CN106832344A - The preparation method and applications of polystyrolsulfon acid graft grapheme/polypyrrole composite aquogel - Google Patents
The preparation method and applications of polystyrolsulfon acid graft grapheme/polypyrrole composite aquogel Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of polystyrolsulfon acid graft grapheme/polypyrrole composite aquogel, the method is first in surface of graphene oxide grafted polystyrene sulfonic acid, the static monitor of polypyrrole is combined with the compound phase of polystyrolsulfon acid graft grapheme again, is obtained target product polystyrolsulfon acid graft grapheme/polypyrrole composite aquogel.There are various effects such as zwitterion interaction, the pi-conjugated effects of π, hydrogen bond in the composite aquogel between polystyrolsulfon acid graft grapheme and polypyrrole, make it have good mechanical strength, Graphene makes it also have electroresponsive with the good chemical property of polypyrrole simultaneously, and the control release of medicine can be realized under electro photoluminescence.
Description
Technical field
The present invention relates to technical field of function materials, and in particular to a kind of drug controlled release material with Electro-stimulate response
Material --- the preparation method of polystyrolsulfon acid graft grapheme/polypyrrole composite aquogel.
Background technology
As people are to the pay attention to day by day of health, for grinding that the system with good drug controlled release performance is carried out
Study carefully more and more deep.By good controlled drug delivery system, can make medicine that time or control spatially are realized in organism
System release, the optium concentration needed for keeping medicine to maintain disease treatment in vivo, so as to during avoiding conventional administration, medicine is dense
The problem failed to respond to any medical treatment when poisoning, drug concentration are low when spending higher, reaches the purpose of controllable therapeutic.More medicine is studied at present
Controlled release material is hydrogel material.Hydrogel is a kind of hydrophily but is not dissolved in the macromolecule network of water, and it has micro-
The advantages of view hole footpath is adjustable with mechanical strength, particularly sensitive aqueous gel have perception environment slight change, and by itself
Volume swelling and shrink and to respond these abilities from environmental stimuli.
It is more currently for the hydrogel research with stimulating responsives such as temperature, pH, ionic strengths, and for electricity
The hydrogel research of the drug controlled release performance of stimuli responsive is less.This is primarily due to common hydrogel material does not have
Electro-chemical activity, does not almost respond to for electro photoluminescence；On the other hand it is by the more difficult reality of the conductive hydrogel reported at present
Existing conductive component being uniformly distributed in hydrogel body, and the conductive hydrogel mechanical strength of gained is poor, limits in fact
Apply on border.
The content of the invention
It is an object of the invention to overcome existing drug controlled release hydrogel material above shortcomings, there is provided a kind of
The preparation method of the polystyrolsulfon acid graft grapheme/polypyrrole compound hydrogel material with Electro-stimulate response.The present invention
First in graphenic surface grafted polystyrene sulfonic acid, then by the static monitor of polypyrrole and polystyrolsulfon acid graft grapheme
Compound phase combine, prepared the polystyrolsulfon acid graft grapheme with excellent mechanical property and electric property/poly-
Pyrroles's composite aquogel.Preparation method of the present invention is simple, and without complex device, the composite aquogel for preparing is in electric field action
Under, can the effectively time of Drug controlled release and dosage.To achieve the above object, the technical solution adopted in the present invention is such as
Under：
The preparation method of polystyrolsulfon acid graft grapheme/polypyrrole composite aquogel, comprises the following steps：(1) will
Graphene oxide, 2- bromine isobutyl acylbromides, triethylamine dispersion obtain containing the oxygen for triggering group in organic solvent, after the completion of reaction
Graphite alkene；(2) it is water-dispersible containing the graphene oxide for triggering group, catalyst, anti-activator, connection are added under protective atmosphere
Two pyridines and SSS are reacted, and obtain the graphene oxide of polystyrolsulfon acid grafting；(3) it is water-dispersible poly-
The graphene oxide of styrene sulfonic acid grafting, adds reducing agent to be reacted, and obtains polystyrolsulfon acid graft grapheme；(4)
Water-dispersible polystyrolsulfon acid graft grapheme, adds pyrroles and oxidant to be reacted, and obtains polystyrolsulfon acid grafting
Graphene/polypyrrole composite aquogel.
