CN110256694A - A kind of stretchable electrically conducting transparent hydrogel and preparation method thereof - Google Patents
A kind of stretchable electrically conducting transparent hydrogel and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/24—Homopolymers or copolymers of amides or imides
- C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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 invention discloses a kind of stretchable electrically conducting transparent hydrogel and preparation method thereof, which is cross-linked polymer network coated with conductive polymer.Wherein cross-linked polymer network can be polyacrylamide (PAAm) or polyacrylic acid (PAA)；Conducting polymer is poly- (3,4- ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS).It is prepared by three-step synthesis method, includes the following steps: that freezing PEDOT:PSS and the mixed solution of ethylene glycol obtains PEDOT:PSS pre-reaction solution；Cross-linked polymer network monomer, initiator, catalyst and accelerator are added in above-mentioned pre-reaction liquid, then carry out thermal polymerization；Thermal polymerization product is finally placed in sulfuric acid solution to impregnate, obtains stretchable electrically conducting transparent hydrogel.The present invention can get the conductive hydrogel of excellent combination property, be embodied in conductivity is high, light transmittance is high, draftability is good, surfacing, shape and thickness it is adjustable etc..
Description
Technical field
The invention belongs to optoelectronic materials technology, in particular to a kind of stretchable electrically conducting transparent hydrogel and its preparation side
Method.
Background technique
With development in science and technology, people are more and more extensive to the application demand of electronic product, especially to flexible, tensility
With wearable requirement.A kind of emerging material-Signa Gel has obtained great application, and Signa Gel has unique soft
Property/advantages such as ductility and conduction, low cost manufacturing technique.However existing main synthesis Signa Gel mode be will be conductive
Polymer and traditional insulation hydrogel are compound.But since the addition of hydrogel leads to the migration of ion and electronics while occurring,
The electrochemical reaction or water electrolysis that may occur will affect electron charge conductive performance.And it is aggregated by conductive elements solidifying
The mode preparation process that glue array prepares high-strength conductive gel is complicated, and conductive compositions connection is discontinuous, is unevenly distributed.These
Problem causes electric conductivity, translucency and tensility undesirable.Electric conductivity, translucency and the tensility being provided simultaneously at present
Electrode still face biggish challenge.
Summary of the invention
For overcome the deficiencies in the prior art, the development of the following wearable electronic product is better met, the present invention provides
A kind of stretchable electrically conducting transparent hydrogel and preparation method thereof, which is excellent combination property.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of stretchable electrically conducting transparent hydrogel, the structure of the conductive hydrogel are the polymerization of cross-linked polymer network coated with conductive
Object.
Preferably, the cross-linked polymer network is polyacrylamide (PAAm) or polyacrylic acid (PAA)；It is described conductive poly-
Closing object is poly- (3,4- ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS).
A kind of preparation method of stretchable electrically conducting transparent hydrogel, the preparation method the following steps are included:
(1) mixed solution for freezing PEDOT:PSS, ethylene glycol and water obtains PEDOT:PSS pre-reaction solution；
(2) cross-linked polymer network monomer, initiator, crosslinking agent and accelerator are added in PEDOT:PSS pre-reaction solution, with
After carry out thermal polymerization；
(3) thermal polymerization product is placed in acid solution and is impregnated.
Preferably, in the step (1), the PEDOT:PSS pre-reaction solution is by PEDOT:PSS, ethylene glycol and water
Subzero 10 ~ 20 after being sufficiently mixed in closed containero24 h are freezed under C, then take out and are filtered by vacuum at normal temperature
It arrives.
Preferably, in the step (1), the volume ratio of PEDOT:PSS, ethylene glycol and water are 3:1:8.
Preferably, in the step (2), the cross-linked polymer network monomer is acrylamide (AAm) or acrylic acid
(AA)；The initiator is ammonium persulfate, sodium peroxydisulfate or potassium peroxydisulfate；The crosslinking agent is N, N- methylene bisacrylamide acyl
Amine；The accelerator is N, N, N’, N’-Tetramethylethylenediamine (TEMED).
Preferably, the concentration of the cross-linked network high polymer monomer is 0.5 ~ 2.5 M；The quality of the initiator is high score
The 4% ~ 8% of sub- monomer mass；The quality of the crosslinking agent is the 3% ~ 5% of high polymer monomer quality；The quality of the accelerator
It is the 2% ~ 4% of high polymer monomer quality.
