CN111961200A - Preparation method of hollow spherical polyaniline/pyrrole nano material - Google Patents
Preparation method of hollow spherical polyaniline/pyrrole nano material Download PDFInfo
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- CN111961200A CN111961200A CN202010881614.0A CN202010881614A CN111961200A CN 111961200 A CN111961200 A CN 111961200A CN 202010881614 A CN202010881614 A CN 202010881614A CN 111961200 A CN111961200 A CN 111961200A
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
Abstract
The invention discloses a preparation method of a hollow spherical polyaniline/pyrrole nano material, which comprises the following steps: firstly, stirring aniline, pyrrole, triton X-100 and deionized water at 0 ℃ to obtain a transparent mixed solution; secondly, carrying out ultrasonic treatment on the mixed solution at the temperature of 5-18 ℃; thirdly, adding an ammonium persulfate solution into the mixed solution after ultrasonic treatment, and reacting at 0 ℃ to obtain a first reaction solution; fourthly, standing the first reaction solution at 0 ℃ for reaction to obtain a second reaction solution; and fifthly, centrifugally precipitating and washing the second reaction solution, and drying to obtain the hollow spherical polyaniline/pyrrole nano material. According to the invention, the triton X-100 is used as a soft template, the aniline and the pyrrole are copolymerized by using the ammonium persulfate as an oxidant, and the hollow spherical polyaniline/pyrrole nano material is prepared, so that the preparation process is simple, the template is not needed, the steps of preparing and removing the template are omitted, the damage to the structural integrity of the hollow spherical polyaniline/pyrrole nano material is avoided, and the method is suitable for large-scale production.
Description
Technical Field
The invention belongs to the technical field of high-molecular conductive materials, and particularly relates to a preparation method of a hollow spherical polyaniline/pyrrole nano material.
Background
Among conductive polymers, polyaniline has the characteristics of wide raw material sources, low price, good environmental stability, excellent corrosion resistance and the like, and polypyrrole has the advantages of easiness in synthesis, excellent conductivity, environmental friendliness and the like. Polyaniline and polypyrrole are used as the most representative materials in conductive polymers, and are widely applied to the fields of gas-sensitive sensing, electrocatalysis, wave absorption, electromagnetic shielding, electric conduction, metal corrosion protection and the like. However, single high molecular polymer has its own disadvantages, and the presence of benzene rings in the polyaniline structure and the strong hydrogen bonding between adjacent molecular chains make the molecular chains thereof have strong rigidity and poor solubility in most organic solvents. Polypyrrole has poor conductive stability, is not dissolved or melted, is difficult to process, and greatly limits the practical application of the polypyrrole.
The high-molecular copolymerization is an important modification method, and can integrate the advantages of different monomers to obtain a copolymer with better performance. The existing methods for preparing the nanometer high molecular polymer mainly comprise a chemical oxidation polymerization method and an electrochemical polymerization method. The electrochemical polymerization method usually adopts anodic oxidation to carry out polymerization reaction, regulates and controls the morphology of a product by controlling current and the like, but is limited by the area of an electrode and is only suitable for preparing small-batch conductive polymers. The chemical oxidation polymerization method has simple operation and low cost, and is easy for large-scale production. Therefore, the method for preparing the copolymer polymer conductive material by adopting the chemical oxidation polymerization method has important significance.
The micro-nano conductive polymer hollow sphere has wide application prospect in the fields of microcapsule coating, micro-reactor, drug slow release, biosensing and the like. Generally, polyaniline and polypyrrole hollow spheres are realized by adopting a template method, the size of the hollow spheres is effectively controlled by selecting a proper template, and the template is removed after the reaction is finished. The preparation and removal processes of the template are complex, and the problems of reduced experimental repeatability, damaged internal hollow structure and the like can be caused.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a method for preparing a hollow spherical polyaniline/pyrrole nano material, aiming at the defects of the prior art. According to the method, Triton X-100 is used as a soft template, and ammonium persulfate is used as an oxidant to enable two monomers, namely aniline and pyrrole, to be copolymerized to prepare the hollow spherical polyaniline/pyrrole nano material, the preparation process is simple, the template is not needed, the steps of preparing and removing the template are omitted, the damage to the structural integrity of the hollow spherical polyaniline/pyrrole nano material is avoided, and the method is suitable for large-scale production.
