CN111974322A - Polypyrrole porous hollow nano-microsphere and preparation method and application thereof - Google Patents
Polypyrrole porous hollow nano-microsphere and preparation method and application thereof Download PDFInfo
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- CN111974322A CN111974322A CN201910449588.1A CN201910449588A CN111974322A CN 111974322 A CN111974322 A CN 111974322A CN 201910449588 A CN201910449588 A CN 201910449588A CN 111974322 A CN111974322 A CN 111974322A
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- polypyrrole
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- polypyrrole porous
- hollow nanospheres
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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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 relates to nanotechnology and polymer technology, in particular to a shell porous polypyrrole hollow nanosphere, a preparation method and application thereof, wherein the preparation process can be carried out according to the following method: under the action of oxidant ferric chloride, pyrrole monomer is polymerized on the surface of nanometer silica template at low temperature, and etched with hydrofluoric acid to form hollow structure and nanometer level holes in polypyrrole shell. The polypyrrole porous hollow nano-microsphere can be used as a filler for preparing gas separation membranes, pervaporation membranes, nanofiltration membranes and the like.
Description
Technical Field
The invention relates to a nanometer technology and a high molecular technology, in particular to a polypyrrole porous hollow nanometer microsphere and a preparation method and application thereof.
Background
Polypyrrole has been used in many applications due to its unique properties. At present, the synthesis method of polypyrrole comprises an electrochemical oxidation polymerization method and a chemical polymerization method, but the prepared polypyrrole has a single structure and cannot be well applied to industrial production. In order to prepare polypyrrole having a specific structure, researchers have developed various methods including template polymerization, interfacial polymerization, seed polymerization, and the like, and in particular, polypyrrole can be prepared by a chemical oxidative polymerization method in a dilute hydrochloric acid environment using ammonium persulfate as an oxidizing agent, but these synthetic methods use toxic and harmful chemicals and bring inevitable harmful effects on the nature, and thus research on green synthesis of polypyrrole having a specific structure has attracted great interest to researchers.
Due to the unique structure of the porous hollow nano microsphere, the porous hollow nano microsphere is added into a membrane matrix, so that the mass transfer path can be reduced, the mass transfer resistance is reduced, and the method is an effective method for improving the membrane flux. The invention mainly relates to polypyrrole porous hollow nano-microspheres prepared by a simple method and application thereof: under the action of oxidant, pyrrole monomer is chemically polymerized on the surface of nanometer silica template at low temperature, and etched with hydrofluoric acid to eliminate template and form hollow structure and leave nanometer level pores in the shell. The method is simple to operate and few in steps, and the prepared nano hollow microspheres can be used as fillers for preparing gas separation membranes, pervaporation membranes, nanofiltration membranes and the like.
Disclosure of Invention
The invention aims to provide a polypyrrole porous hollow nano microsphere which can be prepared by a simple method, and a preparation method and application thereof. The preparation scheme is as follows:
1) mixing silica microspheres (10-100 nm in size) with a certain amount of water;
2) dissolving a certain amount of pyrrole and sodium acetate in a certain amount of water, adding into the mixed solution prepared in the step 1), uniformly mixing by ultrasonic, cooling to below 4 ℃, and reacting for 10-15 hours;
3) Dissolving a certain amount of ferric chloride in water, adding into the mixed solution prepared in the step 2), continuously stirring and reacting for a period of time at 4 ℃, washing, centrifuging, soaking the obtained product in HF for a period of time, centrifuging, and washing to obtain the final product.
The concentration of ferric chloride is 0.1-0.5 mol/L; the concentration of HF is 3-8% (mass fraction). The invention has the following advantages: the hollow and shell layer porous structure is formed by utilizing a one-step template method, the process is simple, and the size of the prepared microspheres is uniform. The hollow size of the polypyrrole porous hollow nano-microspheres can be controlled by controlling the size of the silica template, and the thickness of the shell layer is controlled by the concentration of pyrrole. The polymer microspheres generated by the reaction are good in compatibility with other polymers when being used as a filler for preparing a mixed matrix membrane. The polypyrrole porous hollow nano-microsphere prepared by the invention can be used as a filler to be applied to gas separation membranes, pervaporation membranes, nanofiltration membranes and the like. The following examples are included to further illustrate the practice of the present invention. The following examples further describe and demonstrate embodiments within the scope of the present invention. The examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, as many variations thereof are possible without departing from the spirit and scope of the invention.
