CN1159366C - Preparation method of polyaniline-polyacrylic acid hydrogel - Google Patents
Preparation method of polyaniline-polyacrylic acid hydrogel Download PDFInfo
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- CN1159366C CN1159366C CNB011340290A CN01134029A CN1159366C CN 1159366 C CN1159366 C CN 1159366C CN B011340290 A CNB011340290 A CN B011340290A CN 01134029 A CN01134029 A CN 01134029A CN 1159366 C CN1159366 C CN 1159366C
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- polyacrylic acid
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Abstract
The present invention relates to a preparation method of polyaniline-polyacrylic acid hydrogel, which comprises the following steps: firstly, a water solution of acrylic polymers and a water solution of alkali are mixed; secondly, aniline is added; thirdly, a water solution of an oxidizing agent is added, and the blocky polyaniline-polyacrylic acid hydrogel can be obtained after the reaction. The present invention adopting a non-chemical bonding method has the advantage of simple and convenient preparation. Since the product of the present invention is blocky, impurities contained in the product can be removed by soaking the product in water. Consequently, the hydrogel has the advantages of easy purification and high electric conductivity. The polyaniline in the polyaniline hydrogel prepared with the method is doped with acrylic hydrogel, and therefore, the polyaniline-polyacrylic acid hydrogel has the characteristic of self doping.
Description
Technical field
The present invention relates to a kind of making method of polyaniline-polyacrylic acid hydrogel.
Background technology
At present, people are a lot of to the research for preparing the acrylic acid or the like hydrogel by chemically crosslinked modes such as radiation, initiator initiations, and it is very ripe to adopt this method to prepare hydrogel.For example, in water, add methacrylic acid monomer and a spot of linking agent---ethylenebis methacrylic ester, add initiator---azo-bis-isobutyl cyanide again, after stirring, reacted 8 hours down, can obtain the polymethyl acrylic acid hydrogel at 60 ℃.Owing to need to use chemical cross-linking agent, therefore increased production process and production cost.In recent years, polyaniline forms hot reversible polyaniline gel in organic solution (for example formic acid) and organic acid doped dose report has also appearred, it is with after formic acid (as solvent) mixes with polyaniline and doping agent (dodecyl sodium sulfonate), constant temperature stirred 24 hours under 65 ℃ of conditions, and then, it is on 80 ℃ the hot plate that reaction soln is placed on a temperature, make the formic acid volatilization, at last, in 60 ℃ of following dry 1 weeks of vacuum, just can obtain the polyaniline hydrogel.When being higher than a certain critical temperature when (this critical temperature is formed different and different with gel), this gel can be transformed into fluid; And reduce to below the critical temperature when temperature, above-mentioned fluid can be transformed into gel again.The shortcoming of this method be must use price more expensive and be corrosive, irritating formic acid is as dissolve medium.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of polyaniline-polyacrylic acid hydrogel, the polyaniline in the polyaniline hydrogel is mixed by the acrylic acid or the like hydrogel.
Technical scheme of the present invention is: a kind of preparation method of polyaniline-polyacrylic acid hydrogel comprises the steps:
(1), with 200 parts of concentration be 2%～15% and viscosity-average molecular weight be the aqueous solution of 10,000～500,000 acrylic polymers, the aqueous solution of 0～200 part of alkali, after stirring under 30 ℃～80 ℃ the temperature condition, solution is cooled to 20～30 ℃, the concentration of described alkali is less than 2mol/l;
(2), 0.5～30 part of aniline is added above-mentioned being cooled in 20 ℃～30 ℃ the solution, stir to make it to mix and obtain mixture, then, cool off this mixture, reduce to 0 ℃～5 ℃ until its temperature;
(3), the aqueous solution of 20～260 parts of oxygenants of 0 ℃～5 ℃ is added in the described mixture stir, its oxygen barrier is static, reacted 24～72 hours down at 0 ℃～5 ℃, can obtain blocky polyaniline-polyacrylic acid hydrogel, the concentration of the oxygenant that is added is 0.5～5mol/l.
The method that the present invention adopts, with the aqueous solution of acrylic polymers, the aqueous solution, aniline, oxygenant and the water of alkali is raw material, utilize the effect of keyed jointing non-chemically of acrylic polymers and polyaniline, prepared polyaniline hydrogel and acrylic acid or the like hydrogel mixture.Different with the general preparation method of hydrogel of the prior art, this polyaniline hydrogel and acrylic acid or the like hydrogel mixture are the doping effects by vinylformic acid p-poly-phenyl amine, hydrogen bond action between the acrylic acid or the like macromole, hydrogen bond action between the aniline macromole, the hydrogen bond action between vinylformic acid and aniline and between the two pass through the three-dimensional net structure that waits physical action formation mutually.It combines the volume phase transition performance of the conductivity and the acrylic acid or the like hydrogel of polyaniline.Also find through research: form between polyaniline hydrogel different and the acrylic acid or the like hydrogel mixture and also have potential difference, can form battery with doping level; After sloughing part moisture, this hydrogel can change the thermoplastic body into, and the method for available heat ductile forming is made the electrical conductor of different shape.
