CN107043464A - 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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- 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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- 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 Thiophenes) 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, polystyrolsulfon acid graft grapheme is added again and contains 3, in the mixed solution of 4 Ethylenedioxy Thiophenes and medicine, make 3 under conditions of oxidant presence, the polymerization of 4 Ethylenedioxy Thiophenes and the self assembly of composite aquogel are carried out simultaneously.The composite conducting hydrogel prepared has good mechanical strength, and the control release of medicine 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 Thiophenes) composite conducting hydrogel and preparation method thereof.
Background technology
Composite conducting hydrogel increasingly gets more and more people's extensive concerning as the class in intelligent gel.Current composite guide
The research emphasis of electric hydrogel is also converted to inorganic material addition conductive hydrogel and conduction from initial polyelectrolytes hydrogel
Macromolecule composite aquogel.Composite conducting hydrogel combines conductive material and advantage of both hydrogel, in electro photoluminescence medicine
There is good application prospect in the fields such as thing release, ultracapacitor, but 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 up 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.It is used as the predecessor of synthesizing graphite alkene, oxygen
Containing numerous functional groups such as hydroxyl, carboxyl and epoxy radicals on the molecular structure of graphite alkene, it can well dissolve and be dispersed in water
Or in organic solvent, but it is but difficult to be dispersed in again in water to reduce resulting graphene by graphene oxide.To sum up
It is described, how graphene is introduced into hydrogel matrix and realizes that it is dispersed in hydrogel, while can control multiple
The size and external form and electric property, mechanical property of conductive hydrogel are closed, bigger difficulty is still suffered from.
The content of the invention
It is an object of the invention to overcome above mentioned problem present in existing composite conducting hydrogel preparation process, there is provided one
Polystyrolsulfon acid graft grapheme/poly- (3,4- Ethylenedioxy Thiophenes) composite conducting hydrogel of kind of controlled drug release and
Its preparation method, this method in surface of graphene oxide grafted polystyrene sulfonic acid, is then passed through reduction treatment and had first
There is the polystyrolsulfon acid graft grapheme of excellent dissolution performance, then by polystyrolsulfon acid graft grapheme and contain 3,4- Asias
The medicine mixed solution and oxidant of ethylenedioxy thiophene are reacted, it is ensured that the polymerization of 3,4- Ethylenedioxy Thiophenes with
The self assembly of composite aquogel is carried out simultaneously, finally give controlled drug release polystyrolsulfon acid graft grapheme/poly- (3,
4- Ethylenedioxy Thiophenes) 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 Thiophenes) composite conducting hydrogel
Method, comprises the following steps：(1) graphene oxide, 2- bromine isobutyl acylbromides, triethylamine is scattered in organic solvent, reaction is completed
Obtain afterwards containing the graphene oxide for triggering group；(2) it is water-dispersible containing the graphene oxide for triggering group, in protective atmosphere
Lower addition catalyst, anti-activator, bipyridine and SSS are reacted, and obtain the oxygen of polystyrolsulfon acid grafting
Graphite alkene；(3) graphene oxide of water-dispersible polystyrolsulfon acid grafting, adds reducing agent and is reacted, obtain polyphenyl
Vinyl sulfonic acid graft grapheme；(4) polystyrolsulfon acid graft grapheme is dispersed in containing 3,4- Ethylenedioxy Thiophenes, medicine
In the aqueous solution of thing, add oxidant and reacted, finally give polystyrolsulfon acid graft grapheme/poly- (3,4- sub- second two
Epoxide thiophene) composite conducting hydrogel.
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
For ice-water bath, the reaction time is 24-48h, reaction complete after through centrifugation, washing, it is dry obtain containing trigger group graphite oxide
Alkene.
According to such scheme, contain graphene oxide, catalyst, anti-activator, the bipyridine for triggering group in step (2)
And the mass ratio of SSS is 8-200:2.5-12:1:19-95:206-825, the catalyst be stannous chloride or
Cuprous bromide, the anti-activator is copper chloride or copper bromide.
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,
Product through centrifugation, washing, the grafting of dry polystyrolsulfon acid graphene oxide.
According to such scheme, the graphene oxide and the mass ratio of reducing agent that polystyrolsulfon acid is grafted in step (3) are
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, wherein the reducing agent is specially one kind in ascorbic acid or Tea Polyphenols.