In order to solve the technical problems, the invention adopts the technical scheme that: a preparation method of a hollow spherical polyaniline/pyrrole nano material is characterized by comprising the following steps:
step one, stirring and mixing aniline, pyrrole, triton X-100 and deionized water uniformly to ensure that liquid drops floating in the solution completely disappear to obtain a transparent mixed solution; the temperature for stirring and mixing is 0 ℃;
step two, carrying out ultrasonic treatment on the mixed solution obtained in the step one; the temperature of the ultrasonic treatment is 5-18 ℃;
step three, adding an ammonium persulfate solution into the mixed solution subjected to the ultrasonic treatment in the step two for reaction to obtain a first reaction solution; the temperature of the reaction is 0 ℃;
step four, standing the first reaction solution obtained in the step three for reaction to obtain a second reaction solution; the temperature of the reaction is 0 ℃;
and fifthly, centrifuging the second reaction solution obtained in the fourth step, washing the obtained centrifugal precipitate with deionized water, and drying to obtain the hollow spherical polyaniline/pyrrole nano material.
According to the invention, by utilizing the characteristic that aniline and pyrrole have similar structures, and adopting a copolymerization method, under the action of Triton X-100, aniline and pyrrole monomers are copolymerized by taking ammonium persulfate as an oxidant, the aniline and pyrrole monomers are bonded on the surface of the Triton X-100 of a soft template, and a hollow structure is formed after oxidative polymerization of ammonium persulfate, so that the hollow spherical polyaniline/pyrrole nano material is prepared. The preparation process is simple, does not need a template, omits the steps of preparing and removing the template, avoids the damage to the structural integrity of the hollow spherical polyaniline/pyrrole nano material, and is suitable for large-scale production. In addition, the hollow spherical polyaniline/pyrrole nano material provided by the invention integrates the advantages of good environmental stability and excellent corrosion resistance of single polyaniline and the advantages of excellent conductivity and environmental friendliness of single polypyrrole, and overcomes the defects of strong molecular chain rigidity and poor solubility in most organic solvents due to the existence of benzene rings in the structure of the single polyaniline and strong hydrogen bonding action between adjacent molecular chains, and the defects of poor electrical stability, insolubility, infusibility and difficulty in processing of the single polypyrrole, so that the hollow spherical polyaniline/pyrrole nano material provided by the invention has a wide application prospect.
The preparation method of the hollow spherical polyaniline/pyrrole nano material is characterized in that in the step one, the molar ratio of the aniline, the pyrrole, the triton X-100 to the deionized water is 1: (0.5-2): 0.065 (600-1660).
The preparation method of the hollow spherical polyaniline/pyrrole nano material is characterized in that the molar ratio of the aniline and the pyrrole in the first step to the ammonium persulfate in the ammonium persulfate solution in the third step is 1: (0.5-2): (1.3-4).
The preparation method of the hollow spherical polyaniline/pyrrole nano material is characterized in that the stirring and mixing time in the step one is 20-40 min.
The preparation method of the hollow spherical polyaniline/pyrrole nano material is characterized in that the ultrasonic treatment time in the step two is 20-40 min.
The preparation method of the hollow spherical polyaniline/pyrrole nano material is characterized in that the reaction time in the step three is 60-80 min.
The preparation method of the hollow spherical polyaniline/pyrrole nano material is characterized in that the reaction time in the fourth step is 4-12 h.
The preparation method of the hollow spherical polyaniline/pyrrole nano material is characterized in that in the fifth step, the washing times of the deionized water are not less than 20 times.
The preparation method of the hollow spherical polyaniline/pyrrole nano material is characterized in that in the fifth step, the drying is vacuum drying, and the temperature of the vacuum drying is 60-80 ℃.
Compared with the prior art, the invention has the following advantages:
1. the invention adopts a copolymerization method, under the action of Triton X-100, the aniline and the pyrrole are copolymerized by taking ammonium persulfate as an oxidant, and the hollow spherical polyaniline/pyrrole nano material is prepared.
2. The hollow spherical polyaniline/pyrrole nano material provided by the invention integrates the advantages of good stability and excellent corrosion resistance of polyaniline and polypyrrole, overcomes the defects of poor solubility of polyaniline, poor electrical stability and difficult processing of polypyrrole, and has a wide application prospect.
3. The preparation method has the advantages that the molar ratio range of the raw materials of aniline, pyrrole and deionized water is large, the hollow spherical polyaniline/pyrrole nano materials with various sizes and uniformity are prepared by controlling the molar ratio of the raw materials, the application requirements of different occasions are met, and the preparation method is flexible, convenient and easy to realize.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
Fig. 1 is an SEM image of a hollow spherical polyaniline/pyrrole nanomaterial prepared in example 1 of the present invention.
Fig. 2a is a TEM image 1 of the hollow spherical polyaniline/pyrrole nanomaterial prepared in example 1 of the present invention.
