CN108864425A - A kind of preparation method of poly- hydroxyanilines microballoon - Google Patents
A kind of preparation method of poly- hydroxyanilines microballoon Download PDFInfo
- Publication number
- CN108864425A CN108864425A CN201810748419.3A CN201810748419A CN108864425A CN 108864425 A CN108864425 A CN 108864425A CN 201810748419 A CN201810748419 A CN 201810748419A CN 108864425 A CN108864425 A CN 108864425A
- Authority
- CN
- China
- Prior art keywords
- hydroxyanilines
- poly
- preparation
- acid
- dopant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
- B01J13/18—In situ polymerisation with all reactants being present in the same phase
- B01J13/185—In situ polymerisation with all reactants being present in the same phase in an organic phase
-
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The present invention relates to a kind of preparation methods of poly- hydroxyanilines microballoon, including：Dopant is dissolved in deionized water, the aqueous solution containing dopant is made into；Phenyl amines raw material is added in the aqueous solution containing dopant, the compound containing ferrous ion is slowly inwardly added after 5min is mixed, hydrogen peroxide as oxidant is then added, 24-26h is reacted at normal temperature, is washed, and is filtered, it is dry, obtain the polyaniline of nano-spherical structure.Present method avoids use harsh reagent, such as strong oxidizer（Such as peroxydisulfate）And strong inorganic acid；Entire reaction carries out under room temperature water phase, and controllability is strong, easy to operate, is suitble to industrialized production.Polyaniline prepared by the present invention can play an important role in biosensor, supercapacitor, compliant conductive original part and the fields such as heavy metal ion adsorbed, especially the polyaniline of nanosphere Structure Comparison other structures obtained in the present invention has big specific surface area, density is low and stability is very good, resistance to corrosion is strong, electric conductivity and magnetic property performance are good, preferably application can be obtained in electricity, optics and relevant nanometer component.
Description
Technical field
The present invention relates to a kind of preparation methods of poly- hydroxyanilines microballoon.
Background technique
In recent years, in organic nano material, polyaniline is easy to due to its lower weight, electric conductivity, mechanical flexibility
Synthesis, because of its property, is widely used to energy storage field with low cost and with potential application, electro-catalysis, sensor,
Electromagnetic shielding, flexible electrode, the fields such as antistatic coating and corrosion-inhibiting coating；In the photo-thermal therapy of field of biomedicine, polyphenyl
Amine nanoparticle is because of it with suitable nano-scale and uniform shapes, good dispersion in aqueous solution, in 650-950nm
Near-infrared in range has absorption and has lower damage, high photostability and to the low of life system to surrounding health tissue
Cytotoxicity has more and more important application（Biomaterials, 2013,34,9584）.
It has been reported that a variety of method synthesized polyaniline nano materials in document（Ten thousand plum perfume (or spice) conducting polymer [J] high
Molecule notification, 1999 (3):47-53.）.The approach of the most common synthesized polyaniline is using harsh reagent, such as Strong oxdiative
Agent（Such as peroxydisulfate）And strong inorganic acid, some other oxidants that can polymerize aniline are Fe3 +, Cr2O7 2-, MnO4 -
And IO3 -.All these reactions usually require oxidant and excessive acid more than stoichiometric amount.In polyaniline synthesis most extensively
It uses（NH 4)2S2O8Approach can also generate largely（NH 4）2 SO 4By-product, and gained polyaniline still has difficulty
The disadvantages of molten, easy aggregation, processing performance and bad mechanical property, limit its development and application.In addition some special more function are used
Energy dopant has successfully synthesized the microballoon from one-dimensional polyaniline nano structure to three-dimensional polyaniline rambutan structure, and extensively
Applied to various advanced micromodule equipments, but but rarely has report by the example that common dopants synthesize poly- hydroxyanilines microballoon
Road.
Summary of the invention
In view of the deficiencies of the prior art, the present invention is intended to provide a kind of preparation method of poly- hydroxyanilines microballoon, the present invention
Using a kind of novel, mild ferrous ion compound-hydrogen peroxide green catalysis oxidation system, adulterated using organic acid
Agent makees raw material using aniline and the anil 3- amino phenols, 2- amino phenols, the 4- amino phenols that introduce hydroxyl, obtains difference
The nano-spherical structure polyaniline of size, and product pattern is observed.
