CN109535393B - Preparation method of microporous organic polymer nano-microspheres and product thereof - Google Patents
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Abstract
The invention relates to a method for synthesizing and preparing microporous organic polymer nano microspheres by using silica sol as an auxiliary additive and a product. The silica sol is used as a nano-morphology control agent to be applied to the synthesis of a microporous polymer nano material for the first time, and the method for synthesizing and preparing the microporous polymer nano microspheres with the particle size of about 500 nm in a solution through a metal coupling reaction catalyzed by transition metal by using the silica sol with the particle size of about 10-20 nm as an auxiliary is disclosed. The silica sol is spherical organic silicon particles with the particle size of 10-20 nm, the silica sol plays a role of spherical nucleus in the growth process of microporous polymer molecules, and the molecular chains of the microporous polymer take the silica sol particles as the nucleus in the polymerization growth process and are adsorbed on the surfaces of the organic silicon particles to gradually polymerize and grow into the microporous polymer nano microspheres. The method is simple and easy to operate, good in stability and high in yield, and the synthesized polymer nano microspheres are uniform in appearance.
Description
Technical Field
The invention relates to a preparation method of microporous organic polymer nano microspheres and a product thereof. In particular to a method for synthesizing and preparing microporous organic polymer nano microspheres by using silica sol as an auxiliary additive and a product.
Background
The microporous organic polymer material is prepared by synthesizing two rigid organic monomer molecules containing a plurality of reaction sites in a solution, wherein the polymerization reaction used in the synthesis mainly comprises Sonogashira coupling reaction, oxidaitive coupling reaction, Yamamoto coupling reaction and the like. Because the material is formed by mutually crosslinking and polymerizing two rigid organic monomer molecules and a three-dimensional grid structure is formed between molecular chains, the material contains a microporous structure. In addition, because the polymerization process of the two rigid molecules is disordered multi-reaction-site simultaneous divergent polymerization, the microscopic morphology of the finally synthesized material is disordered and mainly comprises nanospheres, nanosheets, nanowires and irregular nanoparticles.
Due to disordered microscopic nano-morphology of the microporous organic polymer material, the application of the microporous organic polymer material in the fields of catalysis, energy, environment, photoelectric sensors and the like is hindered, and in recent years, people do a great deal of work on the aspect of controlling and synthesizing the nano-morphology of the microporous organic polymer material, such as controlling and synthesizing a microporous polymer nano-membrane by a template method, and synthesizing microporous polymer nanowires and nanospheres by regulating and controlling a monomer molecular structure. However, the above method is very complicated to operate and is difficult to be widely popularized, for example, the method for synthesizing the microporous polymer nanowires or nanospheres by regulating the molecular structure involves complicated molecular structure design and organic synthesis process, not only is time-consuming, low in yield, but also is poor in controllability of the nanometer morphology, thereby greatly limiting the popularization and application of the method. At present, no simple, effective and stable method is available for synthesizing the microporous organic polymer nano microspheres.
Disclosure of Invention
In view of the shortcomings of the prior art, the present invention aims to provide a preparation method of microporous organic polymer nano microspheres.
Yet another object of the present invention is to: provides a microporous organic polymer nano microsphere product prepared by the method.
The purpose of the invention is realized by the following scheme: a preparation method of microporous organic polymer nano-microspheres, which is characterized in that silica sol particles are used as an assistant, and the microporous polymer nano-microspheres with the particle size of about 500 nm are synthesized in a solution through a metal coupling reaction catalyzed by transition metal, and comprises the following steps:
a. weighing silica sol, adding the silica sol into an organic solvent, diluting according to the proportion of 1g of silica sol to 10ml of organic solvent, and performing ultrasonic dispersion for 5-10 min to obtain silica sol dispersion liquid;
b. selecting two rigid organic molecular monomers as polymerization raw materials according to the requirements of transition metal-catalyzed metal coupling reaction, weighing the monomers according to the reaction proportion, adding the monomers into the silica sol dispersion liquid, stirring for 10 min, and adding a catalyst required by the reaction into the silica sol dispersion liquid, wherein the transition metal-catalyzed metal coupling reaction type comprises the following steps: sonogashira coupling reaction, Oxidative coupling reaction, Yamamoto coupling reaction or Suzuki coupling reaction;
c. after the catalyst is added, replacing air in the reaction liquid by vacuumizing and filling nitrogen;
d. then slowly heating to the set temperature of 60-90 ℃ under the protection of nitrogen, and rapidly stirring;
e. after reacting for 6 hours, carrying out suction filtration, collecting solid powder, sequentially washing with acetone, tetrahydrofuran and ethanol, and drying for 12 hours by using a vacuum drying oven to obtain a powder product;
f. adding the prepared powder into a 3% hydrofluoric acid solution, stirring and reacting for 6h, and etching to remove silica sol particles remained on the surface of the microporous polymer nano microsphere to obtain the required product.
