CN106674546B - Polystyrolsulfon acid graft grapheme/layer/polyaniline conductive composite hydrogel preparation method and application - Google Patents
Polystyrolsulfon acid graft grapheme/layer/polyaniline conductive composite hydrogel preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method and applications of polystyrolsulfon acid graft grapheme/layer/polyaniline conductive composite hydrogel, this method first restores graphene oxide after surface of graphene oxide grafted polystyrene sulfonic acid, then by the static monitor of aniline monomer in conjunction with the compound phase of polystyrolsulfon acid graft grapheme, target product polystyrolsulfon acid graft grapheme/layer/polyaniline conductive composite hydrogel is obtained.Polystyrolsulfon acid with negative electrical charge is grafted to graphene surface by the present invention, both the distributing homogeneity of graphene and polyaniline in the solubility property and plural gel matrix of graphene had been improved, the effective compound of graphene and polyaniline is promoted further through a variety of interactions between polystyrolsulfon acid graft grapheme and polyaniline, so that the conduction composite hydrogel has good mechanical strength and electroresponsive, there is the ability that molecule release is controlled under electro photoluminescence.
Description
Technical field
The present invention relates to technical field of function materials, and in particular to a kind of polystyrolsulfon acid with Electro-stimulate response connects
The preparation method and application of branch graphene/polyaniline conductive composite hydrogel.
Background technique
Conducting polymer hydrogel had not only had the water-absorbing-retaining performance of hydrogel material, but also the electrical property with conductive material
Can, thus before the fields such as artificial muscle, electro photoluminescence control release, electrochemical energy storage, sensor have good application
Scape.But common conducting polymer can neither be dissolved in usual vehicle, can occur to thermally decompose and cannot melt again at high temperature
The conducting polymer hydrogel for melting, thus obtaining excellent water-absorbing-retaining performance, mechanical property and electric property still suffers from huge
Challenge.
The conducting polymer hydrogel reported at present is usually that conducting polymer is directly filled into hydrogel matrix,
Or the monomer of conducting polymer is directly carried out to the blend that in-situ polymerization obtains hydrogel in hydrogel matrix.After compound
Obtained conducting polymer hydrogel is generally able to maintain the mechanical properties of hydrogel matrix, solves to a certain extent not
Molten insoluble pure conducting polymer is difficult to the problem of processing.But directly filling is difficult to realize conducting polymer and non-conductive
Hydrogel matrix is uniformly distributed；And in the preparation process polymerizeing in situ, the conducting polymer of formation often blocks water-setting
The surface of matrix body, so that the conducting polymer constituent content inside hydrogel is lower, or even some districts inside hydrogel
Domain does not have conducting polymer component, seriously affects the conductivity uniformity of hydrogel, limits its practical application.
Summary of the invention
It is an object of the invention to solve the distribution of conductive component present in existing conducting polymer hydrogel preparation process
Unevenly, the deficiencies of conductivity difference is big inside and outside hydrogel provides a kind of polystyrolsulfon acid grafting with Electro-stimulate response
The preparation method and application of graphene/polyaniline conductive composite hydrogel.The present invention is first in surface of graphene oxide grafting
Polystyrolsulfon acid, then be reduced into polystyrolsulfon acid graft grapheme, finally by the static polymerization of aniline monomer and poly-
The compound phase of styrene sulfonic acid graft grapheme combines, and it is multiple to finally obtain polystyrolsulfon acid graft grapheme/layer/polyaniline conductive
Heshui gel, the conduction composite hydrogel have good mechanical property and electric property, can effectively control under electric field action
The time of molecule release processed and dosage, it is widely used.To achieve the above object, the technical solution adopted in the present invention is as follows:
Polystyrolsulfon acid graft grapheme/layer/polyaniline conductive composite hydrogel preparation method, comprising the following steps:
(1) in organic solvent by graphene oxide, 2- bromine isobutyl acylbromide, triethylamine dispersion, it is obtained after the reaction was completed containing initiator
The graphene oxide of group；(2) water-dispersible containing the graphene oxide for causing group, catalyst, resistance are added under protective atmosphere
Agent, bipyridine and sodium styrene sulfonate living are reacted, and the graphene oxide of polystyrolsulfon acid grafting is obtained；(3) it uses
The graphene oxide of water dispersion polystyrolsulfon acid grafting is added reducing agent and is reacted, and obtains polystyrolsulfon acid grafting stone
Black alkene；(4) water-dispersible polystyrolsulfon acid graft grapheme, is added aniline and oxidant is reacted, and obtains polystyrene
Sulphonic Acid Functionalized graphene/polyaniline conductive composite hydrogel.
