CN110498921A - A kind of preparation method of the PS@PANI conductive material drawn based on electrostatic self-absorbing - Google Patents
A kind of preparation method of the PS@PANI conductive material drawn based on electrostatic self-absorbing Download PDFInfo
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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Abstract
The invention discloses a kind of preparation methods of PS@PANI conductive material drawn based on electrostatic self-absorbing, the following steps are included: (1) takes sodium hydroxide solution and styrene to stir, mixed liquor is poured into separatory funnel, lower layer's light red liquid is released, colourless upper solution includes styrene solution；(2) styrene solution, deionized water and acrylic acid derivative are mixed, continues to stir under nitrogen protection, Ammonium Persulfate 98.5 solution is added after reaching 70~75 DEG C, is cleaned by ultrasonic after centrifugation, drying is obtained with acetate functional group PS microsphere powder；(3) will be with acetate functional group PS microsphere powder ultrasonic disperse in deionized water, then acid aniline solution is added dropwise, it is stirred at -3~3 DEG C；(4) press ammonium persulfate: ammonium persulfate solution is added in aniline monomer molar ratio 1.2: 1, and the reaction was continued, and eccentric cleaning drying obtains PS@PANI conductive micro-balloons.Present invention eliminates the processes for needing to carry out PS microballoon sulfonation in existing PS@PANI preparation method, avoid brought security risk in sulfuric acid use process.
Description
Technical field
The present invention relates to conducing composite material preparation method, specially a kind of PS@PANI drawn based on electrostatic self-absorbing is conductive
The preparation method of material.
Background technique
Conducing composite material is an extremely active field of current research, wherein being substrate in its surface aggregate using microballoon
The conducing composite material that conductive materials are prepared can not only substantially reduce conductivity threshold, moreover it is possible to keep good electric conductivity.
Polystyrene (PS) microballoon is due to the advantages that its particle diameter distribution is uniform, controllability is strong, mature preparation process, in the system of conductive micro-balloons
It is widely used in standby and application, such as PS@PANI microballoon, PS@rGO microballoon, PS@/MWCNTs and PS@Ag microballoon
Deng wherein synthesizing simple, at low cost and good conductivity for the relatively other conductive materials of polyaniline (PANI), PS@PANI is conductive
The application of method for preparing microsphere probed into for it in conducing composite material, which has, actively promotes effect.But at present with PS
Microballoon is more single for the PS PANI conductive material method of matrix preparation, wherein mostly important step is exactly PS microballoon sulfonation,
The step need to be added the concentrated sulfuric acid simultaneously to operate it is more demanding, this also counteract PS@PANI conductive material preparation research into
Exhibition.
In the research of early period, [the Preparation and characterization of such as Lisha Wang
polyaniline coated microspheres for potential application inanisotropic
Conductive film, J Polym Res, 2011,18:2169-2174] people directly utilizes polystyrene/divinyl of purchase
Base benzene polymer microballoon (PSDVB) is mixed with aniline monomer, and home position polymerization reaction system occurs under the initiation of Ammonium Persulfate 98.5
Standby PS@PANI, but the PSDVB microballoon price of this method commodity in use is higher.[the Hollow such as Chun Yan Gao
submicron-sized spherical conducting polyaniline particles and their
Suspension rheology under applied electric fields, Polymer, 2018,140:80-88] people with
Emulsion polymerization is prepared for Monodisperse Polystyrene Microspheres, is then had by the way that concentrated sulfuric acid progress sulfonation preparation is addedPS microballoon,
The surface that aniline monomer is adsorbed on PS microballoon is subjected to in-situ polymerization preparation PS@PANI conductive material, the system using electrostatic attraction
Standby process sulfonating reaction, which operates the more demanding and concentrated sulfuric acid, has very high security risk, is unfavorable for being mass produced.
Therefore, the preparation of existing PS@PANI conductive micro-balloons is mostly to be commercialized modified PS microballoon or pass through sulfonation
PS microballoon is that substrate carries out polyaniline in the home position polymerization reaction on its surface, there is higher cost or safety during the preparation process
The larger problem of hidden danger.
