CN107312172B - A kind of preparation method of micro-nano structure polyaniline material - Google Patents
A kind of preparation method of micro-nano structure polyaniline material Download PDFInfo
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- CN107312172B CN107312172B CN201710544908.2A CN201710544908A CN107312172B CN 107312172 B CN107312172 B CN 107312172B CN 201710544908 A CN201710544908 A CN 201710544908A CN 107312172 B CN107312172 B CN 107312172B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
Abstract
The invention discloses a kind of preparation method of micro-nano structure polyaniline material, the method for specially a kind of chemical syntheses micro-nano structure polyaniline material in eutectic solvent belongs to technical field of material.This method is summarized as follows: being uniformly mixed synthesis eutectic solvent according to different mol ratio heating with carboxylic acid using quaternary ammonium salt first；Secondly using aniline as monomer, ammonium persulfate is as oxidant, and for eutectic solvent as dopant and solvent, it is micro-nano structure polyaniline material that chemical oxidising polymerisation, which obtains blackish green product,.The method of the present invention has the advantages such as reaction process is simple, controllable, cheap；The polyaniline nano material of preparation has good electro-chemical activity simultaneously, and the conductivity that four-point probe measures polyaniline is 1 ~ 10 S cm‑1, had a good application prospect in fields such as supercapacitor, anti-corrosion of metal, electromagnetic shielding, microwave absorptions.
Description
Technical field
The present invention relates to conductive polymer material field, specially a kind of preparation method of micro-nano structure polyaniline material,
A large amount of preparation and application suitable for polymeric material field polyaniline material.
Background technique
Polyaniline has excellent electric conductivity as a kind of conductive polymer material, the ability of height storage charge and good
Environmental stability the advantages that, show in fields such as supercapacitor, anti-corrosion of metal, electromagnetic shielding, microwave absorption, electrochromism
Good application prospect out, the extensive concern by researcher.In the prior art, the synthetic method of polyaniline mainly has chemistry
Oxidative polymerization method and electrochemical polymerization method.Electrochemical polymerization method is suitble to small lot to prepare the polyaniline of special property, and chemical oxygen
Change polymerization and be suitble to mass production polyaniline, classical chemical oxidative polymerization is usually to utilize oxidant in acidic aqueous solution
Make aniline oxidation polymerization, commonly using oxidant is ammonium persulfate, but this method can generate largely not after preparing polyaniline
The acid waste water of recoverable, this acid waste water seriously endanger ecological environment and water body resource.Therefore a kind of solvent is needed
It can be recycled and method for preparing polyaniline free from environmental pollution.
Summary of the invention
The present invention becomes asking for the not acid waste water of recoverable to solve solvent after traditional method for preparing polyaniline
Topic, provides a kind of method of chemical syntheses micro-nano structure polyaniline material in eutectic solvent.
The present invention is achieved by the following technical solution: a kind of preparation method of micro-nano structure polyaniline material, packet
Include following steps:
1. quaternary ammonium salt is uniformly mixed synthesis eutectic solvent with carboxylic acid heating；
2. aniline monomer is added in the eutectic solvent, aniline solution is formed；
3. ammonium persulfate is added in the eutectic solvent, ammonium persulfate solution is formed；
4. the aniline solution is mixed with ammonium persulfate solution, obtaining blackish green product by chemical oxidising polymerisation is
Micro-nano structure polyaniline material.
Preferably, 1. middle quaternary ammonium salt is choline chloride or glycine betaine to step.
Preferably, step 1. in carboxylic acid be dodecyl benzene sulfonic acid, p-methyl benzenesulfonic acid, salicylic acid, citric acid, tartaric acid,
Succinic acid, acrylic acid, benzoic acid, glutamic acid or adipic acid.
Preferably, 1. the molar ratio of middle quaternary ammonium salt and carboxylic acid is (1 ~ 8) to step: 1.