According to above scheme, graphene oxide in step (1), 2- bromine isobutyl acylbromide, triethylamine amount ratio be 1g:20-
100mL:10-40mL。
According to above scheme, step (1) organic solvent is chloroform or n,N-Dimethylformamide, reaction condition
For ice-water bath, reaction time 24-48h, after the reaction was completed through centrifugation, washing, so dry that contain the graphite oxide for causing group
Alkene.
According to above scheme, contain graphene oxide, catalyst, anti-activator, the bipyridine for causing group in step (2)
And the mass ratio of sodium styrene sulfonate is 8-200:2.5-12:1:19-95:206-825.
According to above scheme, the catalyst is stannous chloride or cuprous bromide, and the anti-activator is copper chloride or bromination
Copper.
According to above scheme, reaction temperature is 10-30 DEG C, reaction time 6-12h in step (2), and protection gas is argon gas,
Graphene oxide of the product through centrifugation, washing, the grafting of dry polystyrolsulfon acid.
According to above scheme, the mass ratio of polystyrolsulfon acid is grafted in step (3) graphene oxide and reducing agent is
1:2.5-8, reaction temperature are 90 DEG C, reaction time 18-24h, and product is through centrifugation, washing, dry that polystyrolsulfon acid connects
Branch graphene.
According to above scheme, the reducing agent is one of ascorbic acid or tea polyphenols.
According to above scheme, the amount ratio of polystyrolsulfon acid graft grapheme, aniline and oxidant is in step (4)
0.25-4g:1mL:0.8-48g stirs 30- after aniline is added into polystyrolsulfon acid graft grapheme dispersion liquid when mixing
60min, adds oxidant stirring 2-5min, reacts 24-36h in 4-10 DEG C of standing, is washed with deionized water to obtain the final product.
According to above scheme, the oxidant is one of iron chloride, ferric nitrate, ferric sulfate or ammonium persulfate.
Above-mentioned polystyrolsulfon acid graft grapheme/layer/polyaniline conductive composite hydrogel is as molecular Control releasable material
Using.
Compared with prior art, the invention has the following advantages: the polystyrolsulfon acid of (1) with negative electrical charge is grafted
To graphene surface, the solubility property of graphene had both been improved, graphene and the uniform of polyaniline in plural gel has been realized and divides
Cloth, further through the zwitterion interaction between polystyrolsulfon acid graft grapheme and polyaniline, π-πconjugation, hydrogen
A variety of effects such as key promote the effective compound of graphene and polyaniline；(2) mechanical property is introduced in conductive composite hydrogel
Excellent graphene makes hydrogel have good mechanical strength；(3) with the graphene and conducting polyaniline of good electrical performance
The control release of molecule can be achieved so that conductive composite hydrogel has electroresponsive in amine collective effect under electro photoluminescence.
Specific embodiment
To make those of ordinary skill in the art fully understand technical solution of the present invention and beneficial effect, below in conjunction with specific
Embodiment is further described.It should be understood that following embodiment is only better embodiment of the present invention, do not constitute to this hair
Bright restriction, on this basis the present invention can also there are many other embodiments, equally fall into protection scope of the present invention it
It is interior.
Source chemicals of the present invention be it is common commercially available, analyze pure, deionized water is self-control.
Embodiment 1
1) triethylamine of 0.5g graphene oxide, the 2- bromine isobutyl acylbromide of 25mL, 10mL are dispersed in three chloromethanes of 50mL
It in alkane, is placed in ice-water bath and reacts 24 hours, obtain after centrifugation, washing, drying containing the graphene oxide for causing group；
2) the 0.02g graphene oxide for containing initiation group is dispersed in the deionized water of 4mL, in argon atmosphere condition
Under be separately added into 3mg stannous chloride, 0.5mg copper chloride, 0.15mmol bipyridine, 1.2mmol sodium styrene sulfonate, at 20 DEG C
Lower reaction 6 hours obtains the graphene oxide of polystyrolsulfon acid grafting after centrifugation, washing, drying；
3) graphene oxide that 0.1g polystyrolsulfon acid is grafted is dispersed in 30mL water, 0.5g ascorbic acid is added,
It is reacted 18 hours at 90 DEG C, obtains polystyrolsulfon acid graft grapheme after centrifugation, washing, drying；
4) 0.05g polystyrolsulfon acid graft grapheme is dispersed in 10mL water, the aniline of 50 μ L is added, stir 30 points
The ferric nitrate of 1mmol is added in Zhong Hou.After being again stirring for 2 minutes, reaction 24 hours are stood at 4 DEG C, are washed with deionized,
Obtain polystyrolsulfon acid graft grapheme/layer/polyaniline conductive composite hydrogel.