Summary of the invention
Goal of the invention: in order to overcome the deficiencies in the prior art, it is an object of the present invention to provide one kind, and sulfuric acid to be avoided to make
With the preparation method for the PS@PANI conductive material that, preparation section is simply drawn based on electrostatic self-absorbing.
Technical solution: a kind of preparation method of the PS@PANI conductive material drawn based on electrostatic self-absorbing of the present invention, packet
Include following steps:
(1) sodium hydroxide solution and 20~40g styrene for taking 10~15wt% of 40~50ml stir 5~10min, will
Sodium hydroxide, styrene mixed liquor pour into separatory funnel, and lower layer's light red liquid is released, and lower layer's light red liquid includes pair
The mixed solution of benzenediol sodium, sodium hydroxide, colourless upper solution include styrene solution, upper solution again with 40~
50ml, 10~15wt% sodium hydroxide solution stirring, repeat liquid separation operate 2~4 times, remove styrene polymerization inhibitor, obtain compared with
For pure styrene solution；
(2) styrene solution, deionized water and acrylic acid derivative are mixed by 1: 60: 1~5 molar ratio, in nitrogen
30~60min of magnetic agitation under protection, 300~400rpm stirring rate, after reaction temperature reaches 70~75 DEG C, addition 5~
10mL concentration is that the Ammonium Persulfate 98.5 solution of 0.05~0.10mol/L continues that the PS microballoon lotion with acetate functional group is made,
It is cleaned by ultrasonic after centrifugation, repeats 2~4 times, centrifugation rate is 7500~10000rpm, and centrifugation time is 7~10min, and ultrasound is clear
The power washed is 350~400W, and ultrasonic time is 5~10min, and 65~70 DEG C of drying are obtained with acetate functional group PS microballoon
Powder；
(3) by with acetate functional group PS microsphere powder ultrasonic disperse in the deionized water of 60~80mL, ultrasonic function
Rate is 350~400W, and ultrasonic time is 30~45min, then acid aniline solution is added drop-wise to acetate functional group PS microballoon point
In dispersion liquid, the mass ratio of acetate functional group PS microsphere powder and aniline monomer is 5~42: 1, is stirred under the conditions of -3~3 DEG C
30~45min；
(4) press ammonium persulfate: ammonium persulfate solution is added in aniline monomer molar ratio 1.2: 1, the reaction was continued 6~36h, centrifugation
Cleaning repeats 2~4 times, dries at 65~70 DEG C, obtains PS@PANI conductive micro-balloons.
Acrylic acid derivative is acrylic acid, methacrylic acid, any one in ethylacrylic acid in step (2).
In step (3) acid aniline solution include hydrochloric acid that concentration is 0.8~1.2mol/L and concentration be 0.005~
The aniline solution of 0.028mol/L.
Reaction principle: by by acrylic acid derivative, styrene and deionized water after evenly mixing under nitrogen protection without
Soap emulsion polymerization prepares the PS microballoon of acetate functional group, causes in-situ polymerization after then utilizing electrostatic attraction adsorption of aniline monomer
It reacts and PS@PANI conductive micro-balloons is made.
The utility model has the advantages that compared to the prior art the present invention, has the characteristics that following conspicuousness:
1, the process for needing to carry out PS microballoon sulfonation in existing PS@PANI preparation method is eliminated, sulfuric acid is avoided to use
Brought security risk in journey；
2, PS@PANI conductive material preparation section is simplified, can be used as conductive compositions applied to electrically conductive ink or conductive painting
The preparation of material has preferable application potential；
3, it is made by emulsifier-free emulsion polymerization with negative electrical charge PS microballoon, is then adsorbed aniline monomer using electrostatic attraction
In-situ polymerization is carried out on the surface of PS microballoon and prepares PS@PANI conductive material, and test obtains its tool after being centrifuged drying tabletting
There is preferable electric conductivity.