According to such scheme, graphene oxide, 2- bromine isobutyl acylbromides, the amount ratio of triethylamine are 1g in step (1):20-
100mL:10-40mL。
According to such scheme, step (1) described organic solvent is chloroform or DMF, reaction condition
It is ice-water bath, the reaction time is 24-48h, reacts after completing through centrifugation, washing, the dry graphite oxide that must contain initiation group
Alkene.
According to such scheme, graphene oxide, catalyst, anti-activator, the bipyridine for triggering group are contained in step (2)
And the mass ratio of SSS is 8-200:2.5-12:1:19-95:206-825.
According to such scheme, the catalyst is stannous chloride or cuprous bromide, and the anti-activator is copper chloride or bromination
Copper.
According to such scheme, reaction temperature is 10-30 DEG C in step (2), and the reaction time is 6-12h, and protection gas is argon gas,
The graphene oxide that product is grafted through centrifugation, washing, dry polystyrolsulfon acid.
According to such scheme, the graphene oxide of polystyrolsulfon acid grafting is with the mass ratio of reducing agent in step (3)
1:2.5-8, reaction temperature is 90 DEG C, and the reaction time is 18-24h, and product is through centrifugation, washing, dry that polystyrolsulfon acid connects
Branch Graphene.
According to such scheme, the reducing agent is the one kind in ascorbic acid or Tea Polyphenols.
According to such scheme, the amount ratio of polystyrolsulfon acid graft grapheme, pyrroles and oxidant is in step (4)
0.25-4g:1mL:Before 0.8-48g reactions 30- is stirred in polystyrolsulfon acid graft grapheme dispersion liquid after addition pyrroles
60min, adds oxidant stirring 2-5min, and reaction 24-36h is stood at 10-20 DEG C, carries out washing with deionized water and obtains final product.
According to such scheme, the oxidant is the one kind in iron chloride, ferric nitrate, ferric sulfate or ammonium persulfate.
Obtained above-mentioned polystyrolsulfon acid graft grapheme/polypyrrole composite aquogel is used as drug controlled release material
Application.
Compared with prior art, the invention has the advantages that：(1) polystyrolsulfon acid is grafted to Graphene table
Face, improves the solubility property of Graphene, and introduces a large amount of functional groups with negative electrical charge in graphenic surface, is conducive to it
With the doping of polypyrrole；(2) polystyrolsulfon acid is connected to graphenic surface by covalent bond, and grafting density is high；(3) polyphenyl second
There are various effects such as zwitterion interaction, π-πconjugation, hydrogen bond between alkene Sulphonic Acid Functionalized Graphene and polypyrrole,
So that composite aquogel has good mechanical strength；(4) Graphene causes Compound Water with the good chemical property of polypyrrole
Gel has electroresponsive, and the control release of medicine is capable of achieving under electro photoluminescence.
Specific embodiment
To make those of ordinary skill in the art fully understand technical scheme and beneficial effect, below in conjunction with specific
Embodiment is further described.It should be understood that following examples are only better embodiment of the present invention, do not constitute to this hair
Bright restriction, on this basis the present invention can also have many other implementation methods, equally fall into protection scope of the present invention it
It is interior.
Reagent used in the present invention is common commercially available, analyzes pure, and deionized water is self-control.
Embodiment 1
1) 0.5g graphene oxides, 25mL 2- bromine isobutyl acylbromides, 10mL triethylamines are dispersed in 50mL chloroforms,
It is transferred in ice-water bath and reacts 24 hours, the graphene oxide containing initiation group is obtained after centrifugation, washing, drying；
2) containing 0.02g triggers the graphene oxide of group to be dispersed in 4mL deionized waters, under the conditions of argon gas atmosphere
3mg stannous chlorides, 0.5mg copper chlorides, 0.15mmol bipyridines, 1.2mmol SSSs are separately added into, are well mixed
Reacted 6 hours at 20 DEG C afterwards, the graphene oxide of polystyrolsulfon acid grafting is obtained after centrifugation, washing, drying；
3) graphene oxide that 0.1g polystyrolsulfon acids are grafted is dispersed in 30mL water, adds 0.5g ascorbic acid,
Reacted 18 hours at 90 DEG C, polystyrolsulfon acid graft grapheme is obtained after centrifugation, washing, drying；
4) 0.05g polystyrolsulfon acid graft graphemes are dispersed in 10mL water, add 50 μ L pyrroles, stirred 30 minutes
Afterwards, the ferric nitrate of 1mmol is added.After being again stirring for 2 minutes, reaction 24 hours are stood at 10 DEG C, be washed with deionized, obtained
To polystyrolsulfon acid graft grapheme/polypyrrole composite aquogel.
