CN107043464B - The preparation method of polystyrolsulfon acid graft grapheme/poly- (3,4- Ethylenedioxy Thiophene) composite conducting hydrogel - Google Patents
The preparation method of polystyrolsulfon acid graft grapheme/poly- (3,4- Ethylenedioxy Thiophene) composite conducting hydrogel Download PDFInfo
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- A61K47/34—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyesters, polyamino acids, polysiloxanes, polyphosphazines, copolymers of polyalkylene glycol or poloxamers
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- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/0002—Galenical forms characterised by the drug release technique; Application systems commanded by energy
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- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/10—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to inorganic materials
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- C—CHEMISTRY; METALLURGY
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- C08J2465/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
Abstract
The present invention relates to a kind of polystyrolsulfon acid graft grapheme/poly- (3 of controlled drug release, 4- Ethylenedioxy Thiophene) composite conducting hydrogel preparation method, this method is first in surface of graphene oxide grafted polystyrene sulfonic acid, the polystyrolsulfon acid graft grapheme with excellent dissolution performance is obtained by reduction treatment, the addition of polystyrolsulfon acid graft grapheme is contained 3 again, in the mixed solution of 4- Ethylenedioxy Thiophene and drug, make 3 under the conditions of existing for the oxidant, the polymerization of 4- Ethylenedioxy Thiophene and the self assembly of composite hydrogel carry out simultaneously.The composite conducting hydrogel being prepared has good mechanical strength, and the control release of drug can be achieved under electro photoluminescence.
Description
Technical field
The present invention relates to hydrogel technical field of function materials, and in particular to a kind of polystyrene sulphur of controlled drug release
Sour graft grapheme/poly- (3,4- Ethylenedioxy Thiophene) composite conducting hydrogel and preparation method thereof.
Background technique
Composite conducting hydrogel is got more and more extensive concerning of people as one kind in intelligent gel.Composite guide at present
The research emphasis of electric hydrogel is also converted to inorganic material addition conductive hydrogel and conduction from initial polyelectrolytes hydrogel
Macromolecule composite hydrogel.Composite conducting hydrogel combines advantage of both conductive material and hydrogel, in electro photoluminescence medicine
There is good application prospect in the fields such as object release, supercapacitor, however how to realize that inorganic material or conducting polymer exist
Being uniformly distributed in hydrogel matrix is still one of difficult point of research.
Graphene is a kind of New Two Dimensional nano inorganic carbon material being made of one layer of carbon atom, is most thin by two in the world
One of material is tieed up, graphene has excellent electric property and excellent mechanical property.As the predecessor of synthesizing graphite alkene, oxygen
Containing numerous functional groups such as hydroxyl, carboxyl and epoxy groups on the molecular structure of graphite alkene, it can dissolve well and be dispersed in water
Or in organic solvent, but by graphene oxide restore obtained graphene be but difficult again it is evenly dispersed in water.To sum up
It is described, how graphene to be introduced into hydrogel matrix and realize that it is evenly dispersed in hydrogel, while can controlled multiple
The size and external form and electric property, mechanical property of conjunction conductive hydrogel, there are still bigger difficulty.
Summary of the invention
It is an object of the invention to overcome the above problem present in existing composite conducting hydrogel preparation process, one is provided
Polystyrolsulfon acid graft grapheme/poly- (3,4- Ethylenedioxy Thiophene) composite conducting hydrogel of kind of controlled drug release and
Preparation method, this method in surface of graphene oxide grafted polystyrene sulfonic acid, are then passed through reduction treatment and are had first
There is the polystyrolsulfon acid graft grapheme of excellent dissolution performance, then by polystyrolsulfon acid graft grapheme and contains the Asia 3,4-
The drug mixed solution and oxidant of ethylenedioxy thiophene are reacted, ensure that the polymerization of 3,4- Ethylenedioxy Thiophene with
The self assembly of composite hydrogel carries out simultaneously, finally obtain controlled drug release polystyrolsulfon acid graft grapheme/it is poly- (3,
4- Ethylenedioxy Thiophene) composite conducting hydrogel.To achieve the above object, the technical solution adopted in the present invention is as follows:
The preparation side of polystyrolsulfon acid graft grapheme/poly- (3,4- Ethylenedioxy Thiophene) composite conducting hydrogel
Method, comprising the following steps: (1) in organic solvent by graphene oxide, 2- bromine isobutyl acylbromide, triethylamine dispersion, reaction is completed
It is obtained afterwards containing the graphene oxide for causing group；(2) water-dispersible containing the graphene oxide for causing group, in protective atmosphere
Lower addition catalyst, anti-activator, bipyridine and sodium styrene sulfonate are reacted, and the oxygen of polystyrolsulfon acid grafting is obtained
Graphite alkene；(3) graphene oxide of water-dispersible polystyrolsulfon acid grafting, is added reducing agent and is reacted, obtain polyphenyl
Vinyl sulfonic acid graft grapheme；(4) polystyrolsulfon acid graft grapheme is dispersed in containing 3,4- Ethylenedioxy Thiophene, medicine
In the aqueous solution of object, oxidant is added and is reacted, polystyrolsulfon acid graft grapheme/poly- (3,4- Asia second two are finally obtained
Oxygroup thiophene) composite conducting 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 be 8-200:2.5-12:1:19-95:206-825, the catalyst be stannous chloride or
Cuprous bromide, the anti-activator are copper chloride or copper bromide.
