CN114044911A - Polyphosphazene microsphere with pH chromogenic response and preparation method thereof - Google Patents
Polyphosphazene microsphere with pH chromogenic response and preparation method thereof Download PDFInfo
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- CN114044911A CN114044911A CN202111339787.0A CN202111339787A CN114044911A CN 114044911 A CN114044911 A CN 114044911A CN 202111339787 A CN202111339787 A CN 202111339787A CN 114044911 A CN114044911 A CN 114044911A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/025—Polyphosphazenes
Abstract
The invention belongs to the technical field of polyphosphazene microspheres with pH chromogenic responses, and particularly relates to polyphosphazene microspheres with pH chromogenic responses and a preparation method thereof, wherein the polyphosphazene microspheres are prepared from the following raw materials in parts by volume: 1-20 parts by volume of hexachlorocyclotriphosphazene solution, 1-70 parts by volume of phenolphthalein compound solution, 50-2000 parts by volume of solvent and 4-50 parts by volume of acid-binding agent solution. The pH color development response characteristic of phenolphthalein substances is embodied; and the polyphosphazene microspheres embedded with the phenolphthalein structure are prepared by the simple and rapid method, part of the phenolphthalein structure is preserved, and the polyphosphazene microspheres still have the characteristic of pH chromogenic response. The product pH color response polyphosphazene microsphere has good monodispersity, uniform size and good stability, and the particle size is mainly distributed in 0.5-3.0 um. The polyphosphazene microsphere with the pH color response obtained by the preparation method can be used as an acid-base indicator which can be recycled for multiple times.
Description
Technical Field
The invention belongs to the technical field of polyphosphazene microspheres with pH chromogenic responses, and particularly relates to polyphosphazene microspheres with pH chromogenic responses and a preparation method thereof.
Background
At present, the preparation and application of various polymers containing phenolphthalein structures, such as polyethersulfone and polyamide, are reported, for example: phenol, aniline and formaldehyde are used as raw materials, and are synthesized by a benzoxazine intermediate, and then are subjected to thermosetting to obtain the polybenzoxazine resin containing a phenolphthalein structure [ Gaoxing, Mengweiwei, Zhangting, Wangdingxia, Luzhou, the synthesis of the polybenzoxazine containing the phenolphthalein structure, material engineering, 2010, (Z1) and 64-67. ]. The patent CN108479432A dissolves and spins phenolphthalein polyethersulfone, sprays cross-linked polyvinylpyrrolidone solution, and carries out hot-pressing treatment to obtain the hydrophilic phenolphthalein polyethersulfone composite nanofiber ultrafiltration membrane. Patent CN113150548A uses an alicyclic dianhydride monomer and an aromatic diamine monomer containing phenolphthalein structure as raw materials, and prepares a flame-retardant and highly transparent polyimide film by a one-step high-temperature solution polycondensation method.
The phenolphthalein compound is a common acid-base indicator, can generate structural change under different pH environments to present different colors, and has pH chromogenic response. However, in the application of the phenolphthalein compound as an indicator, the phenolphthalein compound cannot be recovered, and remains in an aqueous solution, which is likely to cause pollution, so that it is necessary to develop a recyclable and environmentally friendly acid-base indicator having a wide application prospect.
Disclosure of Invention
In view of the above technical problems, the present invention is directed to at least one of the technical problems in the prior art, and therefore an aspect of the present invention is to provide polyphosphazene microspheres with pH chromogenic response, which have good monodispersity, solid structure and good stability.
Another aspect of the present invention is to provide a method for preparing polyphosphazene microspheres with pH chromogenic response, wherein the method is simple, convenient and fast, and prepares polyphosphazene microspheres embedded with phenolphthalein structure, and a part of phenolphthalein structure of the polyphosphazene microspheres is preserved and still has the characteristic of pH chromogenic response.
The polyphosphazene microsphere with the pH chromogenic response is prepared from the following raw materials in parts by volume: 1-20 parts by volume of hexachlorocyclotriphosphazene solution, 1-70 parts by volume of phenolphthalein compound solution, 50-2000 parts by volume of solvent and 4-50 parts by volume of acid-binding agent solution.
