012-10-17 | 项晓睿 | Macromolecule waterproof coating capable of being subjected to microwave heating and preparation method thereof |
CN103951975A (en) * | 2014-04-23 | 2014-07-30 | 苏州羽帆新材料科技有限公司 | Polyaniline-containing electrically conductive plastic |
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1995128A (en) * | 2006-12-19 | 2007-07-11 | 江门市科恒实业有限责任公司 | Conductive plastic material and its preparation method and application |
CN102732155A (en) * | 2012-07-20 | 2012-10-17 | 项晓睿 | Macromolecule waterproof coating capable of being subjected to microwave heating and preparation method thereof |
CN103951975A (en) * | 2014-04-23 | 2014-07-30 | 苏州羽帆新材料科技有限公司 | Polyaniline-containing electrically conductive plastic |
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