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, wherein the reducing agent is specially one of ascorbic acid or tea polyphenols.
According to above scheme, polystyrolsulfon acid graft grapheme, 3,4- Ethylenedioxy Thiophene, drug in step (4)
And the amount ratio of oxidant is 0.25-4g:1mL:0.05-2g:8-240g.
According to above scheme, polystyrolsulfon acid graft grapheme is dispersed in containing the Asia 3,4- second dioxy in step (4)
Base thiophene, drug aqueous solution in, stir 30-60min, be added oxidant after be again stirring for 2-5min, mixed solution is placed in
10-20 DEG C of standing reacts 24-36h, 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.
According to above scheme, the drug is penicillin, nifedipine, dexamethasone, N'-Dimethylguanylguanidine hydrochloride or bigcatkin willow
One of acid, the concentration of drug is 1-5mg/mL in aqueous solution.
Compared with prior art, the invention has the following advantages: (1) graphene and poly- (3,4- ethylenedioxy thiophenes
Pheno) good chemical property makes composite hydrogel that the control release of drug can be achieved under electro photoluminescence；(2) by polystyrene
Sulphonic Acid Functionalized improves the solubility property of graphene to graphene surface；(3) polystyrolsulfon acid graft grapheme and it is poly- (3,
4- Ethylenedioxy Thiophene) between zwitterion interaction, π-πconjugation, hydrogen bond etc. so that composite conducting hydrogel
With good mechanical strength；(4) static monitor of poly- (3,4- Ethylenedioxy Thiophene) and composite conducting hydrogel from group
It fills while carrying out, preparation method is simple.
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.
Raw material used in 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 containing 50 μ L 3,4- Ethylenedioxy Thiophenes and
In the 10mL aqueous solution of 1mg/mL dexamethasone, after stirring 30 minutes, the ferric nitrate of 10mmol is added.After being again stirring for 2 minutes,
Reaction 24 hours are stood at 10 DEG C, are washed with deionized, and the polystyrolsulfon acid grafting graphite for being loaded with dexamethasone is obtained
Alkene/poly- (3,4- Ethylenedioxy Thiophene) composite conducting 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 containing 75 μ L 3,4- Ethylenedioxy Thiophenes and
In the salicylic 15mL aqueous solution of 1mg/mL, after stirring 45 minutes, the ferric sulfate of 15mmol is added.After being again stirring for 3 minutes,
Reaction 30 hours are stood at 20 DEG C, are washed with deionized, and obtain being loaded with salicylic polystyrolsulfon acid graft grapheme/poly-
(3,4- Ethylenedioxy Thiophene) composite conducting 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, 1.6mmo 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 containing 100 μ L 3,4- Ethylenedioxy Thiophenes and
In the 15mL aqueous solution of 5mg/mL penicillin, after forty minutes, the ammonium persulfate of 20mmol is added in stirring.After being again stirring for 4 minutes,
Stand reaction 28 hours at 15 DEG C, be washed with deionized, obtain being loaded with the polystyrolsulfon acid graft grapheme of penicillin/
Poly- (3,4- Ethylenedioxy Thiophene) composite conducting 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, is placed in ice-water bath and reacts 48 hours, obtain 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, 1.6mmo 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 containing 150 μ L 3,4- Ethylenedioxy Thiophenes and
In the 20mL aqueous solution of 2mg/mL N'-Dimethylguanylguanidine hydrochloride, after stirring 50 minutes, the iron chloride of 20mmol is added.It is again stirring for 5
After minute, reaction 36 hours are stood at 20 DEG C, is washed with deionized, obtains the polystyrene for being loaded with N'-Dimethylguanylguanidine hydrochloride
Sulphonic Acid Functionalized graphene/poly- (3,4- Ethylenedioxy Thiophene) composite conducting 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, is placed in ice-water bath and reacts 40 hours, obtain after centrifugation, washing, drying containing the graphite oxide for causing group
Alkene；
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, 2mmo sodium styrene sulfonate, it is anti-at 25 DEG C
It answers 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 containing 200 μ L 3,4- Ethylenedioxy Thiophenes and
In the 20mL aqueous solution of 4mg/mL nifedipine, after sixty minutes, the ferric nitrate of 30mmol is added in stirring.It is again stirring for after five minutes,
Reaction 32 hours are stood at 20 DEG C, are washed with deionized, and the polystyrolsulfon acid grafting graphite for being loaded with nifedipine is obtained
Alkene/poly- (3,4- Ethylenedioxy Thiophene) composite conducting hydrogel.