Preferably, step 1. in quaternary ammonium salt and carboxylic acid be uniformly mixed in 80 DEG C ~ 100 DEG C heating and synthesize eutectic solvent, by
Higher in quaternary ammonium salt content, required temperature is higher, therefore the two molar ratio is combined with temperature, comprehensively considers and obtains
The result of above-mentioned mole of specific capacity and temperature.
Preferably, 2. aniline monomer concentration is 0.2 ~ 2 mol/L to step in aniline solution.
Preferably, 3. the molar ratio of middle ammonium persulfate and aniline is 1:1 to step.
Preferably, 4. middle polymerization temperature is 10 ~ 60 DEG C to step, and polymerization time is 2-10 h.
The technical scheme is that being uniformly mixed the low of synthesis according to different mol ratio heating with carboxylic acid using quaternary ammonium salt
Congruent melting solvent is as dopant and solvent, using the excellent physicochemical characteristics of eutectic solvent, and both be recycled, can also
The characteristic of degradation, using aniline as monomer, for ammonium persulfate as oxidant, it is as micro- that chemical oxidising polymerisation obtains blackish green product
Micro-nano structure polyaniline material.
The beneficial effects of the present invention are: (1) present invention is using cheap, biodegradable eutectic solvent as molten
Agent and acid doping agent, compared with traditional aqueous, eutectic solvent provides new chemical environment, and ion stabilized existing forms are more
Memberization, species nucleate rate faster, are more likely formed ordered structure under hydrogen bond action；(2) present invention have reaction process it is simple, can
Control, the cheap and advantages such as can be recycled；(3) polyaniline nano material prepared by the present invention is living with good electrochemistry
Property, the conductivity that four-point probe measures polyaniline is 1 ~ 10 S cm-1, supercapacitor, anti-corrosion of metal, electromagnetic shielding,
The fields such as microwave absorption have a good application prospect.
Detailed description of the invention
Fig. 1 is the scanning electron microscope diagram of polyaniline in 1 choline chloride of embodiment-p-methyl benzenesulfonic acid eutectic solvent.
Fig. 2 is the scanning electron microscope diagram of polyaniline in 1 choline chloride of embodiment-p-methyl benzenesulfonic acid eutectic solvent.
Fig. 3 is the X-ray diffractogram of polyaniline in 1 choline chloride of embodiment-p-methyl benzenesulfonic acid eutectic solvent.
Specific embodiment
Below with reference to embodiment, description of specific embodiments of the present invention.
A kind of preparation method of micro-nano structure polyaniline material, comprising the following steps:
1. quaternary ammonium salt is uniformly mixed synthesis eutectic solvent with carboxylic acid heating；
2. aniline monomer is added in the eutectic solvent, aniline solution is formed；
3. ammonium persulfate is added in the eutectic solvent, ammonium persulfate solution is formed；
4. the aniline solution is mixed with ammonium persulfate solution, obtaining blackish green product by chemical oxidising polymerisation is
Micro-nano structure polyaniline material.
During in the present invention, preparing micro-nano structure polyaniline material, quaternary ammonium salt is choline chloride or glycine betaine；
Carboxylic acid is dodecyl benzene sulfonic acid, p-methyl benzenesulfonic acid, salicylic acid, citric acid, tartaric acid, succinic acid, acrylic acid, benzoic acid, paddy
Propylhomoserin or adipic acid.Step 1. in, the molar ratio of quaternary ammonium salt and carboxylic acid is (1 ~ 8): 1, and the two is heated at 80 DEG C ~ 100 DEG C
It is uniformly mixed synthesis eutectic solvent；Step 2. in, in eutectic solvent aniline monomer concentration be 0.2 ~ 2 mol/L；Step is 3.
In, the molar ratio of oxidant ammonium persulfate and aniline is 1:1；4. middle polymerization temperature is 10 ~ 60 DEG C to step, polymerization time 2-10
h。
In following embodiment, experimental raw aniline is evaporated under reduced pressure before chemical oxidising polymerisation, remaining reagent be it is commercially available not
Carry out purification processes.