Phenolphthalein compounds include the following:
The solvent is one or more of acetone, tetrahydrofuran, pyridine, acetonitrile, ethanol, methanol, benzene, toluene, N-hexane and N, N-dimethylformamide.
The acid-binding agent is one or a mixture of triethylamine, pyridine, sodium carbonate, sodium bicarbonate, potassium carbonate or sodium bicarbonate.
A preparation method of polyphosphazene microspheres with pH chromogenic response comprises the steps of adding hexachlorocyclotriphosphazene solution, phenolphthalein compound solution and solvent into a container, adding acid-binding agent solution under auxiliary dispersion, and continuing reaction; and after the reaction is finished, filtering or centrifugally separating and washing to obtain the polyphosphazene microspheres with pH chromogenic response.
The auxiliary dispersing mode includes but is not limited to one or more of ultrasonic assistance, magnetic stirring, mechanical stirring or oscillation mixing.
Auxiliary dispersion is carried out at 0-50 ℃.
The reaction time is 10-360 min.
Compared with the prior art, the invention has the beneficial effects that:
the invention embodies the pH color development response characteristic of phenolphthalein substances; and the polyphosphazene microspheres embedded with the phenolphthalein structure are prepared by the simple and rapid method, part of the phenolphthalein structure is preserved, and the polyphosphazene microspheres still have the characteristic of pH chromogenic response.
The product pH color response polyphosphazene microsphere has good monodispersity, uniform size and good stability, and the particle size is mainly distributed in 0.5-3.0 um. The polyphosphazene microsphere with the pH color development response obtained by the preparation method can be used as an acid-base indicator which can be recycled for multiple times, is environment-friendly, and can also be used as a filling agent for developing a pH response color development product.
The preparation method is simple, the phenolphthalein compound and hexachlorocyclotriphosphazene are subjected to polycondensation to form polyphosphazene microspheres, the structure of the internal phenolphthalein compound still has pH color response, and the polyphosphazene microspheres with pH color response can be prepared in batches. The particle size of the polyphosphazene microsphere with pH chromogenic response can be controlled by adjusting the polymerization reaction condition; in addition, the invention prepares all the substances into solution and then carries out polymerization reaction, thereby being beneficial to continuous production.
Drawings
FIG. 1 is a scanning electron micrograph of pH responsive polyphosphazene microspheres prepared according to example 1;
FIG. 2 is a TEM image of the pH color-developing responsive polyphosphazene microspheres prepared in example 1;
FIG. 3 is a thermogravimetric analysis of the pH chromogenic response polyphosphazene microspheres prepared in example 1;
FIG. 4 is an infrared spectrum of the pH color-developing responsive polyphosphazene microsphere prepared in example 1.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
in a 250mL dry round-bottom flask, 1.0mL of a 1.0mM solution of hexachlorocyclotriphosphazene, 1.0mL of a 3.4mM solution of phenolphthalein, and 94mL of absolute ethanol were added, and 4.0mL of a 4.0mM solution of triethylamine was added with the aid of an ultrasonic cleaner at 30 ℃ to react for 120 minutes to obtain a milky turbid solution. And centrifuging, washing and drying to obtain the polyphosphazene microspheres with pH chromogenic response. The result shows that the average particle size of the prepared polyphosphazene microspheres is 2.7um and is mainly distributed in the range of 2-3 um.
FIG. 1 shows a scanning electron micrograph of a pH color-developing responsive polyphosphazene microsphere prepared under the conditions of example 1, and the result shows that the prepared polyphosphazene microsphere has uniform size, good monodispersity and smooth surface.
FIG. 2 shows a TEM photograph of pH-responsive polyphosphazene microspheres prepared under the conditions of example 1, and the result shows that the polyphosphazene microspheres prepared are solid microspheres.
FIG. 3 shows a thermogravimetric analysis of pH-chromogenic-responsive polyphosphazene microspheres prepared under the conditions of example 1.
FIG. 4 shows an infrared spectrum of a pH-responsive polyphosphazene microsphere prepared under the conditions of example 1.
