CN104817695B - A kind of polyaniline composite conducting rubber powder and preparation method thereof - Google Patents
A kind of polyaniline composite conducting rubber powder and preparation method thereof Download PDFInfo
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- CN104817695B CN104817695B CN201510246266.9A CN201510246266A CN104817695B CN 104817695 B CN104817695 B CN 104817695B CN 201510246266 A CN201510246266 A CN 201510246266A CN 104817695 B CN104817695 B CN 104817695B
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Abstract
A kind of polyaniline composite conducting rubber powder is prepared by chemical graft reaction using waste-tyre rubber-powder, aniline and γ-aminopropyl triethoxysilane, can be prepared by following step:(1) vulcanized rubber powder pre-processes;(2) waste-tyre rubber-powder surface activation process;(3) aniline modification of graft.Present invention additionally comprises the preparation method of polyaniline composite conducting rubber powder.Raw material sources of the present invention are extensive, technological process is simple, production cost is relatively low, it is easy to industrialization, and junked tire recycling can be realized, expand rubber powder application, help solve waste tire " black pollution " problem, and new green utilization approach is provided for junked tire comprehensive utilization of resources;Composite granule prepared by the present invention has good electric conductivity, electromagnetic wave shielding etc., can be applied in the industrial circles such as electromagnetic wave shielding, anti-static coatings and product.
Description
Technical field
The present invention relates to a kind of composite conducting rubber powder and preparation method thereof, and in particular to a kind of polyaniline composite conducting rubber powder
Preparation method.
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 reaches 3.13 hundred million (being roughly equal to 9,600,000 tons), is leapt to the first in the world more than the U.S..The damaged tire of bulk deposition is not only
It is not easy to degenerate, and easily triggers fire, breed bacteria, mosquito;It is more next meanwhile junked tire is as the resource for misplacing position
More cause the attention of countries in the world.Since rubber powder development is turned into after junked tire crushes, pulverized rubber industry has flourished, generation
Table the developing direction that junked tire recycles, and has wide market prospects.But because pulverized rubber industry is in China's starting
Relatively, manufacturing enterprise is few, and enterprise disperses its production capacity deficiency, and waste-tyre rubber-powder mainly passes through mechanical-chemical modification, regeneration
Desulfurization is modified, grafting or interpenetrating polymer are modified, gas is modified, core-shell structure copolymer is modified, physics good fortune is penetrated and modified is applied to prepare rubber powder
Modified pavement asphalt or for producing reclaimed rubber, the application of these two aspects belongs to low value-added simple utilization;And waste and old
The fine of tire glue powder, Functionalization research and development etc. substantially lag with developed country, so as to limit rubber powder
Application, junked tire digestion amount are relatively low.Therefore, rubber powder fine, functionalization are realized, and then expands rubber powder application,
Seek the effective way of high-volume green digestion junked tire, it appears particularly urgent.
At present, conductive powder include carbon filler (graphite, carbon black, carbon fiber), metal packing (silver, nickel, copper, aluminium, zinc,
Tin, stainless steel etc.) and metallic compound (tin oxide, oxidation, iron sulfide etc.), the cladded type composite (cloud of tin oxide parcel
Mother, polymer surfaces deposited metal etc.) and antistatic additive etc..And composite conductive powder mainly utilizes metal or metal oxide etc.
Inorganic material powders or organic material are made by the precipitation method, solid phase method, sol-gel, alkoxide decomposition, microemulsion method, hydro-thermal method etc.
It is standby, the shortcomings of production cost is higher, process conditions are harsh, consumed resource is larger be present.Meanwhile also adopted not over to rubber powder
It is directly modified with chemistry, assign rubber powder new conductive sexual function, prepare the report of composite conducting rubber powder.
The content of the invention
The technical problem to be solved by the invention is to provide it is a kind of have good electric conductivity, electromagnet shield effect, it is low into
This polyaniline composite conducting rubber powder.
Further technical problem to be solved of the invention is to provide that a kind of production cost is low, technique is simple, makes full use of
Waste-tyre rubber-powder, the preparation method with good electric conductivity, the composite conducting rubber powder of electromagnet shield effect.