Embodiment 1
Step is 1.: weighing choline chloride 112g, p-methyl benzenesulfonic acid 136g, molar ratio 1:1, nothing is made in 80 DEG C of heating stirrings
Color transparency liquid, as eutectic solvent；Step is 2.: 5ml aniline is added to 45ml choline chloride-p-methyl benzenesulfonic acid eutectic
It is stirred in solvent to clarification, being configured to concentration is 1mol/L aniline solution；Step is 3.: 11.4g ammonium persulfate is added to
It is stirred in 40ml choline chloride-p-methyl benzenesulfonic acid eutectic solvent to clarification, being configured to concentration is 1mol/L ammonium persulfate
Solution；Step is 4.: configured aniline solution and ammonium persulfate solution being mixed, is 10 DEG C in temperature and is stirred to react 8 h, product
Blackish green powdered micro-nano structure polyaniline material is dried to obtain by washing.The scanning electron microscope test of the embodiment
As depicted in figs. 1 and 2；X-ray diffraction test is as shown in Figure 2.The conductivity that four-point probe measures polyaniline is 4.8 S
cm-1。
Embodiment 2
Step is 1.: choline chloride 112g, dodecyl benzene sulfonic acid 132g, molar ratio 2:1 is weighed, in 100 DEG C of heating stirrings
Colourless transparent liquid, as eutectic solvent is made；Step is 2.: 10ml aniline is added to 40 ml choline chlorides-dodecane
It is stirred in base benzene sulfonic acid eutectic solvent to clarification, being configured to concentration is 2mol/L aniline solution；Step is 3.: by 23g mistake
Ammonium sulfate is added in 40ml choline chloride-dodecyl benzene sulfonic acid eutectic solvent and is stirred to clarification, is configured to concentration
For 2 mol/L ammonium persulfate solutions；Step is 4.: configured aniline solution and ammonium persulfate solution being mixed, are 35 in temperature
It DEG C is stirred to react 6h, product is dried to obtain blackish green powdered micro-nano structure polyaniline material by washing.In the embodiment,
The conductivity that four-point probe measures polyaniline is 6.4 S cm-1。
Embodiment 3
Step is 1.: weighing glycine betaine 96g, salicylic acid 28g, molar ratio 4:1, colorless and transparent liquid is made in 95 DEG C of heating stirrings
Body, as eutectic solvent；Step is 2.: 1ml aniline being added in 49ml glycine betaine-salicylic acid eutectic solvent and is stirred
To clarification, being configured to concentration is 0.2mol/L aniline solution；Step is 3.: 2.3g ammonium persulfate is added to 40 ml glycine betaines-water
It is stirred in poplar acid eutectic solvent to clarification, being configured to concentration is 0.2 mol/L ammonium persulfate solution；Step is 4.: will match
Aniline solution and the ammonium persulfate solution mixing set, are 45 DEG C in temperature and are stirred to react 2h, product is dried to obtain by washing
Blackish green powdered micro-nano structure polyaniline material.In the embodiment, the conductivity that four-point probe measures polyaniline is
7.3 S cm-1。
Embodiment 4
Step is 1.: weighing glycine betaine 192g, succinic acid 24g, molar ratio 8:1, is made colorless and transparent in 90 DEG C of heating stirrings
Liquid, as eutectic solvent；Step is 2.: 2.5ml aniline is added in 47.5ml glycine betaine-succinic acid eutectic solvent
It is stirred to clarification, being configured to concentration is 0.5mol/L aniline solution；Step is 3.: 5.7g ammonium persulfate is added to 40 ml
It is stirred in glycine betaine-succinic acid eutectic solvent to clarification, being configured to concentration is 0.5mol/L ammonium persulfate solution；Step
4.: configured aniline solution and ammonium persulfate solution are mixed, is 60 DEG C in temperature and is stirred to react 10h, product is by washing
It is dried to obtain blackish green powdered micro-nano structure polyaniline material.In the embodiment, four-point probe measures polyaniline
Conductivity is 4.4 S cm-1。
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (8)
1. a kind of preparation method of micro-nano structure polyaniline material, it is characterised in that: the following steps are included:
1. quaternary ammonium salt is uniformly mixed synthesis eutectic solvent with carboxylic acid heating；
2. aniline monomer is added in the eutectic solvent, aniline solution is formed；
3. ammonium persulfate is added in the eutectic solvent, ammonium persulfate solution is formed；
4. the aniline solution is mixed with ammonium persulfate solution, obtaining blackish green product by chemical oxidising polymerisation is micro-nano
Structure polyaniline material.