Example 2:
in a 250mL dry round-bottom flask, 1.5mL of a 1.0mM solution of hexachlorocyclotriphosphazene, 1.0mL of a 3.4mM solution of phenolphthalein, and 94mL of absolute ethanol were added, and 4.0mL of a 4.0mM solution of triethylamine was added with the aid of an ultrasonic cleaner at 30 ℃ to react for 120 minutes to obtain a milky turbid solution. And centrifuging, washing and drying to obtain the polyphosphazene microspheres with pH chromogenic response. The result shows that the average particle size of the prepared polyphosphazene microspheres is 2.6um and is mainly distributed in the range of 2-3 um.
Example 3:
in a 250mL dry round bottom flask, 1.0mL of a 1.5mM solution of hexachlorocyclotriphosphazene, 1.0mL of a 3.4mM solution of phenolphthalein, and 94mL of absolute ethanol were added, and 4.0mL of a 4.0mM solution of triethylamine was added with the aid of an ultrasonic cleaner at 30 ℃ to react for 120 minutes to obtain a milky turbid solution. And centrifuging, washing and drying to obtain the polyphosphazene microspheres with pH chromogenic response. The result shows that the average particle size of the prepared polyphosphazene microspheres is 2.6um and is mainly distributed in the range of 2-3 um.
Example 4:
in a 250mL dry round-bottom flask, 1.0mL of a 1.0mM solution of hexachlorocyclotriphosphazene, 1.0mL of a 2.0mM solution of phenolphthalein, and 94mL of absolute ethanol were added, and 4.0mL of a 4.0mM solution of triethylamine was added with the aid of an ultrasonic cleaner at 30 ℃ to react for 120 minutes to obtain a milky turbid solution. And centrifuging, washing and drying to obtain the polyphosphazene microspheres with pH chromogenic response. The result shows that the average particle size of the prepared polyphosphazene microspheres is 2.4um and is mainly distributed in the range of 2-3 um.
Example 5:
in a 250mL dry round-bottom flask, 1.0mL of a 1.0mM solution of hexachlorocyclotriphosphazene, 1.0mL of a 3.4mM solution of α -naphtholphthalein, and 94mL of absolute ethanol were added, and 4.0mL of a 4.0mM solution of triethylamine was added with the aid of an ultrasonic cleaner at 30 ℃ to react for 120 minutes to obtain a milky turbid solution. And centrifuging, washing and drying to obtain the polyphosphazene microspheres with pH chromogenic response. The result shows that the average particle size of the prepared polyphosphazene microspheres is 2.8um and is mainly distributed in the range of 2-3 um.
Example 6:
in a 250mL dry round-bottom flask, 1.0mL of a 1.0mM solution of hexachlorocyclotriphosphazene, 1.0mL of a 3.4mM solution of phenolphthalein, and 94mL of acetonitrile were added, and 4.0mL of a 4.0mM solution of triethylamine was added with the aid of an ultrasonic cleaner at 30 ℃ to react for 120 minutes to obtain a milky turbid solution. And centrifuging, washing and drying to obtain the polyphosphazene microspheres with pH chromogenic response. The result shows that the average particle size of the prepared polyphosphazene microspheres is 2.6um and is mainly distributed in the range of 2-3 um.
Example 7:
1.0mL of a 1.0mM solution of hexachlorocyclotriphosphazene, 1.0mL of a 3.4mM solution of phenolphthalein and 94mL of absolute ethanol were added to a 250mL dry round-bottomed flask, and 6.0mL of a 4.0mM solution of triethylamine was added thereto with the aid of magnetic stirring at a constant temperature of 30 ℃ to react for 120 minutes to obtain a milky turbid solution. And centrifuging, washing and drying to obtain the polyphosphazene microspheres with pH chromogenic response. The result shows that the average particle size of the prepared polyphosphazene microspheres is 2.7um and is mainly distributed in the range of 2-3 um.
Example 8:
in a 250mL dry round-bottom flask, 1.0mL of a 1.0mM solution of hexachlorocyclotriphosphazene, 1.0mL of a 3.4mM solution of phenolphthalein, and 94mL of absolute ethanol were added, and 4.0mL of a 4.0mM solution of pyridine was added with the aid of an ultrasonic cleaner at 30 ℃ to react for 120 minutes to obtain a milky turbid solution. And centrifuging, washing and drying to obtain the polyphosphazene microspheres with pH chromogenic response. The result shows that the average particle size of the prepared polyphosphazene microspheres is 2.7um and is mainly distributed in the range of 2-3 um.