Preferably, in the step (3), the acid solution is sulfuric acid, hydrochloric acid or phosphoric acid, and the acid solution molar concentration is
0.4~1 M。
Compared with prior art, the invention has the following advantages:
(1) structure of conductive hydrogel be cross-linked polymer network coated with conductive polymer, realize PEDOT:PSS electric conductivity and
The high molecular mechanical tensility of cross-linked network organically combines.The conductive hydrogel excellent combination property, is embodied in conduction
Property it is high, translucency is good and tensility is strong；
(2) present invention prepares stretchable clear gel by way of simple aggregation, and preparation method is simple, can effectively reduce production
Cost is suitable for large-scale production, and the patterning production and the adjusting of shape and size of electrode may be implemented by special die, and
By the state modulator of preparation process, the supercapacitor of excellent combination property can get, especially suitable for following flexible, portable
The application of wearable electronic product.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of conductive hydrogel of the invention.
Fig. 2 is the light transmittance test of conductive hydrogel of the invention.
Fig. 3 is the graph of stretch performance of conductive hydrogel of the invention.
Specific embodiment
Below with reference to embodiment, the present invention will be further explained.
Embodiment 1
3 mL PEDOT:PSS, 1 mL ethylene glycol and 8 mL water are sufficiently mixed in closed container, subzero 18oIt is freezed under C
24 h, then vacuum filtration takes out up to PEDOT:PSS pre-reaction liquid at normal temperature.In the PEDOT:PSS pre-reaction liquid of 12 mL
In successively add 0.904 g AAm monomer, 0.053 g sodium peroxydisulfate, 0.034 gN,NMethylene-bisacrylamide and 0.035
G TEMED is rapidly injected in the glass mold of 20*80*0.3 mm, after light rolling uniformly as constant temperature 90 in drying boxoC heating
2 hours.By conductive hydrogel and mould separating after taking-up, then immerse in the sulfuric acid solution of 0.4 M, it is natural after impregnating 24 hours
It is dry, obtain stretchable electrically conducting transparent hydrogel.
The porous microscopic appearance that conductive hydrogel made from the present embodiment presents conducive to charge transmission, such as Fig. 1, conductivity
Excellent, light transmittance reaches 65%, such as Fig. 2；Former long twice of rear performance is being stretchable to without the drop that obviously declines, draftability is good, such as schemes
3。
Embodiment 2
3 mL PEDOT:PSS, 1 mL ethylene glycol and 8 mL water are sufficiently mixed in closed container with volume ratio for 3:1:8,
Subzero 18o24 h are freezed under C, then vacuum filtration takes out up to PEDOT:PSS pre-reaction liquid at normal temperature.12 mL's
0.904 g AAm monomer, 0.053 g sodium peroxydisulfate, 0.035 g are successively added in PEDOT:PSS pre-reaction liquidN,NMethylene
Bisacrylamide and 0.018 g TEMED are rapidly injected in the glass mold of 20*80*0.3 mm after light rolling uniformly, as dry
Constant temperature 90 in dry caseoC is heated 2 hours.By conductive hydrogel and mould separating after taking-up, then immerse the hydrochloric acid solution of 0.5 M
In, it is spontaneously dried after impregnating 12 hours, obtains stretchable electrically conducting transparent hydrogel.
The chemical property of flexible super capacitor made from the present embodiment is close with embodiment 1, and tensility is good,
Its after being stretchable to former long 2 times performance without the drop that obviously declines.
Embodiment 3
3 mL PEDOT:PSS, 1 mL ethylene glycol and 8 mL water are sufficiently mixed in closed container with volume ratio for 3:1:8,
Subzero 18o24 h are freezed under C, then vacuum filtration takes out up to PEDOT:PSS pre-reaction liquid at normal temperature.12 mL's
1.808 g AAm monomers, 0.053 g sodium peroxydisulfate, 0.034 g are successively added in PEDOT:PSS pre-reaction liquidN,NMethylene
Bisacrylamide and 0.034 g TEMED are rapidly injected in the glass mold of 20*80*0.3 mm after light rolling uniformly, as dry
Constant temperature 90 in dry caseoC is heated 2 hours.By conductive hydrogel and mould separating after taking-up, then immerse the sulfuric acid solution of 0.4 M
In, it is spontaneously dried after impregnating 12 hours, obtains stretchable electrically conducting transparent hydrogel.
The chemical property of flexible super capacitor made from the present embodiment is close with embodiment 1, and tensility is good,
Its after being stretchable to former long 2 times performance without the drop that obviously declines.