Detailed description of the invention
Fig. 1 is the poly- hydroxyanilines microballoon to be obtained as dopant using homoanisic acid using 3- amino phenols as raw material
SEM figure.
Fig. 2 is using 2- amino phenols as raw material, is the poly- hydroxyanilines microballoon that dopant obtains with 2,5- dimethyl phenyl acetic acid
SEM figure.
Fig. 3 is using 4- amino phenols as raw material, is the poly- hydroxyanilines microballoon that dopant obtains with 2,5- dimethyl phenyl acetic acid
SEM figure, is designated as (c).
Fig. 4 be using 3- amino phenols as raw material, the poly- hydroxyanilines microballoon that is obtained using homoanisic acid as dopant
Ultraviolet spectrogram.
Fig. 5 is using 2- amino phenols as raw material, is the poly- hydroxyanilines microballoon that dopant obtains with 2,5- dimethyl phenyl acetic acid
Ultraviolet spectrogram.
Fig. 6 is using 4- amino phenols as raw material, is the poly- hydroxyanilines microballoon that dopant obtains with 2,5- dimethyl phenyl acetic acid
Ultraviolet spectrogram.
Fig. 7 be using 3- amino phenols as raw material, the poly- hydroxyanilines microballoon that is obtained using homoanisic acid as dopant
Infrared spectrogram.
Fig. 8 is using 2- amino phenols as raw material, is the poly- hydroxyanilines microballoon that dopant obtains with 2,5- dimethyl phenyl acetic acid
Infrared spectrogram.
Fig. 9 is using 4- amino phenols as raw material, is the poly- hydroxyanilines microballoon that dopant obtains with 2,5- dimethyl phenyl acetic acid
Infrared spectrogram.
Specific embodiment
Embodiment 1：
It take 2,5- dimethyl phenyl acetic acid as the preparation for the nano-spherical structure polyaniline that dopant obtains using aniline as raw material：It will
16.4ml (0.1 mol) 2,5- dimethyl phenyl acetic acid（It is pure）, it is dissolved in and is made into the 2,5- of 0.25mol/L in the deionized water of 400ml
Then 0.3647 ml (4mmol) aniline is added in above-mentioned solution by dimethyl phenyl acetic acid solution, and constantly carry out magnetic force and stir
It mixes, forms homogeneous phase solution after five minutes.Then 0.398g (2mmol) FeSO is added4·4H2O is slowly added into after being completely dissolved
0.95ml(0.01mol)H2O2, solution becomes darkviolet, after reacting for 24 hours under room temperature (25 DEG C), obtains 2, the 5- diformazan of black
The polyaniline of base phenylacetic acid doping.It filters, successively uses distilled water, dehydrated alcohol washs three times.Drying obtains for 24 hours under normal temperature condition
Sample.
Embodiment 2：
Using 3- amino phenols as raw material, using the preparation for the polyaniline nano ball that homoanisic acid is obtained as dopant：It will
16.6ml (0.1 mol) homoanisic acid（It is pure）, be dissolved in be made into the deionized water of 400ml 0.25mol/L to methoxy
Then 0.3647 ml (4mmol) 3- amino phenols is added in above-mentioned solution by base phenylacetic acid solution, and constantly carry out magnetic force and stir
It mixes, forms homogeneous phase solution after five minutes.Then 0.398g (2mmol) is added) FeSO4·4H2O is slowly added into after being completely dissolved
0.95ml(0.01mol)H2O2, solution becomes darkviolet, after being reacted for 24 hours under room temperature (25 DEG C), obtain black to methoxyl group
The polyaniline of phenylacetic acid doping.It filters, successively uses distilled water, dehydrated alcohol washs three times.Drying obtains sample for 24 hours under normal temperature condition
Product.
Embodiment 3：
It take 2,5- dimethyl phenyl acetic acid as the preparation for the polyaniline nano ball that dopant obtains using 3- amino phenols as raw material：It will
16.4ml (0.1 mol) 2,5- dimethyl phenyl acetic acid（It is pure）, it is dissolved in and is made into the 2,5- of 0.25mol/L in the deionized water of 400ml
Then 0.3647 ml (4mmol) 3- amino phenols is added in above-mentioned solution by dimethyl phenyl acetic acid solution, and constantly carry out magnetic
Power stirring, formed homogeneous phase solution after five minutes.Then 0.398g (2mmol) is added) FeSO4·4H2O is to after being completely dissolved, slowly
0.95ml (0.01mol) H is added2O2, solution becomes darkviolet, after reacting for 24 hours under room temperature (25 DEG C), obtains the 2,5- of black
The polyaniline of dimethyl phenyl acetic acid doping.It filters, successively uses distilled water, dehydrated alcohol washs three times.It is dried for 24 hours under normal temperature condition
Obtain sample.
