CN106519666B - A kind of taurine secondary doping polyaniline and preparation method thereof - Google Patents
A kind of taurine secondary doping polyaniline and preparation method thereof Download PDFInfo
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- CN106519666B CN106519666B CN201610883458.5A CN201610883458A CN106519666B CN 106519666 B CN106519666 B CN 106519666B CN 201610883458 A CN201610883458 A CN 201610883458A CN 106519666 B CN106519666 B CN 106519666B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
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Abstract
The invention belongs to polymeric material fields, and in particular to a kind of taurine secondary doping polyaniline and preparation method thereof.The preparation method includes the following steps: the preparation of S1. doped hydrochloride polyaniline;S2. the preparation of polyaniline in eigenstate;S3. the preparation of taurine secondary doping polyaniline.Taurine sulfonic acid group rich in and amino group carry out secondary doping to polyaniline using it as dopant, and sulfonic acid group and polyaniline effect reach doping purpose, and amino provides preferable water-soluble and electric conductivity.The present invention selects taurine to be prepared for taurine secondary doping polyaniline as dopant, test indicate that, it has excellent solubility property and electric conductivity, these performances all increase significantly compared with polyaniline in eigenstate and doped hydrochloride polyaniline;Preparation method of the invention carries out all in water phase, does not add any organic solvent, is a kind of environmental-friendly method;It is cheap to invent the cost of material used, helps to reduce production cost.
Description
Technical field
The invention belongs to polymeric material fields, and in particular to a kind of taurine secondary doping polyaniline and its preparation side
Method.
Background technique
Polyaniline is because of its good thermal stability, environmental stability and electrochemical reversibility, excellent electromagnetic shielding performance,
Raw material is easy to get, and synthetic method is simple and the characteristics such as unique mechanism of doping effect, become study most hot conductive polymer material it
One.But due to the influence of the intermolecular hydrogen bonding between the aromatic rings and amido, imido grpup of polyaniline, lead to polyaniline dissolubility
Energy and its processing performance are poor.In recent years, for these defects of polyaniline, method of modifying emerges one after another, and is concentrated mainly on cream
Liquid polymerization, secondary doping organic or inorganic Bronsted acid, substitutive derivative, composite material etc..Secondary doping organic or inorganic
Bronsted acid has obtained biggish application as a kind of simple and modified apparent method.
Summary of the invention
For the deficiency of polyaniline solubility property difference, the present invention provides a kind of taurine secondary doping polyaniline and its preparation
Method, the solubility property and electric conductivity of the secondary doping polyaniline are excellent.
The technical scheme to solve the above technical problems is that a kind of preparation side of taurine secondary doping polyaniline
Method comprising following steps:
S1. aniline is stirred to react with mixed in hydrochloric acid and under condition of ice bath, after the temperature of reaction solution is down to 5 DEG C or less
Initiator solution is added dropwise into reaction solution, maintaining reaction temperature is at 5 DEG C hereinafter, sufficiently filtering after reaction, filter cake deionized water
It is washed with dehydrated alcohol, is dried in vacuo to obtain doped hydrochloride polyaniline;
S2. by S1 preparation doped hydrochloride polyamine be added ammonium hydroxide in, be sufficiently stirred doping after filter, filter cake ethyl alcohol and
Deionized water is washed to neutrality, and polyaniline in eigenstate is dried in vacuo to obtain;
S3. the polyaniline in eigenstate by S2 preparation is added in the taurine aqueous solution of 0.8-1.2mol/L, eigenstate polyphenyl
Amine and taurine are (1-2) g:(0.05-0.1) mol, stirring 4h or more carries out secondary doping, filters, filter cake ethyl alcohol and go
Ion water washing is dried in vacuo to obtain powdered taurine secondary doping polyaniline to neutrality.
Based on the above technical solution, the present invention can also have following further specific choice.
Specifically, the concentration of the hydrochloric acid in S1 is 1-2mol/L, aniline and hydrochloric acid dosage ratio are (0.05-0.1) mol:
(50-100)mL。
Specifically, the initiator solution in S1 is the aqueous solution of ammonium persulfate, potassium peroxydisulfate or sodium peroxydisulfate.
Specifically, the concentration of the initiator solution in S1 is 1-2mol/L, the amount ratio of aniline and initiator solution is
(0.05-0.1) mol:(25-40) mL.
Specifically, the concentration of ammonium hydroxide is 1-2mol/L in S2, the amount ratio of doped hydrochloride polyaniline and ammonium hydroxide is (1-2) g:
(150-200)mL。
Specifically, vacuum drying temperature is 60 DEG C in S1, S2 and S3, the vacuum drying time is for 24 hours.
The present invention also provides a kind of taurine secondary doping polyanilines, are prepared by the above method.