It is a kind of polyaniline composite conducting rubber powder that the present invention, which solves the technical scheme that its technical problem uses, can be by following
Step is prepared:(1) vulcanized rubber powder pre-processes;(2) using silicone couplet to vulcanized rubber powder activation process;(3) at 0~10 DEG C
Carry out aniline polymerization graft modification.
Further, the silicone couplet is γ-aminopropyl triethoxysilane, also referred to as 3- aminopropyl-triethoxies silicon
Alkane, chemical structural formula NH2CH2CH2CH2Si(OC2H5)3, such as trade name silicone couplet KH-560, using silicone couplet
KH-560 be tentatively modified, and reactive, hydrophilic group can be formed in vulcanized rubber powder.
The technical scheme that the present invention further solves the use of its technical problem is a kind of preparation side of composite conducting rubber powder
Method, comprise the following steps:
(1) vulcanized rubber powder pre-processes:30~50g is taken, the tire glue powder of 100~200 mesh is placed in 600~1000ml, quality
Concentration is in 8~12% alkali lye, stirs 5~10h of lower immersion treatment, filters, washs, dries;
(2) vulcanized rubber powder activation process:Rubber powder after step (1) surface preparation is placed in 400~600ml, methanol-water
Solution, wherein, the volume ratio of methanol and water is 5:1~10:1, and 30~40ml silane coupler is added dropwise, it is slowly stirred lower super
Sound disperses 20~30min;
(3) aniline polymerization graft modification:By activated hydrophilically modified rubber powder in step (2) be placed in 400~600ml,
Mass concentration is that 0.10~0.15mol aniline is added dropwise in 8~12% acid solution, continues 10~20min of supersound process, slowly
Dropwise addition 50ml, 0.1mol/L ammonium persulfate aqueous solution, 8~12h of stirring reaction at 0~10 DEG C, through filtering, washing, dry, i.e.,
Obtain polyaniline composite conducting rubber powder.
Further, in step (1), the alkali lye is sodium hydroxide solution.
Further, in step (3), the acid solution is hydrochloric acid solution.
The present invention is raw material from waste-tyre rubber-powder, and raw material sources are extensive, using polyaniline grafting modification, system
Standby composite conductive powder, technological process is simple, and production cost is relatively low, is easy to industrialization;And junked tire recycling can be realized
Utilize, expand rubber powder application, help solve waste tire " black pollution " problem, and be junked tire comprehensive resource
Using providing new green utilization approach;The present invention assigns rubber powder new performance, the modification of preparation by grafting modification
Composite conductive powder has good electric conductivity, electromagnet shield effect etc., can be applied to the works such as electromagnetic wave shielding, anti-static coatings
In industry field and product.It was verified that the electrical 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
The present invention is further illustrated with reference to embodiment.
Embodiment 1
(1) vulcanized rubber powder pre-processes:30g, the tire glue powder of 100 mesh is taken to be placed in the hydrogen-oxygen that 600ml mass concentrations are 10%
Change in sodium solution, stir lower immersion treatment 5h, filter, wash, dry;
(2) vulcanized rubber powder activation process:Rubber powder after step (1) surface preparation is placed in 400ml methanol-water solutions
(volume ratio of methanol and water is 8:1) in, and 30ml silane coupler is added, is slowly stirred lower ultrasonic disperse 20min.
(3) graft modification:Activated hydrophilically modified rubber powder in step (2) is placed in 500ml, mass concentration 10%
Acid solution in, 0.10mol aniline is added dropwise, continues after being ultrasonically treated 10min, 50ml, 0.1mol/L persulfuric acid is slowly added dropwise
Aqueous ammonium, the stirring reaction 8h at 0 DEG C, through filtering, washing, dry, produce polyaniline composite conducting rubber powder.
The electrical conductivity of polyaniline composite conducting rubber powder prepared by embodiment is 5.384S/cm after measured;In 30-1500MHz
Interior, its electromagnet shield effect is 75dB.