Before the present invention, the report of synthetic blocky polyaniline hydrogel of Shang Weiyou and acrylic acid or the like hydrogel mixture.Owing to be blocky, so can measure its resistivity easily, make battery etc.The specific conductivity of polyaniline hydrogel that makes and acrylic acid or the like hydrogel mixture is 10
-3～10
-2S/cm; Be made up of or the polyaniline hydrogel of different doping levels and the battery that acrylic acid or the like hydrogel mixture is formed difference, its discharge operating voltage is 0.03～0.8V, and specific storage is 10
-4～10
+ 3Ahr/kg; Specific energy is 10
-3～10
+ 3Whr/kg; Internal resistance is 10
2～10
4Ω.This polyaniline hydrogel and acrylic acid or the like hydrogel mixture be (60～100 ℃) drying at a certain temperature, after removing part moisture, has good thermoplastic, and before the present invention, the report of the synthetic block polyaniline hydrogel of Shang Weiyou is so become the report of thermoplastic body after also not drying.
Preparation method's of the present invention advantage is to adopt the method for keyed jointing non-chemically, prepare easy, and its product is block, in water, soak and just can remove its contained impurity, thereby the purifying of this hydrogel is very easy, can remove the by product and the unreacted aniline of the formation in the synthetic reaction process by purifying.Polyaniline has only after peracid or oxidation doping, just can have higher specific conductivity.Mix by the acrylic acid or the like hydrogel by the polyaniline in the polyaniline hydrogel of present method preparation, therefore have the characteristics of auto-doping, like this, the high conduction performance that not only has polyaniline with the polyaniline hydrogel of present method preparation, simultaneously also have the volume phase transition performance of acrylic acid or the like hydrogel, promptly combine the characteristic of polyaniline and acrylic acid or the like hydrogel.
In addition, the polyaniline hydrogel is immersed in the different acid solutions, after carrying out secondary doping, can produce potential difference between the hydrogel of different compositions and doping level, has good prospect as the all-polymer battery, and present polyaniline battery only uses polyaniline as negative pole or positive pole, and the polyaniline hydrogel that present method obtains can be respectively as negative pole and anodal use after difference is mixed.
Embodiment
A kind of preparation method of polyaniline-polyacrylic acid hydrogel comprises the steps:
(1), with 200 parts of concentration be 2%～15% and viscosity-average molecular weight be the aqueous solution of 10,000～500,000 acrylic polymers, the aqueous solution of 0～200 part of alkali, after stirring under 30 ℃～80 ℃ the temperature condition, solution is cooled to 20～30 ℃, the concentration of described alkali is 0～2mol/l;
(2), 0.5～30 part of aniline is added above-mentioned being cooled in 20 ℃～30 ℃ the solution, stir to make it to mix and obtain mixture, then, cool off this mixture, reduce to 0 ℃～5 ℃ until its temperature;
(3), the aqueous solution of 20～260 parts of oxygenants of 0 ℃～5 ℃ is added in the described mixture stir, its oxygen barrier is static, reacted 24～72 hours down at 0 ℃～5 ℃, can obtain blocky polyaniline-polyacrylic acid hydrogel, the concentration of the oxygenant that is added is 0.5～5mol/l.
The viscosity-average molecular weight of described acrylic polymers generally is to be 90,000～110,000, and the best is 100,000, and described acrylic polymers comprises one of polyacrylic acid, polymethyl acrylic acid.
Described alkali comprises a kind of or its mixture in sodium hydroxide, potassium hydroxide, yellow soda ash, the salt of wormwood, and the concentration of described alkali is 0.8～1.2mol/l, and addition is 80～120 parts, preferred 1mol/l, and its addition is 100 parts.
The addition of described aniline is 10～14 parts, preferred 12 parts.
Described oxygenant comprises a kind of or its mixture in ammonium persulphate, Sodium Persulfate, the Potassium Persulphate, and the concentration of described oxygenant is 2.1～2.5mol/l, preferred 2.3mol/l, and its add-on is 110 parts～150 parts, preferred 130 parts.