Embodiment 4：
Using aniline as raw material, using the preparation for the polyaniline nano ball that homoanisic acid is obtained as dopant：By 16.6ml
(0.1 mol) homoanisic acid（It is pure）, be dissolved in be made into the deionized water of 400ml 0.25mol/L to methoxybenzene second
Then 0.3647 ml (4mmol) aniline is added in above-mentioned solution by acid solution, and constantly carry out magnetic agitation, after five minutes
Form homogeneous phase solution.Then 0.398g (2mmol) is added) FeSO4·4H2O is slowly added into 0.95ml to after being completely dissolved
(0.01mol)H2O2, solution becomes darkviolet, after reacting for 24 hours under room temperature (25 DEG C), obtains the homoanisic acid of black
The polyaniline of doping.It filters, successively uses distilled water, dehydrated alcohol washs three times.Drying obtains sample for 24 hours under normal temperature condition.
Embodiment 5：
It take 2,5- dimethyl phenyl acetic acid as the preparation for the polyaniline nano ball that dopant obtains using 2- amino phenols as raw material：It will
16.4ml (0.1 mol) 2,5- dimethyl phenyl acetic acid（It is pure）, it is dissolved in and is made into the 2,5- of 0.25mol/L in the deionized water of 400ml
Then 0.3647 ml (4mmol) 2- amino phenols is added in above-mentioned solution by dimethyl phenyl acetic acid solution, and constantly carry out magnetic
Power stirring, formed homogeneous phase solution after five minutes.Then 0.398g (2mmol) is added) FeSO4·4H2O is to after being completely dissolved, slowly
0.95ml (0.01mol) H is added2O2, solution becomes darkviolet, after reacting for 24 hours under room temperature (25 DEG C), obtains the 2,5- of black
The polyaniline of dimethyl phenyl acetic acid doping.It filters, successively uses distilled water, dehydrated alcohol washs three times.It is dried for 24 hours under normal temperature condition
Obtain sample.
Embodiment 6：
Using 2- amino phenols as raw material, using the preparation for the polyaniline nano ball that homoanisic acid is obtained as dopant：It will
16.6ml (0.1 mol) homoanisic acid（It is pure）, be dissolved in be made into the deionized water of 400ml 0.25mol/L to methoxy
Then 0.3647 ml (4mmol) 2- amino phenols is added in above-mentioned solution by base phenylacetic acid solution, and constantly carry out magnetic force and stir
It mixes, forms homogeneous phase solution after five minutes.Then 0.398g (2mmol) is added) FeSO4·4H2O is slowly added into after being completely dissolved
0.95ml(0.01mol)H2O2, solution becomes darkviolet, after being reacted for 24 hours under room temperature (25 DEG C), obtain black to methoxyl group
The polyaniline of phenylacetic acid doping.It filters, successively uses distilled water, dehydrated alcohol washs three times.Drying obtains sample for 24 hours under normal temperature condition
Product.
Embodiment 7：
Using 4- amino phenols as raw material, using the preparation for the polyaniline nano ball that homoanisic acid is obtained as dopant：It will
16.6ml (0.1 mol) homoanisic acid（It is pure）, be dissolved in be made into the deionized water of 400ml 0.25mol/L to methoxy
Then 0.3647 ml (4mmol) 4- amino phenols is added in above-mentioned solution by base phenylacetic acid solution, and constantly carry out magnetic force and stir
It mixes, forms homogeneous phase solution after five minutes.Then 0.398g (2mmol) is added) FeSO4·4H2O is slowly added into after being completely dissolved
0.95ml(0.01mol)H2O2, solution becomes darkviolet, after being reacted for 24 hours under room temperature (25 DEG C), obtain black to methoxyl group
The polyaniline of phenylacetic acid doping.It filters, successively uses distilled water, dehydrated alcohol washs three times.Drying obtains sample for 24 hours under normal temperature condition
Product.