The beneficial effects of the present invention are: taurine sulfonic acid group rich in and amino group, using it as dopant pair
Polyaniline carries out secondary doping, and sulfonic acid group and polyaniline effect reach doping purpose, and amino provides preferable water-soluble
And electric conductivity.The present invention selects taurine to be prepared for taurine secondary doping polyaniline as dopant, test indicate that, it has
There are excellent solubility property and electric conductivity, these performances have significantly compared with polyaniline in eigenstate and doped hydrochloride polyaniline
Raising;Preparation method of the invention carries out all in water phase, does not add any organic solvent, is a kind of environmental-friendly side
Method;It is cheap to invent the cost of material used, helps to reduce production cost.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, and example is served only for explaining this hair
It is bright, it is not intended to limit the scope of the present invention.
Embodiment 1
A kind of taurine secondary doping polyaniline, is prepared as follows:
S1: the preparation of doped hydrochloride polyaniline: the 2mol/L hydrochloric acid of 0.05mol aniline and 100mL is added to exist in there-necked flask
It is stirred 10 minutes in ice bath, drops to 5 DEG C hereinafter, the 2mol/L ammonium persulfate of prepared 25mL is added dropwise with dropping funel to temperature
Solution keeps reaction temperature at 5 DEG C hereinafter, reaction 4h, product is filtered, washs filter with deionized water and dehydrated alcohol
Cake, 60 DEG C of vacuum drying obtain product hydrochloric acid doped polyaniline for 24 hours.
S2: the preparation of polyaniline in eigenstate: it is 1mol/L that the doped hydrochloride polyaniline after taking 1g dry, which is dissolved in 200mL concentration,
Ammonium hydroxide in, stirring 4h adulterate, and is filtered, then wash filter cake to neutrality with ethyl alcohol and deionized water, 60 DEG C are dried in vacuo
Polyaniline in eigenstate is obtained for 24 hours.
S3: the preparation of taurine secondary doping polyaniline: taking 1g polyaniline in eigenstate to be dissolved in 100mL concentration is 1mol/L's
In taurine solution, stirring 4h carries out secondary doping, and the blackish green polymer filtration that will be obtained is washed with ethyl alcohol and deionized water
Filter cake to neutrality, 60 DEG C of vacuum drying for 24 hours, obtain black powder taurine secondary doping polyaniline.
Embodiment 2
A kind of taurine secondary doping polyaniline, is prepared as follows:
S1: the preparation of doped hydrochloride polyaniline: add the 1mol/L hydrochloric acid of 0.1mol aniline and 100mL in ice in there-necked flask
It is stirred 10 minutes in bath, drops to 5 DEG C hereinafter, the 1.5mol/L ammonium persulfate of prepared 30mL is added dropwise with dropping funel to temperature
Solution keeps reaction temperature at 5 DEG C hereinafter, reaction 4h, product is filtered, washs filter with deionized water and dehydrated alcohol
Cake, 60 DEG C of vacuum drying obtain product hydrochloric acid doped polyaniline for 24 hours.
S2: the preparation of polyaniline in eigenstate: the doped hydrochloride polyaniline after taking 1g dry is dissolved in 150mL concentration and is
In the ammonium hydroxide of 1.5mol/L, stirring 4h adulterate, and is filtered, then washs filter cake to neutrality with ethyl alcohol and deionized water, and 60 DEG C
Vacuum drying obtains polyaniline in eigenstate for 24 hours.
S3: the preparation of taurine secondary doping polyaniline: taking 1g polyaniline in eigenstate to be dissolved in 80mL concentration is 0.8mol/L
Taurine solution in, stirring 4h carries out secondary doping, and the blackish green polymer filtration that will be obtained is washed with ethyl alcohol and deionization
Filter cake is washed to neutrality, 60 DEG C of vacuum drying for 24 hours, obtain black powder taurine secondary doping polyaniline.
Embodiment 3
A kind of taurine secondary doping polyaniline, is prepared as follows:
S1: the preparation of doped hydrochloride polyaniline: add the 2mol/L hydrochloric acid of 0.1mol aniline and 50mL in ice in there-necked flask
It is stirred 10 minutes in bath, drops to 5 DEG C hereinafter, the 1mol/L ammonium persulfate that prepared 40mL is added dropwise with dropping funel is molten to temperature
Liquid, keep reaction temperature at 5 DEG C hereinafter, reaction 4h, product is filtered, washs filter cake with deionized water and dehydrated alcohol,
60 DEG C of vacuum drying obtain product hydrochloric acid doped polyaniline for 24 hours.
S2: the preparation of polyaniline in eigenstate: it is 2mol/L that the doped hydrochloride polyaniline after taking 2g dry, which is dissolved in 200mL concentration,
Ammonium hydroxide in, stirring 4h adulterate, and is filtered, then wash filter cake to neutrality with ethyl alcohol and deionized water, 60 DEG C are dried in vacuo
Polyaniline in eigenstate is obtained for 24 hours.