Embodiment 2
1) 0.6g graphene oxides, 30mL 2- bromine isobutyl acylbromides, 10mL triethylamines are dispersed in 60mLN, N- dimethyl methyls
In acid amides, it is transferred in ice-water bath and reacts 30 hours, the graphene oxide containing initiation group is obtained after centrifugation, washing, drying；
2) containing 0.05g triggers the graphene oxide of group to be dispersed in the deionized water of 6mL, in argon gas atmosphere condition
Under be separately added into 4mg cuprous bromides, 0.6mg copper bromides, 0.2mmol bipyridines, 1.5mmol SSSs, 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 acids are grafted is dispersed in 35mL water, adds 0.6g Tea Polyphenols,
Reacted 20 hours at 90 DEG C, polystyrolsulfon acid graft grapheme is obtained after centrifugation, washing, drying；
4) 0.08g polystyrolsulfon acid graft graphemes are dispersed in 15mL water, add the pyrroles of 75 μ L, stir 45 points
Zhong Hou, adds the ferric sulfate of 1.5mmol.After being again stirring for 3 minutes, reaction 24 hours are stood at 20 DEG C, be washed with deionized water
Wash, obtain polystyrolsulfon acid graft grapheme/polypyrrole composite aquogel.
Embodiment 3
1) triethylamine of 0.8g graphene oxides, the 2- bromine isobutyl acylbromides of 40mL, 18mL is dispersed in the N of 70mL, N- bis-
In NMF, it is transferred in ice-water bath and reacts 24 hours, the oxidation stone containing initiation group is obtained after centrifugation, washing, drying
Black alkene；
2) containing 0.06g triggers the graphene oxide of group to be dispersed in the deionized water of 8mL, in argon gas atmosphere condition
Under be separately added into 5mg stannous chlorides, 1mg copper chlorides, 0.25mmol bipyridines, 1.6mmol SSSs, 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 acids are grafted is dispersed in 35mL water, adds 0.7g ascorbic acid,
Reacted 18-24 hours at 90 DEG C, polystyrolsulfon acid graft grapheme is obtained after centrifugation, washing, drying；
4) 0.1g polystyrolsulfon acid graft graphemes are dispersed in 15mL water, add the pyrroles of 100 μ L, stir 40 points
Zhong Hou, adds the ammonium persulfate of 2mmol.After being again stirring for 4 minutes, reaction 30 hours are stood at 15 DEG C, be washed with deionized water
Wash, obtain polystyrolsulfon acid graft grapheme/polypyrrole composite aquogel.
Embodiment 4
1) triethylamine of 0.75g graphene oxides, the 2- bromine isobutyl acylbromides of 45mL, 20mL is dispersed in three chloromethanes of 80mL
In alkane, it is transferred in ice-water bath and reacts 48 hours, the graphene oxide containing initiation group is obtained after centrifugation, washing, drying；
2) containing 0.08g triggers the graphene oxide of group to be dispersed in the deionized water of 8mL, in argon gas atmosphere condition
Under be separately added into 5mg cuprous bromides, 0.9mg copper bromides, 0.25mmol bipyridines, 1.6mmol SSSs, 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 acids are grafted is dispersed in 30-50mL water, adds 0.5-
0.8g Tea Polyphenols, is reacted 18-24 hours at 90 DEG C, and polystyrolsulfon acid graft grapheme is obtained after centrifugation, washing, drying；
4) 0.15g polystyrolsulfon acid graft graphemes are dispersed in 20mL water, add the pyrroles of 150 μ L, stirring 50
After minute, the iron chloride of 6mmol is added.After being again stirring for 5 minutes, reaction 30 hours are stood at 20 DEG C, be washed with deionized water
Wash, obtain polystyrolsulfon acid graft grapheme/polypyrrole composite aquogel.