Embodiment 8：
It take 2,5- dimethyl phenyl acetic acid as the preparation for the polyaniline nano ball that dopant obtains using 4- amino phenols as raw material：It will
16.4ml (0.1 mol) 2,5- dimethyl phenyl acetic acid（It is pure）, it is dissolved in and is made into the 2,5- of 0.25mol/L in the deionized water of 400ml
Then 0.3647 ml (4mmol) 4- amino phenols is added in above-mentioned solution by dimethyl phenyl acetic acid solution, and constantly carry out magnetic
Power stirring, formed homogeneous phase solution after five minutes.Then 0.398g (2mmol) is added) FeSO4·4H2O is to after being completely dissolved, slowly
0.95ml (0.01mol) H is added2O2, solution becomes darkviolet, after reacting for 24 hours under room temperature (25 DEG C), obtains the 2,5- of black
The polyaniline of dimethyl phenyl acetic acid doping.It filters, successively uses distilled water, dehydrated alcohol washs three times.It is dried for 24 hours under normal temperature condition
Obtain sample.
Claims (9)
1. a kind of preparation method of poly- hydroxyanilines microballoon, including：
（1）Dopant is dissolved in deionized water, the aqueous solution containing dopant is made into；
（2）Phenyl amines raw material is added in the aqueous solution containing dopant, catalysis is slowly inwardly added after 5min is mixed
Agent is then slowly added into oxidant to being completely dissolved, and reacts 24-26h at normal temperature, washs, and filters, dry, obtains nano junction
Structure polyaniline.
2. a kind of preparation method of poly- hydroxyanilines microballoon according to claim 1, which is characterized in that the step（1）
Middle dopant is acetic acid, dichloroacetic acid, p-methyl benzenesulfonic acid, p-aminobenzene sulfonic acid, dodecyl benzene sulfonic acid, naphthalene sulfonic acids, camphor sulphur
Any acid in the organic acids such as acid, salicylic acid, sulfosalicylic acid, 2,5- dimethyl phenyl acetic acid, homoanisic acid.
3. a kind of preparation method of poly- hydroxyanilines microballoon according to claim 1, which is characterized in that the step
（1）In the aqueous solution containing dopant concentration be 0.20-0.30mol/L.
4. a kind of preparation method of poly- hydroxyanilines microballoon according to claim 1, which is characterized in that the step（1）
Middle reaction temperature is room temperature；Reaction time is 10min-1h.
5. a kind of preparation method of poly- hydroxyanilines microballoon according to claim 1, which is characterized in that the step（2）
Middle phenyl amines raw material is aniline, 3- amino phenols, 2- amino phenols, 4- amino phenols.
6. a kind of preparation method of poly- hydroxyanilines microballoon according to claim 1, which is characterized in that the step（2）
The concentration of middle phenyl amines raw material is 0.01-0.05mol/L.
7. a kind of preparation method of poly- hydroxyanilines microballoon according to claim 1, which is characterized in that the step（2）
Middle catalyst is the chemical combination containing ferrous ion such as ferrous gluconate, acetylacetone,2,4-pentanedione ferrous iron, frerrous chloride, ferrous sulfate
Object；Oxidant is H2O2。
8. a kind of preparation method of poly- hydroxyanilines microballoon according to claim 1, which is characterized in that the step（2）
Middle FeSO4·4H2The concentration of O is 0.001-0.005mol/L；H2O2Concentration be 0.020-0.025mol/L.