Drawings
FIG. 1 TEM image of polypyrrole porous hollow nanospheres
FIG. 2 BET analysis of polypyrrole porous hollow nanospheres
FIG. 3 SEM photo of porous hollow nanometer microsphere mixed base film of Pebax/polypyrrole
FIG. 4 is a surface electron microscope photograph of polypiperazine amide-polypyrrole porous hollow nano microsphere/polysulfone composite nanofiltration membrane
Detailed Description
Example 1
Dissolving a certain amount of Pebax1657 in a mixed solution of ethanol/water (70 wt%/30 wt%), heating at 80 ℃ for two hours, adding a certain amount of polypyrrole porous hollow nano microspheres into the mixed solution, ultrasonically stirring and uniformly dispersing, pouring the mixed solution into a polytetrafluoroethylene mold, standing at room temperature for 24 hours, and vacuum-drying in a vacuum oven at 45 ℃ for 24 hours.
TABLE 1 osmotic separation Performance of Pebax/polypyrrole porous hollow nanosphere mixed matrix membranes
Example 2
Polyethylene glycol methacrylate (PEGMEA) is used as a monomer, pentaerythritol triacrylate (PETA) is used as a cross-linking agent, polypyrrole porous hollow nano microspheres are used as a filling material, a certain amount of photoinitiator is added, the mixed solution is poured into a brown bottle to be uniformly dispersed by ultrasound, the brown bottle is placed between two glass plates, and the thickness is controlled by a copper wire to prepare a series of gas separation membranes. The gas permeability test of the membrane finds that N 2、CH4、CO2Compared with the original membrane, the permeability of the membrane is improved by about 2 times to the maximum, and the selectivity of the membrane is kept unchanged.
Example 3
Weighing polydimethylsiloxane, a cross-linking agent thereof and n-heptane in a certain ratio, uniformly stirring, adding polypyrrole porous hollow nano microspheres, stirring, performing ultrasonic treatment, and coating the polypyrrole porous hollow nano microspheres on a PVDF porous basement membrane. The coated membrane was placed in a fume hood, allowed to evaporate naturally for several hours, and then placed in an oven for thermal crosslinking. The mass ratio of the polypyrrole porous hollow nano-microspheres to the polydimethylsiloxane is 1% -5%, and the prepared membrane is dried and then used for pervaporation. Pervaporation test conditions: the vacuum degree of the downstream side is 5mmHg absolute negative pressure, and the cold well is used for condensation and collection; the upstream side operating temperature was 40 ℃ and the feed solution was a 5 wt% ethanol aqueous solution (mass fraction). The properties are shown in Table 2.
TABLE 2 ethanol separation Performance of polydimethylsiloxane/polypyrrole porous hollow nanosphere mixed matrix membranes
Example 4
The polysulfone ultrafiltration membrane is used as a base membrane, and the polysulfone base membrane is firstly washed in distilled water, and the base membrane with a proper area is clamped between two polytetrafluoroethylene plates. Carrying out ultrasonic treatment on polypyrrole porous hollow nano microspheres in a piperazine aqueous solution (0.4 wt%) for 30 minutes to fully disperse the polypyrrole porous hollow nano microspheres to prepare an aqueous solution, pouring a proper amount of the aqueous solution onto a polysulfone basal membrane, keeping the aqueous solution at room temperature for a period of time, then pouring the piperazine aqueous solution from the polysulfone basal membrane, and removing redundant aqueous phase by using a rubber rod; and (3) quickly pouring a proper amount of 0.15 wt% of trimesoyl chloride normal hexane solution onto the base membrane soaked by the piperazine water solution, pouring out the redundant oil phase solution after polymerizing for a certain time, and then putting into a 70 ℃ oven for further polymerizing to obtain the polypiperazine amide composite nanofiltration membrane containing the polypyrrole microspheres.
As the concentration of polypyrrole microspheres increased from 0 to 0.01 wt%, the water flux of the composite membrane increased from 62.6 to 77.3L/(m)2H) and Na)2SO4The retention rate of the catalyst was slightly reduced from 98.5% to 97.7%. When the concentration of the polypyrrole microspheres is increased to 0.02 w/v%, the rejection rate and the water flux of the composite membrane are respectively increased to 98.75L/(m) and 86.2L/(m)2·h)。
The above examples do not indicate a limited scope of application of the patent. Any person skilled in the art can easily apply the teachings of the patent to any other possible system.