According to such scheme, polystyrolsulfon acid graft grapheme, 3,4- Ethylenedioxy Thiophenes, medicine in step (4)
And the amount ratio of oxidant is 0.25-4g:1mL:0.05-2g:8-240g.
According to such scheme, polystyrolsulfon acid graft grapheme is dispersed in containing the sub- second dioxies of 3,4- in step (4)
In base thiophene, the aqueous solution of medicine, 30-60min is stirred, 2-5min is again stirring for after adding oxidant, mixed solution is placed in
10-20 DEG C stands reaction 24-36h, carries out washing with deionized water and produces.
According to such scheme, the oxidant is one kind in iron chloride, ferric nitrate, ferric sulfate or ammonium persulfate.
According to such scheme, the medicine is penicillin, nifedipine, dexamethasone, N'-Dimethylguanylguanidine hydrochloride or bigcatkin willow
The concentration of medicine is 1-5mg/mL in one kind in acid, the aqueous solution.
Compared with prior art, the invention has the advantages that：(1) graphene and poly- (3,4- ethylenedioxy thiophenes
Fen) good chemical property cause composite aquogel under electro photoluminescence can be achieved medicine control release；(2) by polystyrene
Sulphonic Acid Functionalized improves the solubility property of graphene to graphenic surface；(3) polystyrolsulfon acid graft grapheme with it is poly- (3,
4- Ethylenedioxy Thiophenes) 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 Thiophenes) and composite conducting hydrogel are from group
Dress is carried out simultaneously, and preparation method is simple and easy to apply.
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 embodiments, equally fall into protection scope of the present invention it
It is interior.
Raw material 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 triethylamine are dispersed in 50mL three chloromethanes
In alkane, it is placed in ice-water bath and reacts 24 hours, is obtained after centrifugation, washing, drying containing the graphene oxide for triggering group；
2) containing 0.02g triggers the graphene oxide of group to be dispersed in 4mL deionized water, in argon gas atmosphere condition
Under be separately added into 3mg stannous chlorides, 0.5mg copper chlorides, 0.15mmol bipyridines, 1.2mmol SSSs, at 20 DEG C
Lower reaction 6 hours, obtains the graphene oxide of polystyrolsulfon acid grafting after centrifugation, washing, drying；
3) graphene oxide for being grafted 0.1g polystyrolsulfon acids 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 containing 50 μ L 3,4- Ethylenedioxy Thiophenes and
In the 10mL aqueous solution of 1mg/mL dexamethasone, after stirring 30 minutes, 10mmol ferric nitrate is added.It is again stirring for after 2 minutes,
Reaction 24 hours are stood at 10 DEG C, are washed with deionized, obtain being loaded with the polystyrolsulfon acid grafting graphite of dexamethasone
Alkene/poly- (3,4- Ethylenedioxy Thiophenes) composite conducting hydrogel.
Embodiment 2
1) 0.6g graphene oxides, 30mL 2- bromine isobutyl acylbromides, 10mL triethylamine are dispersed in 60mL N, N- bis-
In NMF, it is placed in ice-water bath and reacts 30 hours, is obtained after centrifugation, washing, drying containing the oxidation stone for triggering group
Black alkene；
2) containing 0.05g triggers the graphene oxide of group to be dispersed in 6mL deionized water, 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 for being grafted 0.12g polystyrolsulfon acids 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 containing 75 μ L 3,4- Ethylenedioxy Thiophenes and
In the salicylic 15mL aqueous solution of 1mg/mL, after stirring 45 minutes, 15mmol ferric sulfate is added.It is again stirring for after 3 minutes,
Reaction 30 hours are stood at 20 DEG C, are washed with deionized, obtain being loaded with salicylic polystyrolsulfon acid graft grapheme/poly-
(3,4- Ethylenedioxy Thiophenes) composite conducting hydrogel.