S3: the preparation of taurine secondary doping polyaniline: taking 2g polyaniline in eigenstate to be dissolved in 80mL concentration is 1.2mol/L
Taurine solution in, stirring 4h carries out secondary doping, and the blackish green polymer filtration that will be obtained is washed with ethyl alcohol and deionization
Filter cake is washed to neutrality, 60 DEG C of vacuum drying for 24 hours, obtain black powder taurine secondary doping polyaniline.
Embodiment 4
A kind of taurine secondary doping polyaniline, is prepared as follows:
S1: the preparation of doped hydrochloride polyaniline: the 1.5mol/L hydrochloric acid of 0.1mol aniline and 50mL is added to exist in there-necked flask
It is stirred 10 minutes in ice bath, drops to 5 DEG C hereinafter, the 1.5mol/L persulfuric acid of prepared 35mL is added dropwise with dropping funel to temperature
Potassium solution keeps reaction temperature at 5 DEG C hereinafter, reaction 4h, product is filtered, washs filter with deionized water and dehydrated alcohol
Cake, 60 DEG C of vacuum drying obtain product hydrochloric acid doped polyaniline for 24 hours.
S2: the preparation of polyaniline in eigenstate: the doped hydrochloride polyaniline after taking 1.5g dry is dissolved in 180mL concentration and is
In the ammonium hydroxide of 1.5mol/L, stirring 4h adulterate, and is filtered, then washs filter cake to neutrality with ethyl alcohol and deionized water, and 60 DEG C
Vacuum drying obtains polyaniline in eigenstate for 24 hours.
S3: the preparation of taurine secondary doping polyaniline: taking 1.5g polyaniline in eigenstate to be dissolved in 100mL concentration is 1mol/L
Taurine solution in, stirring 4h carries out secondary doping, and the blackish green polymer filtration that will be obtained is washed with ethyl alcohol and deionization
Filter cake is washed to neutrality, 60 DEG C of vacuum drying for 24 hours, obtain black powder taurine secondary doping polyaniline.
Embodiment 5
A kind of taurine secondary doping polyaniline, is prepared as follows:
S1: the preparation of doped hydrochloride polyaniline: add the 1mol/L hydrochloric acid of 0.75mol aniline and 90mL in ice in there-necked flask
It is stirred 10 minutes in bath, drops to 5 DEG C hereinafter, the 2mol/L sodium peroxydisulfate that prepared 25mL is added dropwise with dropping funel is molten to temperature
Liquid, keep reaction temperature at 5 DEG C hereinafter, reaction 4h, product is filtered, washs filter cake with deionized water and dehydrated alcohol,
60 DEG C of vacuum drying obtain product hydrochloric acid doped polyaniline for 24 hours.
S2: the preparation of polyaniline in eigenstate: it is 2mol/L that the doped hydrochloride polyaniline after taking 2g dry, which is dissolved in 100mL concentration,
Ammonium hydroxide in, stirring 4h adulterate, and is filtered, then wash filter cake to neutrality with ethyl alcohol and deionized water, 60 DEG C are dried in vacuo
Polyaniline in eigenstate is obtained for 24 hours.
S3: it the preparation of taurine secondary doping polyaniline: takes 1.5g polyaniline in eigenstate to be dissolved in 100mL concentration to be
In the taurine solution of 0.8mol/L, stirring 4h carries out secondary doping, and the blackish green polymer filtration that will be obtained with ethyl alcohol and is gone
Ion water washing filter cake to neutrality, 60 DEG C of vacuum drying for 24 hours, obtain black powder taurine secondary doping polyaniline.
The water soluble characteristic for the taurine secondary doping polyaniline that embodiment 1 to 5 obtains is tested, while being tested corresponding
The water solubility of doped hydrochloride polyaniline and polyaniline in eigenstate obtained in embodiment, test method are by polymer 10mg to be measured
It being added in 1mL water, ultrasonic 30min is then allowed to stand the state for observing it for 24 hours, and test result is as follows shown in table, wherein ++ it represents
Be completely dissolved ,+represent and be partly dissolved ,-represent it is insoluble.
Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
Doped hydrochloride polyaniline | + | + | + | + | - |
Polyaniline in eigenstate | - | - | - | - | - |
Taurine secondary doping polyaniline | ++ | ++ | + | ++ | + |
From the test result of upper table it is found that taurine secondary doping polyaniline prepared by the present invention can be completely soluble,
Its solubility property is preferable, hence it is evident that is better than doped hydrochloride polyaniline and polyaniline in eigenstate.