Claims (4)
1, a kind of preparation method of polyaniline-polyacrylic acid hydrogel comprises the steps:
(1), with 200 parts of concentration be 2%～15% and viscosity-average molecular weight be the aqueous solution of 10,000～500,000 acrylic polymers, the aqueous solution of 0～200 part of alkali, after stirring under 30 ℃～80 ℃ the temperature condition, solution is cooled to 20～30 ℃, the concentration of described alkali is less than 2mol/l, the viscosity-average molecular weight of described acrylic polymers is 90,000～110,000, and described acrylic polymers comprises one of polyacrylic acid, polymethyl acrylic acid.
(2), 0.5～30 part of aniline is added above-mentioned being cooled in 20 ℃～30 ℃ the solution, stir to make it to mix and obtain mixture, then, cool off this mixture, reduce to 0 ℃～5 ℃ until its temperature;
(3), the aqueous solution of 20～260 parts of oxygenants of 0 ℃～5 ℃ is added in the described mixture stir, its oxygen barrier is static, reacted 24～72 hours down at 0 ℃～5 ℃, can obtain blocky polyaniline-polyacrylic acid hydrogel, the concentration of the oxygenant that is added is 0.5～5mol/l.
2, the preparation method of polyaniline-polyacrylic acid hydrogel according to claim 1, it is characterized in that: described alkali comprises a kind of or its mixture in sodium hydroxide, potassium hydroxide, yellow soda ash, the salt of wormwood, the concentration of described alkali is 0.8～1.2mol/l, and addition is 80～120 parts.
3, the preparation method of polyaniline-polyacrylic acid hydrogel according to claim 1 is characterized in that: the addition of described aniline is 10～14 parts.
4, the preparation method of polyaniline-polyacrylic acid hydrogel according to claim 1, it is characterized in that: described oxygenant comprises a kind of or its mixture in ammonium persulphate, Sodium Persulfate, the Potassium Persulphate, the concentration of described oxygenant is 2.1～2.5mol/l, and its add-on is 110 parts～150 parts.
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|---|---|---|---|
| CNB011340290A CN1159366C (en) | 2001-10-08 | 2001-10-08 | Preparation method of polyaniline-polyacrylic acid hydrogel |
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|---|---|---|---|
| CNB011340290A CN1159366C (en) | 2001-10-08 | 2001-10-08 | Preparation method of polyaniline-polyacrylic acid hydrogel |
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| CN1159366C true CN1159366C (en) | 2004-07-28 |
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| CN101602876B (en) * | 2009-06-23 | 2011-02-02 | 南京大学 | Multiple network compound aquogel material with high mechanical intensity and electrochemical activity and preparation method thereof |
| CN103224744B (en) * | 2013-04-22 | 2015-09-30 | 常州纳欧新材料科技有限公司 | A kind of polymer coating with conductive stability and preparation method thereof |
| CN104312255B (en) * | 2014-10-29 | 2016-06-01 | 湖北大学 | A kind of aqueous polyacrylamide acid doped polyaniline inhibiter and its preparation method |
| CN104931651B (en) * | 2015-05-27 | 2016-11-09 | 东华大学 | The formaldehyde gas sensitive membrane that a kind of polyamino is material doped |
| CN107418111B (en) * | 2017-08-01 | 2020-03-24 | 中国科学技术大学 | Preparation method of self-healing stretchable conductive polymer composite for strain and/or pressure sensing |
| CN108110234B (en) * | 2017-12-13 | 2020-03-06 | 沈阳化工大学 | Conductive polymer hydrogel and preparation method and application thereof |
| CN110136968B (en) * | 2018-02-08 | 2021-03-09 | 中国科学技术大学 | Conductive polypyrrole hydrogel electrode material, preparation method thereof and stretchable supercapacitor |
| CN108794773B (en) * | 2018-06-29 | 2021-03-23 | 四川理工学院 | Preparation method of conductive hydrogel |
| CN110885476B (en) * | 2019-11-01 | 2021-04-06 | 浙江大学 | Secondary doped graphene oxide/alkali-soluble chitosan-polyaniline-polyacrylamide composite conductive hydrogel prepared by one-pot method |
| CN112755186B (en) * | 2021-01-11 | 2022-12-06 | 南京邮电大学 | Composite nano drug-loading system and preparation method thereof |
| CN113336971B (en) * | 2021-06-11 | 2022-05-24 | 东华大学 | Nano-structure polyaniline composite hydrogel and preparation method and application thereof |
| CN113363574B (en) * | 2021-06-21 | 2023-06-09 | 广东工业大学 | Polymer electrolyte and preparation method thereof |
| CN117050689B (en) * | 2023-07-28 | 2024-03-19 | 江苏理工学院 | Preparation method and application of conductive polymer adhesive |
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