Embodiment 4
3 mL PEDOT:PSS, 1 mL ethylene glycol and 8 mL water are sufficiently mixed in closed container with volume ratio for 3:1:8,
Subzero 18o24 h are freezed under C, then vacuum filtration takes out up to PEDOT:PSS pre-reaction liquid at normal temperature.12 mL's
0.904 g AA monomer, 0.045 g potassium peroxydisulfate, 0.032 g N, N- methylene are successively added in PEDOT:PSS pre-reaction liquid
Bisacrylamide and 0.027 g TEMED are rapidly injected in the glass mold of 20*80*0.3 mm after light rolling uniformly, as dry
Constant temperature 90 in dry caseoC is heated 2 hours.By conductive hydrogel and mould separating after taking-up, then immerse the sulfuric acid solution of 0.4 M
In, it is spontaneously dried after impregnating 12 hours, obtains stretchable electrically conducting transparent hydrogel.
The chemical property of flexible super capacitor made from the present embodiment is close with embodiment 1, and tensility is good,
Its after being stretchable to former long 2 times performance without the drop that obviously declines.
The above is only a preferred embodiment of the present invention, it should be pointed out that: for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (8)
1. a kind of stretchable electrically conducting transparent hydrogel, which is characterized in that the structure of the conductive hydrogel is cross-linked polymer network
Coated with conductive polymer.
2. stretchable electrically conducting transparent hydrogel according to claim 1, which is characterized in that the cross-linked polymer network is
Polyacrylamide or polyacrylic acid；The conducting polymer is poly- (3,4- ethene dioxythiophene)-polystyrolsulfon acid.
3. a kind of preparation method of stretchable electrically conducting transparent hydrogel according to claim 1, which is characterized in that the preparation
Method the following steps are included:
(1) mixed solution for freezing PEDOT:PSS, ethylene glycol and water obtains PEDOT:PSS pre-reaction solution；
(2) cross-linked polymer network monomer, initiator, crosslinking agent and accelerator are added in PEDOT:PSS pre-reaction solution, with
After carry out thermal polymerization；
(3) thermal polymerization product is placed in acid solution and is impregnated.
4. the preparation method of stretchable electrically conducting transparent hydrogel according to claim 3, which is characterized in that the step
(1) in, the PEDOT:PSS pre-reaction solution be after PEDOT:PSS, ethylene glycol and water are sufficiently mixed in closed container
Subzero 10 ~ 20o24 h are freezed under C, then take out and vacuum filtration obtains at normal temperature.
5. the preparation method of stretchable electrically conducting transparent hydrogel according to claim 3, which is characterized in that the step
(1) in, the volume ratio of PEDOT:PSS, ethylene glycol and water are 3:1:8.
6. the preparation method of stretchable electrically conducting transparent hydrogel according to claim 3, which is characterized in that the step
(2) in, the cross-linked polymer network monomer is acrylamide or acrylic acid；The initiator is ammonium persulfate, sodium peroxydisulfate
Or potassium peroxydisulfate；The crosslinking agent is N,N methylene bis acrylamide；The accelerator is N, N, N’, N’-Tetramethyl second two
Amine.
7. the preparation method of stretchable electrically conducting transparent hydrogel according to claim 6, which is characterized in that the cross-linked network
The concentration of network high polymer monomer is 0.5 ~ 2.5 M；The quality of the initiator is the 4% ~ 8% of high polymer monomer quality；The friendship
The quality for joining agent is the 3% ~ 5% of high polymer monomer quality；The quality of the accelerator is the 2% ~ 4% of high polymer monomer quality.