Fig. 2b is a TEM image 2 of the hollow spherical polyaniline/pyrrole nanomaterial prepared in example 1 of the present invention.
Fig. 3 is an SEM image of the hollow spherical polyaniline/pyrrole nanomaterial prepared in example 2 of the present invention.
Fig. 4 is an SEM image of the hollow spherical polyaniline/pyrrole nanomaterial prepared in example 3 of the present invention.
Detailed Description
Example 1
The embodiment comprises the following steps:
step one, stirring and mixing 0.002mol of aniline, 0.004mol of pyrrole, 0.00013mol of triton X-100 and 21.6mL of deionized water at the temperature of 0 ℃ for 20min to ensure that liquid drops floating in the solution completely disappear to obtain a transparent mixed solution;
step two, carrying out ultrasonic treatment on the mixed solution obtained in the step one for 40min at the temperature of 5 ℃;
step three, adding an ammonium persulfate solution into the mixed solution subjected to ultrasonic treatment in the step two, and reacting for 60min at the temperature of 0 ℃ to obtain a first reaction solution; the content of ammonium persulfate in the ammonium persulfate solution is 0.008 mol;
step four, standing and reacting the first reaction liquid obtained in the step three for 4 hours at the temperature of 0 ℃ to obtain a second reaction liquid;
and fifthly, centrifuging the second reaction solution obtained in the fourth step, washing the obtained centrifugal precipitate for 20 times by using deionized water, and then placing the washed centrifugal precipitate in a vacuum drying oven to dry for 12 hours at the temperature of 60 ℃ to obtain the hollow spherical polyaniline/pyrrole nano material.
Fig. 1 is an SEM image of the hollow spherical polyaniline/pyrrole nanomaterial prepared in this embodiment, and it can be seen from fig. 1 that the hollow spherical polyaniline/pyrrole nanomaterial prepared in this embodiment has a nano-spherical morphology, uniform size, and good dispersibility.
Fig. 2a is a TEM image 1 of the hollow spherical polyaniline/pyrrole nanomaterial prepared in this example, and fig. 2b is a TEM image 2 of the hollow spherical polyaniline/pyrrole nanomaterial prepared in this example, and as can be seen from fig. 2a and fig. 2b, the hollow spherical polyaniline/pyrrole nanomaterial prepared in this example has a hollow structure inside, a particle size of about 100nm, and a shell thickness of the hollow spherical shell of about 25 nm.
Example 2
The embodiment comprises the following steps:
step one, stirring and mixing 0.002mol of aniline, 0.001mol of pyrrole, 0.00013mol of triton X-100 and 60mL of deionized water uniformly for 40min at the temperature of 0 ℃ to ensure that liquid drops floating in the solution completely disappear to obtain a transparent mixed solution;
step two, carrying out ultrasonic treatment on the mixed solution obtained in the step one for 20min at the temperature of 18 ℃;
step three, adding an ammonium persulfate solution into the mixed solution subjected to ultrasonic treatment in the step two, and reacting for 80min at the temperature of 0 ℃ to obtain a first reaction solution; the content of ammonium persulfate in the ammonium persulfate solution is 0.0026 mol;
step four, standing and reacting the first reaction liquid obtained in the step three for 15 hours at the temperature of 0 ℃ to obtain a second reaction liquid;
and fifthly, centrifuging the second reaction solution obtained in the fourth step, washing the obtained centrifugal precipitate for 25 times by using deionized water, and then placing the washed centrifugal precipitate in a vacuum drying oven to dry for 12 hours at the temperature of 80 ℃ to obtain the hollow spherical polyaniline/pyrrole nano material.
Fig. 3 is an SEM image of the hollow spherical polyaniline/pyrrole nanomaterial prepared in this example, and it can be seen from fig. 3 that the hollow spherical polyaniline/pyrrole nanomaterial is a nano spherical particle, and has uniform size and good dispersibility.
Example 3
The embodiment comprises the following steps:
step one, stirring and mixing 0.005mol of aniline, 0.004mol of pyrrole, 0.000325mol of triton X-100 and 90mL of deionized water uniformly for 30min at the temperature of 0 ℃ to ensure that liquid drops floating in the solution completely disappear to obtain a transparent mixed solution;
step two, carrying out ultrasonic treatment on the mixed solution obtained in the step one for 30min at the temperature of 8 ℃;
step three, adding an ammonium persulfate solution into the mixed solution subjected to ultrasonic treatment in the step two, and reacting for 70min at the temperature of 0 ℃ to obtain a first reaction solution; the content of ammonium persulfate in the ammonium persulfate solution is 0.012 mol;
step four, standing the first reaction solution obtained in the step three at the temperature of 0 ℃ for reaction for 12 hours to obtain a second reaction solution;
and fifthly, centrifuging the second reaction solution obtained in the fourth step, washing the obtained centrifugal precipitate for 23 times by using deionized water, and then placing the washed centrifugal precipitate in a vacuum drying oven to dry for 12 hours at 70 ℃ to obtain the hollow spherical polyaniline/pyrrole nano material.