Embodiment 5
1) triethylamine of 1g graphene oxides, the 2- bromine isobutyl acylbromides of 50mL, 20mL is dispersed in the N of 90mL, N- diformazans
In base formamide, it is transferred in ice-water bath and reacts 40 hours, the graphite oxide containing initiation group is obtained after centrifugation, washing, drying
Alkene；
2) containing 0.1g triggers the graphene oxide of group to be dispersed in the deionized water of 10mL, in argon gas atmosphere condition
Under be separately added into 6mg cuprous bromides, 1.2mg copper bromides, 0.3mmol bipyridines, 2mmol SSSs, 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 acids are grafted is dispersed in 50mL water, adds 0.8g ascorbic acid,
Reacted 24 hours at 90 DEG C, polystyrolsulfon acid graft grapheme is obtained after centrifugation, washing, drying；
4) 0.2g polystyrolsulfon acid graft graphemes are dispersed in 20mL water, add the pyrroles of 200 μ L, stir 60 points
Zhong Hou, adds the ferric nitrate of 5mmol.After being again stirring for 5 minutes, reaction 36 hours are stood at 20 DEG C, are washed with deionized,
Obtain polystyrolsulfon acid graft grapheme/polypyrrole composite aquogel.
Embodiment 6
1) triethylamine of 0.6g graphene oxides, the 2- bromine isobutyl acylbromides of 35mL, 16mL is dispersed in three chloromethanes of 80mL
In alkane, it is transferred in ice-water bath and reacts 24 hours, the graphene oxide containing initiation group is obtained after centrifugation, washing, drying；
2) containing 0.04g triggers the graphene oxide of group to be dispersed in the deionized water of 7mL, in argon gas atmosphere condition
Under be separately added into 4mg cuprous bromides, 0.8mg copper bromides, 0.2mmol bipyridines, 1.4mmol SSSs, 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 acids are grafted is dispersed in 40mL water, adds 0.7g ascorbic acid,
Reacted 18 hours at 90 DEG C, polystyrolsulfon acid graft grapheme is obtained after centrifugation, washing, drying；
4) 0.1g polystyrolsulfon acid graft graphemes are dispersed in 10-20mL water, add the pyrroles of 100 μ L, stirring
After 40 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/polypyrrole composite aquogel.
To understand the Electro-stimulate response of polystyrolsulfon acid graft grapheme/polypyrrole composite aquogel prepared by the present invention
And drug controlled release performance, We conducted related experiment.Take the polystyrolsulfon acid grafting stone of the preparation of 50mg embodiments 5
Black alkene/polypyrrole composite aquogel, places it in containing immersion one hour in salicylic PBS, then taken
Go out to be placed in not salicylated PBS, carry out electro photoluminescence release.Regulation applied voltage is 0V or 1.0V, every
2mL solution is drawn from solution within 0.5 hour, determine salicylic content, while supplementing the PBS of same volume.It is salicylic to contain
Amount is determined using ultraviolet spectrophotometry at 298nm, is released according to the accumulation that the salicylic acid content for determining calculates different time
Medicine percentage.Result shows, in 0V by after 6 hours, salicylic cumulative release percentage is 11%；In 1.0V, warp
After spending 6 hours, salicylic cumulative release percentage is 57%, shows obvious electroresponsive release behavior.This
Because under high electric field, polypyrrole strand shows the state more expanded, be conducive to the release of small-molecule drug.By water
Poplar acid is changed to dexamethasone or quadracycline and has also drawn same conclusion.
Claims (10)
1. the preparation method of polystyrolsulfon acid graft grapheme/polypyrrole composite aquogel, it is characterised in that including following step
Suddenly：(1) graphene oxide, 2- bromine isobutyl acylbromides, triethylamine dispersion are obtained containing initiation in organic solvent, after the completion of reaction
The graphene oxide of group；(2) it is water-dispersible containing trigger group graphene oxide, under protective atmosphere add catalyst,
Anti-activator, bipyridine and SSS are reacted, and obtain the graphene oxide of polystyrolsulfon acid grafting；(3)
The graphene oxide of water-dispersible polystyrolsulfon acid grafting, adds reducing agent to be reacted, and obtains polystyrolsulfon acid grafting
Graphene；(4) water-dispersible polystyrolsulfon acid graft grapheme, adds pyrroles and oxidant to be reacted, and obtains polyphenyl second
Alkene Sulphonic Acid Functionalized Graphene/polypyrrole composite aquogel.