Embodiment 3
1) 0.8g graphene oxides, 40mL 2- bromine isobutyl acylbromides, 18mL triethylamine are dispersed in 70mL N, N- bis-
In NMF, it is placed in ice-water bath and reacts 24 hours, is obtained after centrifugation, washing, drying containing the oxidation stone for triggering group
Black alkene；
2) containing 0.06g triggers the graphene oxide of group to be dispersed in 8mL deionized water, in argon gas atmosphere condition
Under be separately added into 5mg stannous chlorides, 1mg copper chlorides, 0.25mmol bipyridines, 1.6mmo SSSs, at 25 DEG C
Reaction 6-12 hours, obtains the graphene oxide of polystyrolsulfon acid grafting after centrifugation, washing, drying；
3) graphene oxide for being grafted 0.1g polystyrolsulfon acids 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 containing 100 μ L 3,4- Ethylenedioxy Thiophenes and
In the 15mL aqueous solution of 5mg/mL penicillin, after stirring 40 minutes, 20mmol ammonium persulfate is added.It is again stirring for after 4 minutes,
Reaction 28 hours are stood at 15 DEG C, are washed with deionized, obtain being loaded with the polystyrolsulfon acid graft grapheme of penicillin/
Poly- (3,4- Ethylenedioxy Thiophenes) composite conducting hydrogel.
Embodiment 4
1) 0.75g graphene oxides, 45mL 2- bromine isobutyl acylbromides, 20mL triethylamine are dispersed in 80mL three chloromethanes
In alkane, it is placed in ice-water bath and reacts 48 hours, is obtained after centrifugation, washing, drying containing the graphene oxide for triggering group；
2) containing 0.08g triggers the graphene oxide of group to be dispersed in 8mL deionized water, in argon gas atmosphere condition
Under be separately added into 5mg cuprous bromides, 0.9mg copper bromides, 0.25mmol bipyridines, 1.6mmo SSSs, at 30 DEG C
Lower reaction 10 hours, obtains the graphene oxide of polystyrolsulfon acid grafting after centrifugation, washing, drying；
3) graphene oxide for being grafted 0.1-0.2g polystyrolsulfon acids 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 containing 150 μ L 3,4- Ethylenedioxy Thiophenes and
In the 20mL aqueous solution of 2mg/mL N'-Dimethylguanylguanidine hydrochlorides, after stirring 50 minutes, 20mmol iron chloride is added.It is again stirring for 5
After minute, reaction 36 hours are stood at 20 DEG C, is washed with deionized, obtains being loaded with the polystyrene of N'-Dimethylguanylguanidine hydrochloride
Sulphonic Acid Functionalized graphene/poly- (3,4- Ethylenedioxy Thiophenes) composite conducting hydrogel.
Embodiment 5
1) 1g graphene oxides, 50mL 2- bromine isobutyl acylbromides, 20mL triethylamine are dispersed in 90mL N, N- diformazans
In base formamide, it is placed in ice-water bath and reacts 40 hours, is obtained after centrifugation, washing, drying containing the graphite oxide for triggering group
Alkene；
2) containing 0.1g triggers the graphene oxide of group to be dispersed in 10mL deionized water, in argon gas atmosphere condition
Under be separately added into 6mg cuprous bromides, 1.2mg copper bromides, 0.3mmol bipyridines, 2mmo SSSs, it is anti-at 25 DEG C
Answer 12 hours, the graphene oxide of polystyrolsulfon acid grafting is obtained after centrifugation, washing, drying；
3) graphene oxide for being grafted 0.2g polystyrolsulfon acids 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 containing 200 μ L 3,4- Ethylenedioxy Thiophenes and
In the 20mL aqueous solution of 4mg/mL nifedipines, after stirring 60 minutes, 30mmol ferric nitrate is added.It is again stirring for after 5 minutes,
Reaction 32 hours are stood at 20 DEG C, are washed with deionized, obtain being loaded with the polystyrolsulfon acid grafting graphite of nifedipine
Alkene/poly- (3,4- Ethylenedioxy Thiophenes) composite conducting hydrogel.
Claims (10)
- The preparation method of polystyrolsulfon acid graft grapheme/poly- 1. (3,4- Ethylenedioxy Thiophene) composite conducting hydrogel, It is characterised in that it includes following steps：It is (1) graphene oxide, 2- bromine isobutyl acylbromides, triethylamine is scattered in organic solvent, Obtained after the completion of reaction containing the graphene oxide for triggering group；(2) the water-dispersible graphene oxide containing initiation group, Catalyst, anti-activator, bipyridine and SSS are added under protective atmosphere to be reacted, and obtain polystyrolsulfon acid The graphene oxide of grafting；(3) graphene oxide of water-dispersible polystyrolsulfon acid grafting, adds reducing agent and is reacted, Obtain polystyrolsulfon acid graft grapheme；(4) polystyrolsulfon acid graft grapheme is dispersed in containing the sub- second dioxies of 3,4- In base thiophene, the aqueous solution of medicine, add oxidant and reacted, finally give polystyrolsulfon acid graft grapheme/poly- (3, 4- Ethylenedioxy Thiophenes) composite conducting hydrogel.