Fig. 4 is an SEM image of the hollow spherical polyaniline/pyrrole nanomaterial prepared in this example, and it can be seen from fig. 4 that the hollow spherical polyaniline/pyrrole nanomaterial is a nano spherical particle, and has a uniform size and a uniform dispersion.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (9)
1. A preparation method of a hollow spherical polyaniline/pyrrole nano material is characterized by comprising the following steps:
step one, stirring and mixing aniline, pyrrole, triton X-100 and deionized water uniformly to ensure that liquid drops floating in the solution completely disappear to obtain a transparent mixed solution; the temperature for stirring and mixing is 0 ℃;
step two, carrying out ultrasonic treatment on the mixed solution obtained in the step one; the temperature of the ultrasonic treatment is 5-18 ℃;
step three, adding an ammonium persulfate solution into the mixed solution subjected to the ultrasonic treatment in the step two for reaction to obtain a first reaction solution; the temperature of the reaction is 0 ℃;
step four, standing the first reaction solution obtained in the step three for reaction to obtain a second reaction solution; the temperature of the reaction is 0 ℃;
and fifthly, centrifuging the second reaction solution obtained in the fourth step, washing the obtained centrifugal precipitate with deionized water, and drying to obtain the hollow spherical polyaniline/pyrrole nano material.
2. The method for preparing the hollow spherical polyaniline/pyrrole nanomaterial according to claim 1, wherein the molar ratio of the aniline, the pyrrole, the triton X-100 and the deionized water in the first step is 1: (0.5-2): 0.065 (600-1660).
3. The method for preparing the hollow spherical polyaniline/pyrrole nano-material according to claim 1, wherein the molar ratio of the aniline, the pyrrole and the ammonium persulfate in the ammonium persulfate solution in the step one is 1: (0.5-2): (1.3-4).
4. The method for preparing a hollow spherical polyaniline/pyrrole nano-material according to claim 1, wherein the stirring and mixing time in the first step is 20min to 40 min.
5. The method for preparing the hollow spherical polyaniline/pyrrole nano-material according to claim 1, wherein the time of the ultrasonic treatment in the second step is 20min to 40 min.
6. The method for preparing the hollow spherical polyaniline/pyrrole nano-material according to claim 1, wherein the reaction time in step three is 60-80 min.
7. The method for preparing the hollow spherical polyaniline/pyrrole nano-material according to claim 1, wherein the reaction time in the fourth step is 4-12 h.
8. The method for preparing a hollow spherical polyaniline/pyrrole nano-material as claimed in claim 1, wherein the number of times of deionized water washing in step five is not less than 20.
9. The method for preparing a hollow spherical polyaniline/pyrrole nano-material according to claim 1, wherein the drying in step five is vacuum drying, and the temperature of the vacuum drying is 60-80 ℃.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3954648A (en) * | 1969-12-22 | 1976-05-04 | Pennwalt Corporation | Coatings removal composition containing an alkali metal hydroxide, an oxygenated organic solvent, and an amine |
| CN103374129A (en) * | 2012-04-11 | 2013-10-30 | 中国科学院合肥物质科学研究院 | Preparation method of polyaniline micro hollow sphere |
| CN107146892A (en) * | 2017-05-23 | 2017-09-08 | 广东工业大学 | The preparation method and microbiological fuel cell of a kind of hollow-core construction carbon nano-particle |
-
2020
- 2020-08-26 CN CN202010881614.0A patent/CN111961200A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3954648A (en) * | 1969-12-22 | 1976-05-04 | Pennwalt Corporation | Coatings removal composition containing an alkali metal hydroxide, an oxygenated organic solvent, and an amine |
| CN103374129A (en) * | 2012-04-11 | 2013-10-30 | 中国科学院合肥物质科学研究院 | Preparation method of polyaniline micro hollow sphere |
| CN107146892A (en) * | 2017-05-23 | 2017-09-08 | 广东工业大学 | The preparation method and microbiological fuel cell of a kind of hollow-core construction carbon nano-particle |
Non-Patent Citations (1)
| Title |
|---|
| CHUANQIANG ZHOU等: ""Fabrication of Poly(aniline-co-pyrrole) Hollow Nanospheres with Triton X-100 Micelles as Templates"", 《JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY》 * |
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