Detailed description of the invention
Fig. 1 is the microscopic appearance figure of P of the present invention (St-MAA) microballoon.
Fig. 2 is the infrared spectrogram of P of the present invention (St-MAA) microballoon.
Fig. 3 is P of the present invention (St-MAA)@PANI microballoon SEM.
Fig. 4 is the electric conductivity test chart of PS@PANI conductive material of the present invention.
Specific embodiment
Embodiment 1
A kind of preparation method of the PS@PANI conductive material drawn based on electrostatic self-absorbing, comprising the following steps:
(1) removing of styrene polymerization inhibitor: the sodium hydroxide solution of the 10wt% of 40ml and 20g styrene is taken to stir
5min pours into sodium hydroxide, styrene mixed liquor in separatory funnel, lower layer's light red liquid is released, lower layer's light red liquid
Body includes the mixed solution of hydroquinone sodium, sodium hydroxide, and colourless upper solution includes styrene solution, upper solution again with
The sodium hydroxide solution of 40ml, 10wt% stir, and repeat liquid separation and operate 2 times, remove styrene polymerization inhibitor, obtain more pure
Styrene solution；
(2) it is prepared with the PS microballoon of acetate functional group: styrene solution, deionized water and acrylic acid is pressed 1: 60: 1
Molar ratio mixing, magnetic agitation 30min adds after reaction temperature reaches 70 DEG C under nitrogen protection, 300rpm stirring rate
Enter the Ammonium Persulfate 98.5 solution that 5mL concentration is 0.05mol/L to continue that the PS microballoon lotion with acetate functional group is made, after centrifugation
Ultrasonic cleaning, is repeated 2 times, centrifugation rate 7500rpm, centrifugation time 7min, and the power of ultrasonic cleaning is 350W, when ultrasonic
Between be 5min, 65 DEG C of drying obtain with acetate functional group PS microsphere powder；
(3) preparation of PS@PANI conductive material: by with acetate functional group PS microsphere powder ultrasonic disperse 60mL's
In deionized water, ultrasonic power 350W, ultrasonic time 30min, then acid aniline solution is added drop-wise to acetate functional group
In PS microballoon dispersion liquid, the aniline that acid aniline solution includes the hydrochloric acid that concentration is 0.8mol/L and concentration is 0.005mol/L is molten
The mass ratio of liquid, acetate functional group PS microsphere powder and aniline monomer is 42: 1, stirs 30min under the conditions of -3 DEG C, pressed
Sulfate of ammoniac: ammonium persulfate solution is added in aniline monomer molar ratio 1.2: 1, and the reaction was continued 6h, eccentric cleaning is repeated 2 times, at 65 DEG C
Drying, obtains PS@PANI conductive micro-balloons.
Embodiment 2
A kind of preparation method of the PS@PANI conductive material drawn based on electrostatic self-absorbing, comprising the following steps:
(1) removing of styrene polymerization inhibitor: the sodium hydroxide solution of the 15wt% of 50ml and 40g styrene is taken to stir
10min pours into sodium hydroxide, styrene mixed liquor in separatory funnel, lower layer's light red liquid is released, lower layer's light red liquid
Body includes the mixed solution of hydroquinone sodium, sodium hydroxide, and colourless upper solution includes styrene solution, upper solution again with
The sodium hydroxide solution of 50ml, 15wt% stir, and repeat liquid separation and operate 4 times, remove styrene polymerization inhibitor, obtain more pure
Styrene solution；
(2) it is prepared with the PS microballoon of acetate functional group: styrene solution, deionized water and methacrylic acid is pressed 1:
60: 5 molar ratio mixing, the magnetic agitation 60min under nitrogen protection, 400rpm stirring rate reach 75 DEG C to reaction temperature
Afterwards, the Ammonium Persulfate 98.5 solution that 10mL concentration is 0.10mol/L is added to continue that the PS microballoon lotion with acetate functional group is made,
It is cleaned by ultrasonic after centrifugation, is repeated 4 times, the power of centrifugation rate 10000rpm, centrifugation time 10min, ultrasonic cleaning is
400W, ultrasonic time 10min, 70 DEG C of drying are obtained with acetate functional group PS microsphere powder；
(3) preparation of PS@PANI conductive material: by with acetate functional group PS microsphere powder ultrasonic disperse 80mL's
In deionized water, ultrasonic power 400W, ultrasonic time 45min, then acid aniline solution is added drop-wise to acetate functional group
In PS microballoon dispersion liquid, the aniline that acid aniline solution includes the hydrochloric acid that concentration is 1.2mol/L and concentration is 0.028mol/L is molten
The mass ratio of liquid, acetate functional group PS microsphere powder and aniline monomer is 5: 1,45min is stirred under the conditions of 3 DEG C, by over cure
Sour ammonia: ammonium persulfate solution is added in aniline monomer molar ratio 1.2: 1, and the reaction was continued 36h, eccentric cleaning is repeated 4 times, at 70 DEG C
Drying, obtains PS@PANI conductive micro-balloons.