The particle size of the silica sol particles is 10-20 nm, and the organic solvent of the silica sol is one or any combination of benzene, toluene and xylene.
The invention provides a microporous organic polymer nano microsphere, which is prepared by any one of the methods to obtain the microporous polymer nano microsphere with the grain diameter of about 500 nm.
The invention firstly utilizes the silica sol with the grain diameter of about 10-20 nm as the nano-morphology control agent, and synthesizes and prepares the microporous polymer nano-microsphere with the grain diameter of about 500 nm in the solution through the metal coupling reaction catalyzed by transition metal.
The mechanism of the invention is as follows: the silica sol is spherical organic silicon particles with the particle size of 10-20 nm, the silica sol plays a role of spherical nucleus in the growth process of microporous polymer molecules, and the molecular chains of the microporous polymer take the silica sol particles as the nucleus in the polymerization growth process and are adsorbed on the surfaces of the organic silicon particles to gradually polymerize and grow into the microporous polymer nano microspheres.
The invention has the advantages that: the method is simple and easy to operate, good in stability and high in yield, and the synthesized polymer nano microspheres are uniform in appearance.
Drawings
FIG. 1 is an SEM image of a microporous polymer nanosphere synthesized in example 1 of the present invention;
FIG. 2 is an SEM image of the synthesized microporous polymer nanospheres of example 3 of the present invention.
Detailed Description
The present invention is described in detail below with reference to specific examples, but the scope of the present invention is not limited to these examples.
Example 1
A preparation method of microporous organic polymer nano microspheres, which synthesizes and prepares microporous polymer nano microspheres with the particle size of about 500 nm in a solution through a metal coupling reaction catalyzed by transition metal, comprises the following steps:
a. weighing 2.0g of silica sol with the particle size of about 20 nm dispersed in a toluene solvent, adding the silica sol into 20ml of a xylene solvent, and carrying out ultrasonic dispersion for 10 min;
b. weighing 52 mg of 1,3, 5-triacetylbenzene monomer and 135mg of 4,4 '-diiodobiphenyl monomer according to the requirements of the Sonogashira coupling reaction, adding the 1,3, 5-triacetylbenzene monomer and the 135mg of 4, 4' -diiodobiphenyl monomer into the dispersion liquid of the silica sol, stirring for 5 min, and adding a catalytic amount of triphenylphosphine palladium dichloride, cuprous iodide catalyst and 10ml of triethylamine into the dispersion liquid;
c. after the catalyst is added, replacing air in the reaction liquid by vacuumizing and filling nitrogen;
d. then under the protection of nitrogen, slowly heating the reaction solution to 60 ℃, rapidly stirring, and rapidly stirring;
e. after reacting for 6 hours, filtering the reaction solution, collecting the solid, washing the solid with acetone, tetrahydrofuran and ethanol in sequence, and drying the powder for 12 hours in a vacuum drying oven;
f. adding the prepared powder into a 3% hydrofluoric acid solution, stirring and reacting for 6h, and aiming at etching and removing the silica sol particles remained on the surface of the microporous polymer nano microsphere. The SEM picture of the synthesized microporous polymer nano-microspheres is shown in figure 1, and the microporous polymer nano-microspheres have the characteristic of uniform appearance.