Claims (7)
1. A preparation method of polypyrrole porous hollow nano-microspheres is characterized by comprising the following steps:
1) mixing silica microspheres (10-100 nm in size) with a certain amount of water;
2) dissolving a certain amount of pyrrole and sodium acetate in a certain amount of water, adding into the mixed solution prepared in the step 1), uniformly mixing by ultrasonic waves, and cooling to below 4 ℃;
3) dissolving a certain amount of ferric chloride in water, adding into the mixed solution prepared in the step 2), continuously stirring and reacting for a period of time at 4 ℃, washing, centrifuging, soaking the obtained product in HF for a period of time, centrifuging, and washing to obtain the final product.
2. The preparation method of the polypyrrole porous hollow nanospheres of claim 1, wherein the preparation method comprises the following steps: the concentration of the ferric chloride is 0.1-0.5 mol/L.
3. The preparation method of the polypyrrole porous hollow nanospheres according to claim 1, wherein: the reaction time is 10-15 hours.
4. The preparation method of the polypyrrole porous hollow nanospheres according to claim 1, wherein: the concentration of HF is 3-8% (mass fraction).
5. The polypyrrole porous hollow nanospheres prepared by the preparation method of polypyrrole porous hollow nanospheres according to claim 1, wherein: the size of the hollow structure of the microsphere can be regulated and controlled by the size of the silicon dioxide template, and the thickness of the shell layer can be controlled by the concentration of pyrrole.
6. The polypyrrole porous hollow nanospheres prepared according to claims 1 to 5, wherein the polypyrrole porous hollow nanospheres have a hollow structure, the shell material is polypyrrole, and the shell has nanometer-sized pores.
7. The application of the polypyrrole porous hollow nanospheres according to claims 1 to 6, wherein the polypyrrole porous hollow nanospheres are applied in preparation of separation membranes. Specifically, the polypyrrole porous hollow nanospheres are used as fillers to be blended with other polymer membrane materials to prepare the separation membrane, and can be used for gas membrane separation, nanofiltration and pervaporation.
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Citations (7)
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|---|---|---|---|---|
| CN1631951A (en) * | 2004-12-02 | 2005-06-29 | 同济大学 | Hollow polymer microsphere and method for preparing same |
| CN101165092A (en) * | 2006-10-16 | 2008-04-23 | 中南大学 | Method for preparing electric polypyrrole nano hollow sphere |
| CN102863617A (en) * | 2011-07-04 | 2013-01-09 | 中国科学院宁波材料技术与工程研究所 | Preparation method and application of polypyrrole nanometer microspheres |
| CN103259000A (en) * | 2013-04-25 | 2013-08-21 | 浙江师范大学 | Polypyrrole hollow microsphere/ sulfur composite material as well as preparation method and application thereof |
| CN104624068A (en) * | 2015-01-22 | 2015-05-20 | 天津大学 | Method for polypyrrole nano material modified polymer ultrafiltration membrane |
| CN107281940A (en) * | 2016-03-30 | 2017-10-24 | 天津工业大学 | A kind of polymer/polymer hollow microsphere hybridized film and application |
| CN108912330A (en) * | 2018-07-14 | 2018-11-30 | 桂林理工大学 | The preparation method and application of polypyrrole hollow mesoporous silica microsphere |
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- 2019-05-23 CN CN201910449588.1A patent/CN111974322A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1631951A (en) * | 2004-12-02 | 2005-06-29 | 同济大学 | Hollow polymer microsphere and method for preparing same |
| CN101165092A (en) * | 2006-10-16 | 2008-04-23 | 中南大学 | Method for preparing electric polypyrrole nano hollow sphere |
| CN102863617A (en) * | 2011-07-04 | 2013-01-09 | 中国科学院宁波材料技术与工程研究所 | Preparation method and application of polypyrrole nanometer microspheres |
| CN103259000A (en) * | 2013-04-25 | 2013-08-21 | 浙江师范大学 | Polypyrrole hollow microsphere/ sulfur composite material as well as preparation method and application thereof |
| CN104624068A (en) * | 2015-01-22 | 2015-05-20 | 天津大学 | Method for polypyrrole nano material modified polymer ultrafiltration membrane |
| CN107281940A (en) * | 2016-03-30 | 2017-10-24 | 天津工业大学 | A kind of polymer/polymer hollow microsphere hybridized film and application |
| CN108912330A (en) * | 2018-07-14 | 2018-11-30 | 桂林理工大学 | The preparation method and application of polypyrrole hollow mesoporous silica microsphere |
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Application publication date: 20201124 |