Embodiment 3
A kind of preparation method of the PS@PANI conductive material drawn based on electrostatic self-absorbing, comprising the following steps:
(1) removing of styrene polymerization inhibitor: the sodium hydroxide solution of the 13wt% of 45ml and 30g styrene is taken to stir
7min pours into sodium hydroxide, styrene mixed liquor in separatory funnel, lower layer's light red liquid is released, lower layer's light red liquid
Body includes the mixed solution of hydroquinone sodium, sodium hydroxide, and colourless upper solution includes styrene solution, upper solution again with
The sodium hydroxide solution of 45ml, 13wt% stir, and repeat liquid separation and operate 3 times, remove styrene polymerization inhibitor, obtain more pure
Styrene solution；
(2) it is prepared with the PS microballoon of acetate functional group: styrene solution, deionized water and ethylacrylic acid is pressed 1:
60: 3 molar ratio mixing, the magnetic agitation 45min under nitrogen protection, 350rpm stirring rate reach 73 DEG C to reaction temperature
Afterwards, the Ammonium Persulfate 98.5 solution that 7mL concentration is 0.07mol/L is added to continue that the PS microballoon lotion with acetate functional group is made,
It is cleaned by ultrasonic after centrifugation, is repeated 3 times, centrifugation rate 8750rpm, centrifugation time 8min, the power of ultrasonic cleaning are 375W,
Ultrasonic time is 7min, and 67 DEG C of drying are obtained with acetate functional group PS microsphere powder；
(3) preparation of PS@PANI conductive material: by with acetate functional group PS microsphere powder ultrasonic disperse 70mL's
In deionized water, ultrasonic power 375W, ultrasonic time 37min, then acid aniline solution is added drop-wise to acetate functional group
In PS microballoon dispersion liquid, the aniline that acid aniline solution includes the hydrochloric acid that concentration is 1.0mol/L and concentration is 0.016mol/L is molten
The mass ratio of liquid, acetate functional group PS microsphere powder and aniline monomer is 23: 1,37min is stirred under the conditions of 0 DEG C, by over cure
Sour ammonia: ammonium persulfate solution is added in aniline monomer molar ratio 1.2: 1, and the reaction was continued 21h, eccentric cleaning is repeated 3 times, at 67 DEG C
Drying, obtains PS@PANI conductive micro-balloons.