Example 2
A preparation method of microporous organic polymer nano microspheres comprises the following steps:
a. weighing 2.0g of silica sol with the particle size of about 10 nm dispersed in a toluene solvent, adding the silica sol into 20ml of a xylene solvent, and carrying out ultrasonic dispersion for 10 min;
b. according to the requirements of the Sonogashira coupling reaction, 109 mg of 1, 4-diiodobenzene monomer and 52 mg of 1,3, 5-triacetylbenzene monomer are weighed and added into the dispersion liquid of the silica sol, after stirring for 5 min, a catalytic amount of triphenylphosphine palladium dichloride, cuprous iodide catalyst and 10ml of triethylamine are added into the dispersion liquid;
c. after the catalyst is added, replacing air in the reaction liquid by vacuumizing and filling nitrogen;
d. then, under the protection of nitrogen, slowly heating the reaction solution to 60 ℃, and quickly stirring;
e. after reacting for 6 hours, filtering the reaction solution, collecting the solid, washing the solid with acetone, tetrahydrofuran and ethanol in sequence, and drying the solid for 12 hours by using a vacuum drying oven;
f. adding the prepared powder into a 3% hydrofluoric acid solution, stirring and reacting for 6h, and aiming at etching and removing the silica sol particles remained on the surface of the microporous polymer nano microsphere.
Example 3
A preparation method of microporous organic polymer nano microspheres comprises the following steps:
a. weighing 2.0g of silica sol with the particle size of about 20 nm dispersed in a toluene solvent, adding the silica sol into 40 ml of the toluene solvent, and performing ultrasonic dispersion for 10 min;
b. weighing 91 mg of 1,3, 5-triiodobenzene monomer and 50 mg of terephthalic acid diboronic acid monomer according to the requirement of Suzuki coupling reaction, adding the 1,3, 5-triiodobenzene monomer and the 50 mg of terephthalic acid diboronic acid monomer into the dispersion liquid of the silica sol, performing ultrasonic dispersion for 10 min, adding a catalytic amount of triphenylphosphine palladium dichloride catalyst and 1 ml of potassium carbonate aqueous solution with the concentration of 10 mg/ml into the dispersion liquid, and performing ultrasonic dissolution for 5 min;
c. after the catalyst is added, replacing air in the reaction liquid by vacuumizing and filling nitrogen;
d. then under the protection of nitrogen, slowly heating the reaction solution to 90 ℃ and rapidly stirring;
e. after reacting for 6 hours, filtering the reaction solution, collecting the solid, washing the solid with acetone, tetrahydrofuran and ethanol in sequence, and drying the solid for 12 hours by using a vacuum drying oven;
f. adding the prepared powder into a 3% hydrofluoric acid solution, stirring and reacting for 6h, and aiming at etching and removing the silica sol particles remained on the surface of the microporous polymer nano microsphere. The SEM image of the synthesized microporous polymer nano-microsphere is shown in figure 2, and the microsphere has the characteristic of uniform appearance.
Claims (4)
1. A preparation method of microporous organic polymer nano microspheres is characterized in that silica sol particles are used as assistance, and microporous polymer nano microspheres with the particle size of 500 nm are synthesized in a solution through a metal coupling reaction catalyzed by transition metal, and the preparation method comprises the following steps:
a. weighing silica sol, adding the silica sol into an organic solvent with a certain volume, diluting according to the proportion of 1g of silica sol to 10ml of organic solvent, and performing ultrasonic dispersion for 5-10 min to obtain silica sol dispersion liquid;
b. selecting two rigid organic molecular monomers as polymerization raw materials according to the requirements of transition metal-catalyzed metal coupling reaction, weighing the monomers according to the reaction proportion, adding the monomers into silica sol dispersion liquid, stirring for 10 min, and adding a catalyst required by the reaction into the silica sol dispersion liquid, wherein the transition metal-catalyzed metal coupling reaction type comprises: sonogashira coupling reaction, Oxidative coupling reaction, Yamamoto coupling reaction or Suzuki coupling reaction;
c. after the catalyst is added, replacing air in the reaction liquid by vacuumizing and filling nitrogen;
d. then slowly heating to the set temperature of 60-90 ℃ under the protection of nitrogen, and rapidly stirring;
e. after reacting for 6 hours, carrying out suction filtration, collecting solid powder, sequentially washing with acetone, tetrahydrofuran and ethanol, and drying for 12 hours by using a vacuum drying oven;
f. adding the prepared powder into a 3% hydrofluoric acid solution, stirring and reacting for 6h, and etching to remove silica sol particles remained on the surface of the microporous polymer nano microsphere to obtain a required product; wherein the content of the first and second substances,
the particle size of the silica sol particles is 10-20 nm, and the organic solvent of the silica sol is one or any combination of benzene, toluene and xylene.