Example 9:
in a 250mL dry round-bottom flask, 1.0mL of a 1.0mM solution of hexachlorocyclotriphosphazene, 1.0mL of a 3.4mM solution of phenolphthalein, and 94mL of absolute ethanol were added, and 4.0mL of a 4.0mM solution of triethylamine was added with the aid of an ultrasonic cleaner at 20 ℃ to react for 120 minutes to obtain a milky turbid solution. And centrifuging, washing and drying to obtain the polyphosphazene microspheres with pH chromogenic response. The result shows that the average particle size of the prepared polyphosphazene microspheres is 2.5um and is mainly distributed in the range of 2-3 um.
Example 10:
in a 250mL dry round-bottom flask, 1.0mL of a 1.0mM solution of hexachlorocyclotriphosphazene, 1.0mL of a 3.4mM solution of phenolphthalein, and 94mL of absolute ethanol were added, and 4.0mL of a 4.0mM solution of triethylamine was added with the aid of an ultrasonic cleaner at 30 ℃ to react for 60 minutes to obtain a milky turbid solution. And centrifuging, washing and drying to obtain the polyphosphazene microspheres with pH chromogenic response. The result shows that the average particle size of the prepared polyphosphazene microspheres is 2.4um and is mainly distributed in the range of 2-3 um.
Although only the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art, and all changes are encompassed in the scope of the present invention.
Claims (8)
1. The polyphosphazene microsphere with the pH chromogenic response is characterized by comprising the following raw materials in parts by volume: 1-20 parts by volume of hexachlorocyclotriphosphazene solution, 1-70 parts by volume of phenolphthalein compound solution, 50-2000 parts by volume of solvent and 4-50 parts by volume of acid-binding agent solution.
2. The polyphosphazene microsphere with pH chromogenic response according to claim 1, wherein: phenolphthalein compounds include the following:
3. the polyphosphazene microsphere with pH chromogenic response according to claim 1, wherein: the solvent is one or more of acetone, tetrahydrofuran, pyridine, acetonitrile, ethanol, methanol, benzene, toluene, N-hexane and N, N-dimethylformamide.
4. The polyphosphazene microsphere with pH chromogenic response according to claim 1, wherein: the acid-binding agent is one or a mixture of triethylamine, pyridine, sodium carbonate, sodium bicarbonate, potassium carbonate or sodium bicarbonate.
5. A method for preparing polyphosphazene microspheres with pH chromogenic response according to claim 1, wherein: adding a hexachlorocyclotriphosphazene solution, a phenolphthalein compound solution and a solvent into a container, adding an acid-binding agent solution under auxiliary dispersion, and continuing to react; and after the reaction is finished, filtering or centrifugally separating and washing to obtain the polyphosphazene microspheres with pH chromogenic response.
6. The method for preparing polyphosphazene microspheres with pH chromogenic response according to claim 5, wherein the method comprises the following steps: the auxiliary dispersing mode includes but is not limited to one or more of ultrasonic assistance, magnetic stirring, mechanical stirring or oscillation mixing.
7. The method for preparing polyphosphazene microspheres with pH chromogenic response according to claim 5, wherein the method comprises the following steps: auxiliary dispersion is carried out at 0-50 ℃.
8. The method for preparing polyphosphazene microspheres with pH chromogenic response according to claim 5, wherein the method comprises the following steps: the reaction time is 10-360 min.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004048432A2 (en) * | 2002-11-22 | 2004-06-10 | Parallel Solutions, Inc. | Preparation of polyphosphazene microspheres |
| CN106519240A (en) * | 2016-11-04 | 2017-03-22 | 江南大学 | PH responding type polyphosphazene particle emulsifier and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004048432A2 (en) * | 2002-11-22 | 2004-06-10 | Parallel Solutions, Inc. | Preparation of polyphosphazene microspheres |
| CN106519240A (en) * | 2016-11-04 | 2017-03-22 | 江南大学 | PH responding type polyphosphazene particle emulsifier and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 秦蓓等: ""荧光性聚磷腈纳米粒子的制备及性能研究"", 《化工新型材料》 * |
| 马世昌主编: "《化学物质辞典》", 30 April 1999 * |
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