Embodiment 4
A kind of preparation method of the PS@PANI conductive material drawn based on electrostatic self-absorbing, comprising the following steps:
(1) removing of styrene polymerization inhibitor: the sodium hydroxide solution of the 11wt% of 42ml and 22g styrene is taken to stir
6min pours into sodium hydroxide, styrene mixed liquor in separatory funnel, lower layer's light red liquid is released, lower layer's light red liquid
Body includes the mixed solution of hydroquinone sodium, sodium hydroxide, and colourless upper solution includes styrene solution, upper solution again with
The sodium hydroxide solution of 43ml, 11wt% stir, and repeat liquid separation and operate 2 times, remove styrene polymerization inhibitor, obtain more pure
Styrene solution；
(2) it is prepared with the PS microballoon of acetate functional group: styrene solution, deionized water and acrylic acid is pressed 1: 60: 2
Molar ratio mixing, magnetic agitation 35min adds after reaction temperature reaches 71 DEG C under nitrogen protection, 310rpm stirring rate
Enter the Ammonium Persulfate 98.5 solution that 6mL concentration is 0.06mol/L to continue that the PS microballoon lotion with acetate functional group is made, after centrifugation
Ultrasonic cleaning, is repeated 3 times, centrifugation rate 7900rpm, centrifugation time 8min, and the power of ultrasonic cleaning is 360W, when ultrasonic
Between be 6min, 66 DEG C of drying obtain with acetate functional group PS microsphere powder；
(3) preparation of PS@PANI conductive material: by with acetate functional group PS microsphere powder ultrasonic disperse 62mL's
In deionized water, ultrasonic power 360W, ultrasonic time 34min, then acid aniline solution is added drop-wise to acetate functional group
In PS microballoon dispersion liquid, the aniline that acid aniline solution includes the hydrochloric acid that concentration is 0.9mol/L and concentration is 0.010mol/L is molten
The mass ratio of liquid, acetate functional group PS microsphere powder and aniline monomer is 12: 1, stirs 33min under the conditions of -1 DEG C, pressed
Sulfate of ammoniac: ammonium persulfate solution is added in aniline monomer molar ratio 1.2: 1, and the reaction was continued 9h, eccentric cleaning is repeated 2 times, at 67 DEG C
Drying, obtains PS@PANI conductive micro-balloons.
Embodiment 5
A kind of preparation method of the PS@PANI conductive material drawn based on electrostatic self-absorbing, comprising the following steps:
(1) removing of styrene polymerization inhibitor: the sodium hydroxide solution of the 14wt% of 48ml and 35g styrene is taken to stir
9min pours into sodium hydroxide, styrene mixed liquor in separatory funnel, lower layer's light red liquid is released, lower layer's light red liquid
Body includes the mixed solution of hydroquinone sodium, sodium hydroxide, and colourless upper solution includes styrene solution, upper solution again with
The sodium hydroxide solution of 48ml, 14wt% stir, and repeat liquid separation and operate 4 times, remove styrene polymerization inhibitor, obtain more pure
Styrene solution；
(2) it is prepared with the PS microballoon of acetate functional group: styrene solution, deionized water and methacrylic acid is pressed 1:
60: 4 molar ratio mixing, the magnetic agitation 52min under nitrogen protection, 390rpm stirring rate reach 74 DEG C to reaction temperature
Afterwards, the Ammonium Persulfate 98.5 solution that 9mL concentration is 0.09mol/L is added to continue that the PS microballoon lotion with acetate functional group is made,
It is cleaned by ultrasonic after centrifugation, is repeated 4 times, centrifugation rate 9500rpm, centrifugation time 9min, the power of ultrasonic cleaning are 390W,
Ultrasonic time is 9min, and 69 DEG C of drying are obtained with acetate functional group PS microsphere powder；
(3) preparation of PS@PANI conductive material: by with acetate functional group PS microsphere powder ultrasonic disperse 75mL's
In deionized water, ultrasonic power 390W, ultrasonic time 42min, then acid aniline solution is added drop-wise to acetate functional group
In PS microballoon dispersion liquid, the aniline that acid aniline solution includes the hydrochloric acid that concentration is 1.1mol/L and concentration is 0.025mol/L is molten
The mass ratio of liquid, acetate functional group PS microsphere powder and aniline monomer is 40: 1,43min is stirred under the conditions of 2 DEG C, by over cure
Sour ammonia: ammonium persulfate solution is added in aniline monomer molar ratio 1.2: 1, and the reaction was continued 30h, eccentric cleaning is repeated 4 times, at 69 DEG C
Drying, obtains PS@PANI conductive micro-balloons.