2. The method for preparing microporous organic polymer nano-microspheres according to claim 1, wherein the transition metal-catalyzed metal coupling reaction is a Sonogashira coupling reaction, and according to the coupling reaction requirement, 52 mg of 1,3, 5-triacetylbenzene monomer and 109-135mg of 4, 4' -diiodobiphenyl monomer are weighed and added into the dispersion of the 20ml of silica sol, and after stirring for 5 min, catalytic amounts of triphenylphosphine palladium dichloride and cuprous iodide catalyst and 10ml of triethylamine are added.
3. The preparation method of microporous organic polymer nano-microspheres according to claim 1, wherein the transition metal-catalyzed metal coupling reaction type is Suzuki coupling reaction, 91 mg of 1,3, 5-triiodobenzene monomer and 50 mg of p-phenylboronic acid monomer are weighed and added into the dispersion of the above 40 ml of silica sol, after ultrasonic dispersion for 10 min, a catalytic amount of triphenylphosphine palladium dichloride catalyst and 1 ml of potassium carbonate aqueous solution with a concentration of 10 mg/ml are added.
4. A microporous organic polymer nanosphere characterized in that a microporous polymer nanosphere having a particle size of 500 nm is prepared according to the method of any of claims 1-3.
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| CN110183715B (en) * | 2019-05-31 | 2022-07-01 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of microporous organic polymer with moon-like surface pit morphology and product thereof |
| CN110180474A (en) * | 2019-06-02 | 2019-08-30 | 上海纳米技术及应用国家工程研究中心有限公司 | The preparation method and product of the micropore organic polymer nano-hollow microballoon of titanium dioxide nanometer microballoons auxiliary |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104795247A (en) * | 2015-04-28 | 2015-07-22 | 中科院广州化学有限公司南雄材料生产基地 | Polyaniline nano-composite electrode material with porous structure, preparation method of polyaniline nano-composite electrode material and application of polyaniline nano-composite electrode material |
| CN104785301A (en) * | 2015-03-13 | 2015-07-22 | 苏州至善化学有限公司 | Magnetic palladium composite catalyst, and preparation method and use thereof |
| CN107151313A (en) * | 2017-06-08 | 2017-09-12 | 吉林师范大学 | A kind of organic microporous polymer of nitrogenous conjugation, preparation method and application |
| CN107814933A (en) * | 2017-11-22 | 2018-03-20 | 兰州理工大学 | The Preparation method and use of conjugation microporous polymer with bacteriostatic activity |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104785301A (en) * | 2015-03-13 | 2015-07-22 | 苏州至善化学有限公司 | Magnetic palladium composite catalyst, and preparation method and use thereof |
| CN104795247A (en) * | 2015-04-28 | 2015-07-22 | 中科院广州化学有限公司南雄材料生产基地 | Polyaniline nano-composite electrode material with porous structure, preparation method of polyaniline nano-composite electrode material and application of polyaniline nano-composite electrode material |
| CN107151313A (en) * | 2017-06-08 | 2017-09-12 | 吉林师范大学 | A kind of organic microporous polymer of nitrogenous conjugation, preparation method and application |
| CN107814933A (en) * | 2017-11-22 | 2018-03-20 | 兰州理工大学 | The Preparation method and use of conjugation microporous polymer with bacteriostatic activity |
Non-Patent Citations (2)
| Title |
|---|
| Hollow Microporous Organic Networks Bearing Triphenylamines and Anthraquinones: Diffusion Pathway Effect in Visible Light-Driven Oxidative Coupling of Benzylamines;Ju Hong Ko et al.;《ACS Macro Letters》;20150610;第670页的左栏和Supporting Information * |
| Ju Hong Ko et al..Hollow Microporous Organic Networks Bearing Triphenylamines and Anthraquinones: Diffusion Pathway Effect in Visible Light-Driven Oxidative Coupling of Benzylamines.《ACS Macro Letters》.2015, * |
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