2. the preparation method of polystyrolsulfon acid graft grapheme/polypyrrole composite aquogel as claimed in claim 1, it is special
Levy and be：Graphene oxide, 2- bromine isobutyl acylbromides, the amount ratio of triethylamine are 1g in step (1):20-100mL:10-40mL.
3. the preparation method of polystyrolsulfon acid graft grapheme/polypyrrole composite aquogel as claimed in claim 1, it is special
Levy and be：Step (1) described organic solvent is chloroform or DMF, and reaction condition is ice-water bath, reaction
Time is 24-48h, is reacted after completing through centrifugation, washing, the dry graphene oxide that must contain initiation group.
4. the preparation method of polystyrolsulfon acid graft grapheme/polypyrrole composite aquogel as claimed in claim 1, it is special
Levy and be：Contain graphene oxide, catalyst, anti-activator, bipyridine and the styrene sulfonic acid for triggering group in step (2)
The mass ratio of sodium is 8-200:2.5-12:1:19-95:206-825.
5. the preparation method of polystyrolsulfon acid graft grapheme/polypyrrole composite aquogel as claimed in claim 1, it is special
Levy and be：Reaction temperature is 10-30 DEG C in step (2), and the reaction time is 6-12h, and protection gas is argon gas, and product is through being centrifuged, washing
Wash, the graphene oxide of dry polystyrolsulfon acid grafting.
6. the preparation method of polystyrolsulfon acid graft grapheme/polypyrrole composite aquogel as claimed in claim 1, it is special
Levy and be：The graphene oxide of polystyrolsulfon acid grafting and the mass ratio of reducing agent are 1 in step (3):2.5-8, reaction temperature
It is 90 DEG C to spend, and the reaction time is 18-24h, and product is through centrifugation, washing, dry polystyrolsulfon acid graft grapheme.
7. the preparation method of polystyrolsulfon acid graft grapheme/polypyrrole composite aquogel as claimed in claim 1, it is special
Levy and be：Step (2) described catalyst is stannous chloride or cuprous bromide, and the anti-activator is copper chloride or copper bromide, step
(3) reducing agent is the one kind in ascorbic acid or Tea Polyphenols.
8. the preparation method of polystyrolsulfon acid graft grapheme/polypyrrole composite aquogel as claimed in claim 1, it is special
Levy and be：The amount ratio of polystyrolsulfon acid graft grapheme, pyrroles and oxidant is 0.25-4g in step (4):1mL:
0.8-48g, to pyrrolo- stirring 30-60min is added in polystyrolsulfon acid graft grapheme dispersion liquid before reaction, adds oxygen
Agent stirs 2-5min, and reaction 24-36h is stood at 10-20 DEG C, carries out washing with deionized water and obtains final product.
9. the preparation method of polystyrolsulfon acid graft grapheme/polypyrrole composite aquogel as claimed in claim 1, it is special
Levy and be：Step (4) described oxidant is the one kind in iron chloride, ferric nitrate, ferric sulfate or ammonium persulfate.
10. the polystyrolsulfon acid graft grapheme/polypyrrole composite aquogel described in any one of claim 1-9 is used as medicine
The application of controlled release material.
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| CN102543463A (en) * | 2011-12-13 | 2012-07-04 | 武汉工程大学 | Water-soluble graphene used for super capacitor electrode material and preparation method thereof |
| CN105733260A (en) * | 2016-03-02 | 2016-07-06 | 廖彩芬 | Graphene/conducive macromolecular polymer aerogel and preparation method thereof |
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| CN102543463A (en) * | 2011-12-13 | 2012-07-04 | 武汉工程大学 | Water-soluble graphene used for super capacitor electrode material and preparation method thereof |
| CN105733260A (en) * | 2016-03-02 | 2016-07-06 | 廖彩芬 | Graphene/conducive macromolecular polymer aerogel and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| SUN HWA LEE ET AL.: "Polymer Brushes via Controlled, Surface-Initiated Atom Transfer Radical Polymerization (ATRP) from Graphene Oxide", 《MACROMOLECULAR RAPID COMMUNICATIONS》 * |
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