Embodiment 6
A kind of preparation method of the PS@PANI conductive material drawn based on electrostatic self-absorbing, comprising the following steps:
(1) the sodium hydroxide solution 150ml for configuring 12wt%, take wherein 50ml be added in the beaker of 200ml, then to burning
35g styrene is added in cup and according to 150rpm progress magnetic agitation 5min polymerization inhibitor is sufficiently reacted with sodium hydroxide, finally
Mixing liquid is poured into separatory funnel, lower layer's light red liquid is released, upper solution, which is reentered into beaker, is added hydrogen-oxygen
Change sodium solution 50ml, repeats the both available more pure styrene solutions of aforesaid operations 2 times；
(2) styrene, deionized water and the methacrylic acid (MAA) that remove polymerization inhibitor are carried out according to molar ratio 1: 60: 1
It pours into four round flask after evenly mixing, it is dense that 5mL is added after 300rpm/min stirring the reaction was continued 1h under nitrogen protection
Degree be 0.1mol/L APS solution continue be made with acetate functional group PS microballoon lotion, by its according to 10000rpm from
It is cleaned by ultrasonic after heart 7min, acquisition is with acetate functional group PS microballoon lotion, 70 DEG C of drying after repeating centrifugation, cleaning 2 times
It obtains with acetate functional group PS microsphere powder；
(3) it takes and is dispersed in going for 60mL again by 400w ultrasound 30min with acetate functional group PS microsphere powder in right amount
In ionized water, aniline monomer configuration 60mL is weighed according to the mass ratio 42: 1 of acetate functional group PS microsphere powder and aniline monomer
Acid aniline solution, including concentration of hydrochloric acid be 1mol/L and concentration of aniline is 0.028mol/L.Then by acid aniline
Solution is added drop-wise in acetate functional group PS microballoon dispersion liquid, is stirred 30min under the conditions of 0 DEG C, is utilized the principle of electrostatic attraction
Aniline monomer is adsorbed on to the surface of PS microballoon, then press ammonium persulfate: aniline monomer molar ratio 1.2: 1 be added APS solution after
Continuous reaction 6h, being then centrifuged for cleaning, drying obtains PS@PANI conductive micro-balloons three times.
Embodiment 7
A kind of preparation method of the PS@PANI conductive material drawn based on electrostatic self-absorbing, comprising the following steps:
(1) the sodium hydroxide solution 150ml for configuring 12wt%, take wherein 50ml be added in the beaker of 200ml, then to burning
35g styrene is added in cup and according to 150rpm progress magnetic agitation 5min polymerization inhibitor is sufficiently reacted with sodium hydroxide, finally
Mixing liquid is poured into separatory funnel, lower layer's light red liquid is released, upper solution, which is reentered into beaker, is added hydrogen-oxygen
Change sodium solution 50ml, repeats the both available more pure styrene solutions of aforesaid operations 2 times；
(2) styrene, deionized water and the methacrylic acid (MAA) that remove polymerization inhibitor are carried out according to molar ratio 1: 60: 5
It pours into four round flask after evenly mixing, it is dense that 5mL is added after 350rpm/min stirring the reaction was continued 1h under nitrogen protection
Degree be 0.1mol/L APS solution continue be made with acetate functional group PS microballoon lotion, by its according to 10000rpm from
It is cleaned by ultrasonic after heart 7min, acquisition is with acetate functional group PS microballoon lotion, 70 DEG C of drying after repeating centrifugation, cleaning 2 times
It obtains with acetate functional group PS microsphere powder；
(3) it takes and is dispersed in going for 60mL again by 400w ultrasound 30min with acetate functional group PS microsphere powder in right amount
In ionized water, aniline monomer configuration 60mL is weighed according to the mass ratio 30: 1 of acetate functional group PS microsphere powder and aniline monomer
Acid aniline solution, wherein being 1mol/L including concentration of hydrochloric acid and concentration of aniline is 0.028mol/L.It then will be acid
Aniline solution is added drop-wise in acetate functional group PS microballoon dispersion liquid, is stirred 30min under the conditions of 0 DEG C, is utilized electrostatic attraction
Aniline monomer is adsorbed on the surface of PS microballoon by principle, and then press ammonium persulfate: it is molten that APS is added in aniline monomer molar ratio 1.2: 1
The reaction was continued for liquid for 24 hours, and being then centrifuged for cleaning, drying obtains PS@PANI (P (St-MAA)) conductive micro-balloons three times.