Embodiment 2
1) triethylamine of 0.6g graphene oxide, the 2- bromine isobutyl acylbromide of 30mL, 10mL are dispersed in the N of 60mL, N- bis-
It in methylformamide, is placed in ice-water bath and reacts 30 hours, obtain after centrifugation, washing, drying containing the oxidation stone for causing group
Black alkene；
2) the 0.05g graphene oxide for containing initiation group is dispersed in the deionized water of 6mL, in argon atmosphere condition
Under be separately added into 4mg cuprous bromide, 0.6mg copper bromide, 0.2mmol bipyridine, 1.5mmol sodium styrene sulfonate, at 20 DEG C
Lower reaction 8 hours obtains the graphene oxide of polystyrolsulfon acid grafting after centrifugation, washing, drying；
3) graphene oxide that 0.12g polystyrolsulfon acid is grafted is dispersed in 35mL water, 0.6g tea polyphenols is added,
It is reacted 20 hours at 90 DEG C, obtains polystyrolsulfon acid graft grapheme after centrifugation, washing, drying；
4) 0.08g polystyrolsulfon acid graft grapheme is dispersed in 15mL water, the aniline of 75 μ L is added, stir 45 points
The ferric sulfate of 2mmol is added in Zhong Hou.After being again stirring for 3 minutes, reaction 24 hours are stood at 10 DEG C, are washed with deionized,
Obtain polystyrolsulfon acid graft grapheme/layer/polyaniline conductive composite hydrogel.
Embodiment 3
1) triethylamine of 0.8g graphene oxide, the 2- bromine isobutyl acylbromide of 40mL, 18mL are dispersed in the N of 70mL, N- bis-
It in methylformamide, is placed in ice-water bath and reacts 24 hours, obtain after centrifugation, washing, drying containing the oxidation stone for causing group
Black alkene；
2) the 0.06g graphene oxide for containing initiation group is dispersed in the deionized water of 8mL, in argon atmosphere condition
Under be separately added into 5mg stannous chloride, 1mg copper chloride, 0.25mmol bipyridine, 1.6mmol sodium styrene sulfonate, at 25 DEG C
Reaction 6-12 hours obtains the graphene oxide of polystyrolsulfon acid grafting after centrifugation, washing, drying；
3) graphene oxide that 0.1g polystyrolsulfon acid is grafted is dispersed in 35mL water, 0.7g ascorbic acid is added,
It is reacted 18-24 hours at 90 DEG C, obtains polystyrolsulfon acid graft grapheme after centrifugation, washing, drying；
4) 0.1g polystyrolsulfon acid graft grapheme is dispersed in 15mL water, the aniline of 100 μ L is added, stir 40 points
The ammonium persulfate of 6mmol is added in Zhong Hou.After being again stirring for 4 minutes, reaction 30 hours are stood at 8 DEG C, are washed with deionized water
It washs, obtains polystyrolsulfon acid graft grapheme/layer/polyaniline conductive composite hydrogel.
Embodiment 4
1) triethylamine of 0.75g graphene oxide, the 2- bromine isobutyl acylbromide of 45mL, 20mL are dispersed in three chloromethanes of 80mL
It in alkane, reacts 48 hours in ice-water bath, obtains after centrifugation, washing, drying containing the graphene oxide for causing group；
2) the 0.08g graphene oxide for containing initiation group is dispersed in the deionized water of 8mL, in argon atmosphere condition
Under be separately added into 5mg cuprous bromide, 0.9mg copper bromide, 0.25mmol bipyridine, 1.6mmol sodium styrene sulfonate, at 30 DEG C
Lower reaction 10 hours obtains the graphene oxide of polystyrolsulfon acid grafting after centrifugation, washing, drying；
3) graphene oxide that 0.1-0.2g polystyrolsulfon acid is grafted is dispersed in 30-50mL water, 0.5- is added
0.8g tea polyphenols react 18-24 hours at 90 DEG C, obtain polystyrolsulfon acid graft grapheme after centrifugation, washing, drying；
4) 0.15g polystyrolsulfon acid graft grapheme is dispersed in 20mL water, the aniline of 150 μ L, stirring 50 is added
After minute, the iron chloride of 3mmol is added.It is again stirring for after five minutes, stands reaction 36 hours at 5 DEG C, be washed with deionized water
It washs, obtains polystyrolsulfon acid graft grapheme/layer/polyaniline conductive composite hydrogel.