- Polystyrolsulfon acid graft grapheme as claimed in claim 1/poly- 2. (3,4- Ethylenedioxy Thiophenes) composite conducting The preparation method of hydrogel, it is characterised in that：Graphene oxide, 2- bromine isobutyl acylbromides, the amount ratio of triethylamine are in step (1) 1g：20-100mL：10-40mL.
- Polystyrolsulfon acid graft grapheme as claimed in claim 1/poly- 3. (3,4- Ethylenedioxy Thiophenes) composite conducting The preparation method of hydrogel, it is characterised in that：Step (1) described organic solvent be chloroform or DMF, Reaction condition is ice-water bath, the reaction time is 24-48h, reaction complete after through centrifugation, washing, it is dry must be containing triggering group Graphene oxide.
- Polystyrolsulfon acid graft grapheme as claimed in claim 1/poly- 4. (3,4- Ethylenedioxy Thiophenes) composite conducting The preparation method of hydrogel, it is characterised in that：In step (2) containing trigger the graphene oxide of group, catalyst, anti-activator, The mass ratio of bipyridine and SSS is 8-200:2.5-12:1:19-95:206-825, the catalyst is chlorine Change cuprous or cuprous bromide, the anti-activator is copper chloride or copper bromide.
- Polystyrolsulfon acid graft grapheme as claimed in claim 1/poly- 5. (3,4- Ethylenedioxy Thiophenes) composite conducting The preparation method of hydrogel, it is characterised in that：Reaction temperature is 10-30 DEG C in step (2), and the reaction time is 6-12h, protects gas For argon gas, the graphene oxide that product is grafted through centrifugation, washing, dry polystyrolsulfon acid.
- Polystyrolsulfon acid graft grapheme as claimed in claim 1/poly- 6. (3,4- Ethylenedioxy Thiophenes) composite conducting The preparation method of hydrogel, it is characterised in that：Polystyrolsulfon acid is grafted in step (3) graphene oxide and the matter of reducing agent Amount is than being 1:2.5-8, reaction temperature is 90 DEG C, and the reaction time is 18-24h, and product is through centrifugation, washing, dry polystyrene Sulphonic Acid Functionalized graphene, wherein reducing agent are one kind in ascorbic acid or Tea Polyphenols.
- Polystyrolsulfon acid graft grapheme as claimed in claim 1/poly- 7. (3,4- Ethylenedioxy Thiophenes) composite conducting The preparation method of hydrogel, it is characterised in that：Polystyrolsulfon acid graft grapheme, 3,4- ethylenedioxy thiophenes in step (4) The amount ratio of fen, medicine and oxidant is 0.25-4g:1mL:0.05-2g:8-240g.
- Polystyrolsulfon acid graft grapheme as claimed in claim 1/poly- 8. (3,4- Ethylenedioxy Thiophenes) composite conducting The preparation method of hydrogel, it is characterised in that：Polystyrolsulfon acid graft grapheme is dispersed in containing 3,4- Asias in step (4) In ethylenedioxy thiophene, the aqueous solution of medicine, 30-60min is stirred, 2-5min is again stirring for after adding oxidant, will mix molten Liquid is placed in 10-20 DEG C and stands reaction 24-36h, carries out washing with deionized water and produces.
- Polystyrolsulfon acid graft grapheme as claimed in claim 1/poly- 9. (3,4- Ethylenedioxy Thiophenes) 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 claimed in claim 1/poly- 10. (3,4- Ethylenedioxy Thiophenes) composite conducting The preparation method of hydrogel, it is characterised in that：The medicine is penicillin, nifedipine, dexamethasone, N'-Dimethylguanylguanidine hydrochloride Or one kind in salicylic acid, the concentration of medicine is 1-5mg/mL in the aqueous solution.
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