8. the preparation method of stretchable electrically conducting transparent hydrogel according to claim 3, which is characterized in that in step (3),
The acid solution is sulfuric acid, hydrochloric acid or phosphoric acid, and the acid solution molar concentration is 0.4 ~ 1 M.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111675797A (en) * | 2020-05-27 | 2020-09-18 | 武汉工程大学 | Preparation method and application of MAA/PEDOT/PSS-based conductive hydrogel |
| CN111718497A (en) * | 2020-05-29 | 2020-09-29 | 东南大学 | PAMPS/PHEMA/PEDOT hydrogel polyelectrolyte, and preparation method and application thereof |
| CN111763334A (en) * | 2020-07-06 | 2020-10-13 | 中北大学 | Preparation of double-network conductive hydrogel and application of double-network conductive hydrogel in strain sensor |
| US20200401042A1 (en) * | 2019-05-09 | 2020-12-24 | The Board Of Trustees Of The Leland Stanford Junior University | Directly photo-patternable, stretchable, electrically conductive polymer |
| CN113337059A (en) * | 2021-06-17 | 2021-09-03 | 南京邮电大学 | Stretchable self-healing conductive polymer hydrogel, preparation method and application thereof |
| CN113402732A (en) * | 2021-05-20 | 2021-09-17 | 北京脑陆科技有限公司 | Preparation method of conductive hydrogel |
| CN113527605A (en) * | 2021-07-22 | 2021-10-22 | 华南理工大学 | Tissue adhesion conductive porous hydrogel and preparation method thereof |
| CN113637181A (en) * | 2021-07-23 | 2021-11-12 | 武汉工程大学 | Polyvinyl alcohol-based conductive hydrogel and preparation method and application thereof |
| CN113759632A (en) * | 2021-10-21 | 2021-12-07 | 中山大学 | Washable stretchable electronic paper display equipment and preparation method thereof |
| CN113769120A (en) * | 2021-09-18 | 2021-12-10 | 北京脑陆科技有限公司 | Preparation method of double-layer conductive hydrogel |
| CN113817180A (en) * | 2021-09-15 | 2021-12-21 | 大连理工大学 | Preparation of biocompatible conductive hydrogel for electroencephalogram signal sensor |
| CN114561718A (en) * | 2022-02-28 | 2022-05-31 | 中国科学技术大学 | Composite fiber material, preparation method thereof and high-stretchability fibrous supercapacitor |
| CN115260692A (en) * | 2022-08-16 | 2022-11-01 | 北京航空航天大学 | Composite hydrogel, preparation method, electromagnetic shielding device and displacement sensor |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20200401042A1 (en) * | 2019-05-09 | 2020-12-24 | The Board Of Trustees Of The Leland Stanford Junior University | Directly photo-patternable, stretchable, electrically conductive polymer |
| CN111675797B (en) * | 2020-05-27 | 2022-07-08 | 武汉工程大学 | Preparation method and application of MAA/PEDOT/PSS-based conductive hydrogel |
| CN111675797A (en) * | 2020-05-27 | 2020-09-18 | 武汉工程大学 | Preparation method and application of MAA/PEDOT/PSS-based conductive hydrogel |
| CN111718497A (en) * | 2020-05-29 | 2020-09-29 | 东南大学 | PAMPS/PHEMA/PEDOT hydrogel polyelectrolyte, and preparation method and application thereof |
| CN111718497B (en) * | 2020-05-29 | 2022-09-09 | 东南大学 | PAMPS/PHEMA/PEDOT hydrogel polyelectrolyte, and preparation method and application thereof |
| CN111763334A (en) * | 2020-07-06 | 2020-10-13 | 中北大学 | Preparation of double-network conductive hydrogel and application of double-network conductive hydrogel in strain sensor |
| CN113402732A (en) * | 2021-05-20 | 2021-09-17 | 北京脑陆科技有限公司 | Preparation method of conductive hydrogel |
| CN113337059A (en) * | 2021-06-17 | 2021-09-03 | 南京邮电大学 | Stretchable self-healing conductive polymer hydrogel, preparation method and application thereof |
| CN113527605A (en) * | 2021-07-22 | 2021-10-22 | 华南理工大学 | Tissue adhesion conductive porous hydrogel and preparation method thereof |
| CN113637181A (en) * | 2021-07-23 | 2021-11-12 | 武汉工程大学 | Polyvinyl alcohol-based conductive hydrogel and preparation method and application thereof |
| CN113817180A (en) * | 2021-09-15 | 2021-12-21 | 大连理工大学 | Preparation of biocompatible conductive hydrogel for electroencephalogram signal sensor |
| CN113769120A (en) * | 2021-09-18 | 2021-12-10 | 北京脑陆科技有限公司 | Preparation method of double-layer conductive hydrogel |
| CN113759632A (en) * | 2021-10-21 | 2021-12-07 | 中山大学 | Washable stretchable electronic paper display equipment and preparation method thereof |
| CN113759632B (en) * | 2021-10-21 | 2024-03-12 | 中山大学 | Washable stretchable electronic paper display device and preparation method thereof |
| CN114561718A (en) * | 2022-02-28 | 2022-05-31 | 中国科学技术大学 | Composite fiber material, preparation method thereof and high-stretchability fibrous supercapacitor |
| CN115260692A (en) * | 2022-08-16 | 2022-11-01 | 北京航空航天大学 | Composite hydrogel, preparation method, electromagnetic shielding device and displacement sensor |
| CN115260692B (en) * | 2022-08-16 | 2023-10-24 | 北京航空航天大学 | Composite hydrogel, preparation method, electromagnetic shielding device and displacement sensor |
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Application publication date: 20190920 |