Embodiment 5
1) triethylamine of 1g graphene oxide, the 2- bromine isobutyl acylbromide of 50mL, 20mL are dispersed in the N of 90mL, N- diformazan
It in base formamide, reacts 40 hours in ice-water bath, obtains after centrifugation, washing, drying containing the graphene oxide for causing group；
2) the 0.1g graphene oxide for containing initiation group is dispersed in the deionized water of 10mL, in argon atmosphere condition
Under be separately added into 6mg cuprous bromide, 1.2mg copper bromide, 0.3mmol bipyridine, 2mmol sodium styrene sulfonate, at 25 DEG C
Reaction 12 hours obtains the graphene oxide of polystyrolsulfon acid grafting after centrifugation, washing, drying；
3) graphene oxide that 0.2g polystyrolsulfon acid is grafted is dispersed in 50mL water, 0.8g ascorbic acid is added,
It is reacted 24 hours at 90 DEG C, obtains polystyrolsulfon acid graft grapheme after centrifugation, washing, drying；
4) 0.2g polystyrolsulfon acid graft grapheme is dispersed in 20mL water, the aniline of 200 μ L is added, stir 60 points
The ferric nitrate of 10mmol is added in Zhong Hou.It is again stirring for after five minutes, reaction 36 hours is stood at 4 DEG C, are washed with deionized,
Obtain polystyrolsulfon acid graft grapheme/layer/polyaniline conductive composite hydrogel.
Embodiment 6
1) triethylamine of 0.6g graphene oxide, the 2- bromine isobutyl acylbromide of 35mL, 16mL are dispersed in three chloromethanes of 80mL
It in alkane, reacts 24 hours in ice-water bath, obtains after centrifugation, washing, drying containing the graphene oxide for causing group；
2) the 0.04g graphene oxide for containing initiation group is dispersed in the deionized water of 7mL, in argon atmosphere condition
Under be separately added into 4mg cuprous bromide, 0.8mg copper bromide, 0.2mmol bipyridine, 1.4mmol sodium styrene sulfonate, at 15 DEG C
Lower reaction 12 hours obtains the graphene oxide of polystyrolsulfon acid grafting after centrifugation, washing, drying；
3) graphene oxide that 0.16g polystyrolsulfon acid is grafted is dispersed in 40mL water, 0.7g ascorbic acid is added,
It is reacted 18 hours at 90 DEG C, obtains polystyrolsulfon acid graft grapheme after centrifugation, washing, drying；
4) 0.1g polystyrolsulfon acid graft grapheme is dispersed in 10-20mL water, the aniline of 100 μ L, stirring is added
After forty minutes, the ammonium persulfate of 4mmol is added.After being again stirring for 2 minutes, reaction 24 hours are stood at 10 DEG C, use deionization
Water washing obtains polystyrolsulfon acid graft grapheme/conduction composite hydrogel.
For the electro photoluminescence for understanding polystyrolsulfon acid graft grapheme/layer/polyaniline conductive composite hydrogel prepared by the present invention
Response and molecular Control releasability, we have carried out relevant test for the conduction composite hydrogel made from the embodiment 4.
Take the graft grapheme of polystyrolsulfon acid made from 50mg embodiment 4/layer/polyaniline conductive composite hydrogel, by its be placed in containing
It is impregnated one hour in the phosphate buffer solution of rhodamine B, taking-up is placed in the phosphate buffer solution without rhodamine B,
Carry out electro photoluminescence release.Adjusting applied voltage is 0V or 2.0V, draws 2mL solution from solution at regular intervals, measures sieve
The content of red bright B, while supplementing the PBS of same volume.The content of rhodamine B is surveyed at 554nm using ultraviolet spectrophotometry
It is fixed, the cumulative release percentage of different time is calculated according to the rhodamine B content of measurement.In 0V, after 10 hours, sieve
The cumulative release percentage of red bright B is 4.8%；In 2.0V, after 10 hours, the cumulative release percentage of rhodamine B is
12.7%.Above-mentioned experimental result shows apparent electroresponsive release behavior, this is because the polyphenyl under high electric field
The strand of amine shows the state of expansion, is conducive to the release of small molecule.