The conductivity row for the taurine secondary doping polyaniline that embodiment 1 to 5 obtains is tested to reflect its electric conductivity,
The conductivity of doped hydrochloride polyaniline and polyaniline in eigenstate obtained in corresponding embodiment is tested simultaneously, test result is as follows table
It is shown:
Conductivity (S/cm) | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
Doped hydrochloride polyaniline | 10 | 9.4 | 9.2 | 9.6 | 8.8 |
Polyaniline in eigenstate | 5.3 | 4.8 | 4.9 | 4.8 | 4.3 |
Taurine secondary doping polyaniline | 32.3 | 31.2 | 31.9 | 31.8 | 31 |
By the data in upper table it is found that the electric conductivity of taurine secondary doping polyaniline prepared by the present invention is preferable,
Conductivity is apparently higher than doped hydrochloride and takes aniline and polyaniline in eigenstate.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (7)
1. a kind of preparation method of taurine secondary doping polyaniline, which comprises the steps of:
S1. aniline is stirred to react with mixed in hydrochloric acid and under condition of ice bath, the temperature to reaction solution is down to 5 DEG C or less backward instead
It answers and initiator solution is added dropwise in liquid, maintaining reaction temperature is at 5 DEG C hereinafter, sufficiently filtering after reaction, filter cake deionized water and nothing
Water-ethanol washing, is dried in vacuo to obtain doped hydrochloride polyaniline;
S2. the doped hydrochloride polyaniline by S1 preparation is added in ammonium hydroxide, filters, filter cake ethyl alcohol and goes after doping is sufficiently stirred
Ion water washing is dried in vacuo to obtain polyaniline in eigenstate to neutrality;
S3. by S2 preparation polyaniline in eigenstate be added 0.8-1.2mol/L taurine aqueous solution in, polyaniline in eigenstate with
Taurine is (1-2) g:(0.05-0.1) mol, it stirs 4h or more and carries out secondary doping, filter, filter cake ethyl alcohol and deionization
Water washing is dried in vacuo to obtain powdered taurine secondary doping polyaniline to neutrality.
2. a kind of preparation method of taurine secondary doping polyaniline according to claim 1, which is characterized in that in S1
The concentration of hydrochloric acid is 1-2mol/L, and aniline and hydrochloric acid dosage ratio are (0.05-0.1) mol:(50-100) mL.
3. a kind of preparation method of taurine secondary doping polyaniline according to claim 1, which is characterized in that in S1
Initiator solution is the aqueous solution of ammonium persulfate, potassium peroxydisulfate or sodium peroxydisulfate.
4. a kind of preparation method of taurine secondary doping polyaniline according to claim 1, which is characterized in that in S1
The concentration of initiator solution is 1-2mol/L, and the amount ratio of aniline and initiator solution is (0.05-0.1) mol:(25-40) mL.
5. a kind of preparation method of taurine secondary doping polyaniline according to claim 1, which is characterized in that ammonia in S2
The concentration of water is 1-2mol/L, and the amount ratio of doped hydrochloride polyaniline and ammonium hydroxide is (1-2) g:(150-200) mL.
6. a kind of preparation method of taurine secondary doping polyaniline according to any one of claims 1 to 5, feature exist
In vacuum drying temperature is 60 DEG C in S1, S2 and S3, the vacuum drying time is for 24 hours.
7. a kind of taurine secondary doping polyaniline, which is characterized in that pass through method such as claimed in any one of claims 1 to 6
It is prepared.
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CN107227104A (en) * | 2017-07-18 | 2017-10-03 | 大悟县新生农业科技有限公司 | A kind of citric acid secondary doping polyaniline and its application in anticorrosive paint |
CN112143341B (en) * | 2020-10-14 | 2022-04-01 | 湖南科技大学 | Preparation method of secondary POSS-doped modified polyaniline anticorrosive coating |
CN113140666B (en) * | 2021-03-30 | 2023-09-26 | 武汉工程大学 | Composite thermoelectric material and preparation method thereof |
CN113659066A (en) * | 2021-07-27 | 2021-11-16 | 武汉工程大学 | Phytic acid partially-doped polyaniline thermoelectric material and preparation method thereof |
CN114790591B (en) * | 2022-04-07 | 2024-01-30 | 烟台哈尔滨工程大学研究院 | Polyimide/polyaniline composite conductive fiber membrane material and preparation method thereof |
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CN1415645A (en) * | 2002-11-14 | 2003-05-07 | 华东理工大学 | Method for preparing fusible conductive polyaniline |
CN104884490A (en) * | 2012-10-12 | 2015-09-02 | 加州大学评议会 | Polyaniline membranes, uses, and methods thereto |
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CN1415645A (en) * | 2002-11-14 | 2003-05-07 | 华东理工大学 | Method for preparing fusible conductive polyaniline |
CN104884490A (en) * | 2012-10-12 | 2015-09-02 | 加州大学评议会 | Polyaniline membranes, uses, and methods thereto |
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