The microscopic appearance of P obtained by the present embodiment (St-MAA) microballoon as shown in Figure 1, P (St-MAA) microballoon size compared with
To be uniform, schemochrome is showed after drying.Such as Fig. 2, from the FTIR of P (St-MAA): wave number 1384.2cm-1With
1452.8cm-1Place is the characteristic peak of phenyl ring, 2923.3cm-1And 3025.8cm-1Place is the stretching vibration absworption peak of-CH, is shown
There are the skeleton structures of polystyrene (C8H8) n in microballoon.In 3439cm-1Locate Qiang Erkuan characteristic peak, correspond to carboxyl (-
COOH) in functional group hydroxyl (- OH) vibration absorption peak；Meanwhile 1697.8cm-1The strong peak at place belongs to carboxyl (- COOH) official
The stretching vibration absworption peak of carbonyl (- C=O) in capable of rolling into a ball.The microscopic appearance and electric conductivity of P (St-MAA)@PANI conductive micro-balloons are such as
Fig. 3, shown in 4, polyaniline is distributed less uniform at P (St-MAA), but has certain electric conductivity.
In conclusion methacrylic acid (MAA) and styrene (St) monomer, which are copolymerized to close to react, has successfully been made P (St-
MAA) conductive micro-balloons.
Embodiment 8
A kind of preparation method of the PS@PANI conductive material drawn based on electrostatic self-absorbing, comprising the following steps:
The sodium hydroxide solution 150ml for configuring 12wt%, take wherein 50ml be added in the beaker of 200ml, then to beaker
Middle addition 35g styrene carries out magnetic agitation 5min according to 150rpm and polymerization inhibitor is sufficiently reacted with sodium hydroxide, finally will
Mixing liquid is poured into separatory funnel, lower layer's light red liquid is released, upper solution, which is reentered into beaker, is added hydroxide
Sodium solution 50ml repeats the both available more pure styrene solutions of aforesaid operations 2 times；
The styrene, deionized water and the acrylic acid (AA) that remove polymerization inhibitor are carried out according to certain molar ratio 1: 60: 5
It is poured into four round flask after even mixing, 5mL concentration is added after 400rpm/min stirring the reaction was continued 1h under nitrogen protection
For the APS solution of 0.1mol/L continue that the PS microballoon lotion with acetate functional group is made, it is centrifuged according to 10000rpm
It is cleaned by ultrasonic after 7min, with acetate functional group PS microballoon lotion, 70 DEG C are dried for acquisition after repeating centrifugation, cleaning 2 times
To with acetate functional group PS microsphere powder；
Take the appropriate deionization for being dispersed in 60mL again by 400w ultrasound 30min with acetate functional group PS microsphere powder
In water, the acid of aniline monomer configuration 60mL is weighed according to the mass ratio 5: 1 of acetate functional group PS microsphere powder and aniline monomer
Property aniline solution, including concentration of hydrochloric acid be 1mol/L and concentration of aniline is 0.028mol/L.Then by acid aniline solution
It is added drop-wise in acetate functional group PS microballoon dispersion liquid, stirs 30min under the conditions of 0 DEG C, using the principle of electrostatic attraction by benzene
Amine monomers are adsorbed on the surface of PS microballoon, and then press ammonium persulfate: aniline monomer molar ratio 1.2: 1 is added APS solution and continues instead
Should for 24 hours, being then centrifuged for cleaning, drying obtains PS@PANI conductive micro-balloons three times.