2. a kind of preparation method of micro-nano structure polyaniline material according to claim 1, it is characterised in that: step 1. in
The quaternary ammonium salt is choline chloride or glycine betaine.
3. a kind of preparation method of micro-nano structure polyaniline material according to claim 1, it is characterised in that: step 1. in
The carboxylic acid is dodecyl benzene sulfonic acid, p-methyl benzenesulfonic acid, salicylic acid, citric acid, tartaric acid, succinic acid, acrylic acid, benzene first
Acid, glutamic acid or adipic acid.
4. a kind of preparation method of micro-nano structure polyaniline material according to claim 1, it is characterised in that: step 1. in
The molar ratio of the quaternary ammonium salt and carboxylic acid is (1 ~ 8): 1.
5. a kind of preparation method of micro-nano structure polyaniline material according to claim 1 or 4, it is characterised in that: step
1. quaternary ammonium salt described in is uniformly mixed synthesis eutectic solvent in 80 DEG C ~ 100 DEG C heating with carboxylic acid.
6. a kind of preparation method of micro-nano structure polyaniline material according to claim 1, it is characterised in that: step 2. in
Aniline monomer concentration is 0.2 ~ 2 mol/L in the aniline solution.
7. a kind of preparation method of micro-nano structure polyaniline material according to claim 1, it is characterised in that: step 3. in
The molar ratio of the ammonium persulfate and aniline is 1:1.
8. a kind of preparation method of micro-nano structure polyaniline material according to claim 1, it is characterised in that: step 4. in
Polymerization temperature is 10 ~ 60 DEG C, and polymerization time is 2-10 h.
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| CN113621100B (en) * | 2021-08-24 | 2023-08-01 | 华南理工大学 | Polymerizable eutectic solvent, dry ion conductor prepared by polymerizable eutectic solvent and preparation method of dry ion conductor |
| CN114276522B (en) * | 2021-12-29 | 2023-05-19 | 河北大学 | Eutectic solvent modified acidic hydroxyl conjugated microporous polymer and preparation method thereof |
| CN115322370B (en) * | 2022-08-30 | 2023-10-13 | 南京林业大学 | Preparation method of antifreeze high-conductivity cellulose-based ionic elastomer |
| CN115448291B (en) * | 2022-10-13 | 2023-08-01 | 宁夏中星显示材料有限公司 | Carbon oxide quantum dot, carbon oxide quantum dot/sepiolite composite material, and preparation method and application thereof |
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| CN105916807A (en) * | 2013-09-24 | 2016-08-31 | 康斯乔最高科学研究公司 | Exfoliation of graphite with deep eutectic solvents |
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| CN105916807A (en) * | 2013-09-24 | 2016-08-31 | 康斯乔最高科学研究公司 | Exfoliation of graphite with deep eutectic solvents |
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| Biodegradable deep-eutectic mixtures as electrolytes for the electrochemical synthesis of conducting polymers;Paula M. V. Fernandes et al;《J Appl Electrochem》;20121231;第42卷;第997-1003页 * |
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