Claims (8)
1. polystyrolsulfon acid graft grapheme/layer/polyaniline conductive composite hydrogel preparation method, which is characterized in that including with
Lower step:
(1) in organic solvent by graphene oxide, 2- bromine isobutyl acylbromide, triethylamine dispersion, it is obtained after the reaction was completed containing drawing
Send out the graphene oxide of group；
(2) water-dispersible containing the graphene oxide for causing group, catalyst, anti-activator, union II pyrrole are added under protective atmosphere
Pyridine and sodium styrene sulfonate are reacted, and the graphene oxide of polystyrolsulfon acid grafting is obtained；
(3) graphene oxide of water-dispersible polystyrolsulfon acid grafting, is added reducing agent and is reacted, obtain polystyrene sulphur
Sour graft grapheme；
(4) water-dispersible polystyrolsulfon acid graft grapheme, is added aniline and oxidant is reacted, and obtains polystyrene sulphur
Sour graft grapheme/layer/polyaniline conductive composite hydrogel；
The amount ratio of polystyrolsulfon acid graft grapheme, aniline and oxidant is 0.25-4g:1mL:0.8- in step (4)
80g stirs 30-60min after aniline is added into polystyrolsulfon acid graft grapheme dispersion liquid when mixing, adds oxidant
Stir 2-5min, react 24-36h in 4-10 DEG C of standing, washed to obtain the final product with deionized water, the oxidant be iron chloride,
One of ferric nitrate, ferric sulfate or ammonium persulfate.
2. the preparation method of polystyrolsulfon acid graft grapheme/layer/polyaniline conductive composite hydrogel as described in claim 1,
It is characterized by: the amount ratio of graphene oxide in step (1), 2- bromine isobutyl acylbromide, triethylamine is 1g:20-100mL:10-
40mL。
3. the preparation method of polystyrolsulfon acid graft grapheme/layer/polyaniline conductive composite hydrogel as described in claim 1,
It is characterized by: step (1) organic solvent is chloroform or n,N-Dimethylformamide, reaction condition is ice-water bath,
Reaction time is 24-48h, after the reaction was completed through centrifugation, washing, dry contain the graphene oxide for causing group.
4. the preparation method of polystyrolsulfon acid graft grapheme/layer/polyaniline conductive composite hydrogel as described in claim 1,
It is characterized by: containing graphene oxide, catalyst, anti-activator, bipyridine and the styrene for causing group in step (2)
The mass ratio of sodium sulfonate is 8-200:2.5-12:1:19-95:206-825.
5. the preparation method of polystyrolsulfon acid graft grapheme/layer/polyaniline conductive composite hydrogel as described in claim 1,
It is characterized by: in step (2) reaction temperature be 10-30 DEG C, reaction time 6-12h, protection gas be argon gas, product through from
The heart, washing, the grafting of dry polystyrolsulfon acid graphene oxide.
6. the preparation method of polystyrolsulfon acid graft grapheme/layer/polyaniline conductive composite hydrogel as described in claim 1,
It is characterized by: the mass ratio of polystyrolsulfon acid is grafted in step (3) graphene oxide and reducing agent is 1:2.5-8, instead
Answering temperature is 90 DEG C, reaction time 18-24h, and product is through centrifugation, washing, dry polystyrolsulfon acid graft grapheme.
7. the preparation method of polystyrolsulfon acid graft grapheme/layer/polyaniline conductive composite hydrogel as described in claim 1,
It is characterized by: step (2) catalyst be stannous chloride or cuprous bromide, the anti-activator be copper chloride or copper bromide,
Step (3) reducing agent is ascorbic acid or tea polyphenols.
8. polystyrolsulfon acid graft grapheme/layer/polyaniline conductive that preparation method according to claim 1 is prepared is compound
Application of the hydrogel as molecular Control releasable material.
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| CN108164811A (en) * | 2017-11-29 | 2018-06-15 | 贵州晟扬管道科技有限公司 | A kind of production method of graphene functionalized polypropylene bellows |
| CN108155289B (en) * | 2017-12-25 | 2021-06-01 | 武汉工程大学 | Storage device based on graphene oxide/polyaniline/gold nanoparticle composite material and preparation method thereof |
| CN110627977A (en) * | 2019-09-27 | 2019-12-31 | 黔南民族师范学院 | Preparation method of graphene oxide grafted styrene |
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| CN103935987A (en) * | 2014-03-10 | 2014-07-23 | 同济大学 | CO2-responsive functionalized graphene oxide preparation method |
| CN105733260A (en) * | 2016-03-02 | 2016-07-06 | 廖彩芬 | Graphene/conducive macromolecular polymer aerogel and preparation method thereof |
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