Embodiment 2
(1) vulcanized rubber powder pre-processes:50g, the tire glue powder of 200 mesh is taken to be placed in the hydrogen-oxygen that 1000ml mass concentrations are 10%
Change in sodium solution, stir lower immersion treatment 10h, filter, wash, dry;
(2) vulcanized rubber powder activation process:Rubber powder after step (1) surface preparation is placed in 500ml methanol-water solutions
(volume ratio of methanol and water is 8:1) in, and 40ml silane coupler is added, is slowly stirred lower ultrasonic disperse 30min.
(3) graft modification:Activated hydrophilically modified rubber powder in step (2) is placed in 500ml, mass concentration 10%
Acid solution in, 0.15mol aniline is added dropwise, continues after being ultrasonically treated 20min, 50ml, 0.1mol/L persulfuric acid is slowly added dropwise
Aqueous ammonium, the stirring reaction 12h at 10 DEG C, through filtering, washing, dry, produce polyaniline composite conducting rubber powder.
The electrical conductivity of polyaniline composite conducting rubber powder prepared by embodiment 2 is 5.657S/cm after measured;In 30-1500MHz
Interior, its electromagnet shield effect is 79dB.
Embodiment 3
(1) vulcanized rubber powder pre-processes:40g, the tire glue powder of 150 mesh is taken to be placed in the hydrogen-oxygen that 800ml mass concentrations are 10%
Change in sodium solution, stir lower immersion treatment 8h, filter, wash, dry;
(2) vulcanized rubber powder activation process:Rubber powder after step (1) surface preparation is placed in 500ml methanol-water solutions
(volume ratio of methanol and water is 8:1) in, and 35ml silane coupler is added, is slowly stirred lower ultrasonic disperse 25min.
(3) graft modification:Activated hydrophilically modified rubber powder in step (2) is placed in 500ml, mass concentration 10%
Acid solution in, 0.12mol aniline is added dropwise, continues after being ultrasonically treated 15min, 50ml, 0.1mol/L persulfuric acid is slowly added dropwise
Aqueous ammonium, stirring reaction 10h, through filtering, washing, dry, produces polyaniline composite conducting rubber powder at 5 DEG C.
The electrical conductivity of polyaniline composite conducting rubber powder prepared by embodiment 3 is 5.462S/cm after measured;In 30-1500MHz
Interior, its electromagnet shield effect is 76dB.
Claims (3)
1. a kind of preparation method of polyaniline composite conducting rubber powder, it is characterised in that comprise the following steps:
(1) vulcanized rubber powder pre-processes:30~50g, the tire glue powder of 100~200 mesh is taken to be placed in 600~1000ml, mass concentration
In 8~12% alkali lye, to stir 5~10h of lower immersion treatment, filter, wash, dry;
(2) vulcanized rubber powder activation process:It is molten that rubber powder after step (1) surface preparation is placed in 400~600ml, methanol-water
Liquid, wherein, the volume ratio of methanol and water is 5:1~10:1, and 30~40ml γ-aminopropyl triethoxysilane is added dropwise, delay
20~30min of the lower ultrasonic disperse of slow stirring;
(3) aniline polymerization graft modification:Activated hydrophilically modified rubber powder in step (2) is placed in 400~600ml, quality
Concentration is that 0.10~0.15mol aniline is added dropwise in 8~12% acid solution, continues 10~20min of supersound process, is slowly added dropwise
50ml, 0.1mol/L ammonium persulfate aqueous solution, 8~12h of stirring reaction at 0~10 DEG C, through filtering, washing, dry, produce poly-
Aniline composite conducting rubber powder.
2. the preparation method of polyaniline composite conducting rubber powder according to claim 1, it is characterised in that in step (1), institute
It is sodium hydroxide solution to state alkali lye.
3. the preparation method of polyaniline composite conducting rubber powder according to claim 1, it is characterised in that in step (3), institute
It is hydrochloric acid solution to state acid solution.
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CN100516134C (en) * | 2006-12-19 | 2009-07-22 | 江门市科恒实业股份有限公司 | Conductive plastic material and its preparation method and application |
CN102732155B (en) * | 2012-07-20 | 2013-11-27 | 浙江鲁班建筑防水有限公司 | 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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