9. a kind of preparation method of poly- hydroxyanilines microballoon according to claim 1, which is characterized in that the step（2）
Middle nanostructure is globular nanostructures.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810748419.3A CN108864425A (en) | 2018-07-10 | 2018-07-10 | A kind of preparation method of poly- hydroxyanilines microballoon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810748419.3A CN108864425A (en) | 2018-07-10 | 2018-07-10 | A kind of preparation method of poly- hydroxyanilines microballoon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108864425A true CN108864425A (en) | 2018-11-23 |
Family
ID=64300289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810748419.3A Pending CN108864425A (en) | 2018-07-10 | 2018-07-10 | A kind of preparation method of poly- hydroxyanilines microballoon |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108864425A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112094408A (en) * | 2020-09-03 | 2020-12-18 | 哈尔滨工业大学（深圳） | Aromatic aminophenol polymer, preparation method thereof and noble metal ion adsorption recovery agent |
| CN112490450A (en) * | 2020-10-26 | 2021-03-12 | 温州大学 | Adhesive for microbial fuel cell, application, cathode and microbial fuel cell |
| CN114797694A (en) * | 2022-05-27 | 2022-07-29 | 西南交通大学 | Reduced graphene oxide aerogel wave-absorbing microsphere with chiral spiral structure, preparation method and application |
-
2018
- 2018-07-10 CN CN201810748419.3A patent/CN108864425A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112094408A (en) * | 2020-09-03 | 2020-12-18 | 哈尔滨工业大学（深圳） | Aromatic aminophenol polymer, preparation method thereof and noble metal ion adsorption recovery agent |
| CN112490450A (en) * | 2020-10-26 | 2021-03-12 | 温州大学 | Adhesive for microbial fuel cell, application, cathode and microbial fuel cell |
| CN112490450B (en) * | 2020-10-26 | 2022-05-10 | 温州大学 | Adhesive for microbial fuel cell, application, cathode and microbial fuel cell |
| CN114797694A (en) * | 2022-05-27 | 2022-07-29 | 西南交通大学 | Reduced graphene oxide aerogel wave-absorbing microsphere with chiral spiral structure, preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gemeay et al. | Preparation and characterization of polyaniline/manganese dioxide composites via oxidative polymerization: Effect of acids | |
| CN101798462B (en) | Graphene/conductive polymer composite film and preparation method thereof | |
| Manivel et al. | Conducting polyaniline-graphene oxide fibrous nanocomposites: preparation, characterization and simultaneous electrochemical detection of ascorbic acid, dopamine and uric acid | |
| Tran et al. | The oxidation of aniline to produce “polyaniline”: a process yielding many different nanoscale structures | |
| Wan et al. | Surface modification of carbon nanotubes via combination of mussel inspired chemistry and chain transfer free radical polymerization | |
| Zujovic et al. | Structure of ultralong polyaniline nanofibers using initiators | |
| CN108864425A (en) | A kind of preparation method of poly- hydroxyanilines microballoon | |
| CN105885043B (en) | The preparation method of polyaniline nano microballoon with nucleocapsid | |
| KR20100078444A (en) | Method to produce aqueous graphene solution and aqueous conductive polymer solution | |
| Karim et al. | Conducting polyaniline‐titanium dioxide nanocomposites prepared by inverted emulsion polymerization | |
| CN104555985B (en) | The preparation method that a kind of boron phosphate is carbon nano-tube modified | |
| Peng et al. | Template-confined growth of poly (4-aminodiphenylamine) nanosheets as positive electrode toward superlong-life asymmetric supercapacitor | |
| Paik et al. | Polyaniline nanotubes with rectangular-hollow-core and its self-assembled surface decoration: High conductivity and dielectric properties | |
| Wang et al. | Metal oxide-assisted PEDOT nanostructures via hydrolysis-assisted vapor-phase polymerization for energy storage | |
| Choi et al. | Electrochemical activity of a polyaniline/polyaniline-grafted multiwalled carbon nanotube mixture produced by a simple suspension polymerization | |
| Liao | Green preparation of sulfonated polystyrene/polyaniline/silver composites with enhanced anticorrosive properties | |
| Bhandari et al. | Synergistic effect of simultaneous dual doping in solvent-free mechanochemical synthesis of polyaniline supercapacitor comparable to the composites with multiwalled carbon nanotube | |
| Zhou et al. | Solid phase mechanochemical synthesis of polyaniline branched nanofibers | |
| Huang et al. | Synthesis, characterization and application in electrocatalysis of polyaniline/Au composite nanotubes | |
| Guo et al. | Improved electrocatalytic performance from graphene quantum dots/three-dimensional graphene/polyaniline doped powder to layer-by-layer self-assembled membrane materials | |
| Ali et al. | Novel sulfonated polyimide-nafion nanocomposite membranes: Fabrication, morphology and physiochemical investigations for fuel cell applications | |
| Kokubo | Water soluble single-nano carbon particles: fullerenol and its derivatives | |
| Lai et al. | Application of electroactive Au/aniline tetramer–graphene oxide composites as a highly efficient reusable catalyst | |
| Ghebache et al. | Effect of hematite on the energy storage performance of polyaniline/zeolite HY/α-Fe2O3 nanocomposite supercapacitor electrode | |
| CN102328960A (en) | Synthesis method of trimanganese tetroxide material with 3D (three-dimensional) flower-shaped structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20181123 |
|
| WD01 | Invention patent application deemed withdrawn after publication |