Claims (10)
1. a kind of preparation method of the PS@PANI conductive material drawn based on electrostatic self-absorbing, it is characterised in that the following steps are included:
(1) sodium hydroxide solution and 20~40g styrene, 5~10min of stirring that 40~50mL concentration is 10~15wt% are taken, it will
Sodium hydroxide, styrene mixed liquor pour into separatory funnel, lower layer's light red liquid are released, colourless upper solution includes benzene
Vinyl solution；
(2) styrene solution, deionized water and acrylic acid derivative are mixed by 1: 60: 1~5 molar ratio, in nitrogen protection
Under continue 30~60min of stirring, after reaction temperature reaches 70~75 DEG C, addition 5~10mL concentration be 0.05~0.10mol/L
Ammonium Persulfate 98.5 solution continue be made with acetate functional group PS microballoon lotion, be cleaned by ultrasonic after centrifugation, 65~70 DEG C baking
It is dry to obtain with acetate functional group PS microsphere powder；
(3) by with acetate functional group PS microsphere powder ultrasonic disperse in the deionized water of 60~80mL, then by acid benzene
Amine aqueous solution is added drop-wise in acetate functional group PS microballoon dispersion liquid, the quality of acetate functional group PS microsphere powder and aniline monomer
Than being 5~42: 1,30~45min is stirred under the conditions of -3~3 DEG C；
(4) press ammonium persulfate: ammonium persulfate solution is added in aniline monomer molar ratio 1.2: 1, and the reaction was continued, eccentric cleaning, 65
~70 DEG C of drying, obtain PS@PANI conductive micro-balloons.
2. a kind of preparation method of PS@PANI conductive material drawn based on electrostatic self-absorbing according to claim 1, feature
Be: lower layer's light red liquid includes the mixed solution of hydroquinone sodium, sodium hydroxide in the step (1).
3. a kind of preparation method of PS@PANI conductive material drawn based on electrostatic self-absorbing according to claim 1, feature
Be: the upper solution in the step (1) is stirred with the sodium hydroxide solution of 40~50ml, 10~15wt% again, repeats to divide
Liquid operates 2~4 times.
4. a kind of preparation method of PS@PANI conductive material drawn based on electrostatic self-absorbing according to claim 1, feature
Be: stirring is magnetic agitation in the step (2), and stirring rate is 300~400rpm.
5. a kind of preparation method of PS@PANI conductive material drawn based on electrostatic self-absorbing according to claim 1, feature
Be: centrifugation, ultrasonic cleaning repeat 2~4 times in the step (2), and centrifugation rate is 7500~10000rpm, and centrifugation time is
7~10min, the power of ultrasonic cleaning are 350~400W, and ultrasonic time is 5~10min.
6. a kind of preparation method of PS@PANI conductive material drawn based on electrostatic self-absorbing according to claim 1, feature
Be: acrylic acid derivative is acrylic acid, methacrylic acid, any one in ethylacrylic acid in the step (2).
7. a kind of preparation method of PS@PANI conductive material drawn based on electrostatic self-absorbing according to claim 1, feature
Be: ultrasonic power is 350~400W in the step (3), and ultrasonic time is 30~45min.
8. a kind of preparation method of PS@PANI conductive material drawn based on electrostatic self-absorbing according to claim 1, feature
Be: in the step (3) acid aniline solution include hydrochloric acid that concentration is 0.8~1.2mol/L and concentration be 0.005~
The aniline solution of 0.028mol/L.
9. a kind of preparation method of PS@PANI conductive material drawn based on electrostatic self-absorbing according to claim 1, feature
Be: the reaction time is 6~36h in the step (4).
10. a kind of preparation method of PS@PANI conductive material drawn based on electrostatic self-absorbing according to claim 1, special
Sign is: eccentric cleaning repeats 2~4 times in the step (4).
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