Claims (9)
- The preparation method of polystyrolsulfon acid graft grapheme/poly- 1. (3,4- Ethylenedioxy Thiophene) composite conducting hydrogel, Characterized by 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 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) by polystyrolsulfon acid graft grapheme be dispersed in containing 3,4- Ethylenedioxy Thiophene, drug aqueous solution in, add Enter oxidant to be reacted, finally obtains polystyrolsulfon acid graft grapheme/poly- (3,4- Ethylenedioxy Thiophene) composite guide Electric hydrogel；Wherein, polystyrolsulfon acid graft grapheme in step (4), 3,4- Ethylenedioxy Thiophene, drug and oxidant Amount ratio is 0.25-4g:1mL:0.05-2g:8-240g.
- Polystyrolsulfon acid graft grapheme as described in claim 1/poly- 2. (3,4- Ethylenedioxy Thiophene) composite conducting The preparation method of hydrogel, it is characterised in that: graphene oxide in step (1), 2- bromine isobutyl acylbromide, triethylamine amount ratio be 1g:20-100mL:10-40mL.
- Polystyrolsulfon acid graft grapheme as described in claim 1/poly- 3. (3,4- Ethylenedioxy Thiophene) composite conducting The preparation method of hydrogel, it is characterised in that: step (1) organic solvent be chloroform or n,N-Dimethylformamide, Reaction condition is ice-water bath, reaction time 24-48h, after the reaction was completed through centrifugation, washing, dry containing causing group Graphene oxide.
- Polystyrolsulfon acid graft grapheme as described in claim 1/poly- 4. (3,4- Ethylenedioxy Thiophene) composite conducting The preparation method of hydrogel, it is characterised in that: in step (2) containing cause the graphene oxide of group, catalyst, anti-activator, Bipyridine and the mass ratio of sodium styrene sulfonate are 8-200:2.5-12:1:19-95:206-825, and the catalyst is chlorine Change cuprous or cuprous bromide, the anti-activator is copper chloride or copper bromide.
- Polystyrolsulfon acid graft grapheme as described in claim 1/poly- 5. (3,4- Ethylenedioxy Thiophene) composite conducting The preparation method of hydrogel, it is characterised in that: reaction temperature is 10-30 DEG C, reaction time 6-12h in step (2), protects gas For argon gas, graphene oxide that product is grafted through centrifugation, washing, dry polystyrolsulfon acid.
- Polystyrolsulfon acid graft grapheme as described in claim 1/poly- 6. (3,4- Ethylenedioxy Thiophene) composite conducting The preparation method of hydrogel, it is characterised in that: the matter of polystyrolsulfon acid is grafted in step (3) graphene oxide and reducing agent Amount is than being 1:2.5-8, and reaction temperature is 90 DEG C, reaction time 18-24h, and product is through centrifugation, washing, dry polystyrene Sulphonic Acid Functionalized graphene, wherein reducing agent is one of ascorbic acid or tea polyphenols.
- Polystyrolsulfon acid graft grapheme as described in claim 1/poly- 7. (3,4- Ethylenedioxy Thiophene) composite conducting The preparation method of hydrogel, it is characterised in that: polystyrolsulfon acid graft grapheme is dispersed in containing the Asia 3,4- in step (4) Ethylenedioxy thiophene, drug aqueous solution in, stir 30-60min, be added oxidant after be again stirring for 2-5min, will mix molten Liquid is placed in 10-20 DEG C of standing reaction 24-36h, is washed with deionized water to obtain the final product.
- Polystyrolsulfon acid graft grapheme as described in claim 1/poly- 8. (3,4- Ethylenedioxy Thiophene) composite conducting The preparation method of hydrogel, it is characterised in that: the oxidant is one in iron chloride, ferric nitrate, ferric sulfate or ammonium persulfate Kind.
- Polystyrolsulfon acid graft grapheme as described in claim 1/poly- 9. (3,4- Ethylenedioxy Thiophene) composite conducting The preparation method of hydrogel, it is characterised in that: the drug is penicillin, nifedipine, dexamethasone, N'-Dimethylguanylguanidine hydrochloride Or one of salicylic acid, the concentration of drug is 1-5mg/mL in aqueous solution.
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