阅读说明：本技术 一种高比表面积微孔有机聚合物的常温快速制备方法 (Normal-temperature rapid preparation method of microporous organic polymer with high specific surface area ) 是由 徐宇曦 张磊 孙甜 于 2021-09-18 设计创作，主要内容包括：本发明公开了一种高比表面积微孔有机聚合物的常温快速制备方法。将单体a溶于无水有机溶剂c中得到溶液A,将催化剂b分散在一定量无水有机溶剂c中形成分散液B；将溶液A加入分散液B中,开放体系静置反应,然后加入去离子水搅拌终止反应,获得反应物；将反应物转移至50mL样品瓶中,洗涤反应物；将洗涤后的反应物置于真空干燥箱中干燥一段时间后得到微孔有机聚合物。本发明方法制备的微孔有机聚合物具有高比表面积、化学稳定性良好及结构可控的特性,材料可应用于甲烷等气体的存储及运输等领域。(The invention discloses a normal-temperature rapid preparation method of a microporous organic polymer with a high specific surface area. Dissolving a monomer a in an anhydrous organic solvent c to obtain a solution A, and dispersing a catalyst B in a certain amount of the anhydrous organic solvent c to form a dispersion liquid B; adding the solution A into the dispersion liquid B, opening a system, standing for reaction, adding deionized water, stirring and stopping the reaction to obtain a reactant; transferring the reactant to a 50mL sample bottle, and washing the reactant; and (3) placing the washed reactant in a vacuum drying oven for drying for a period of time to obtain the microporous organic polymer. The microporous organic polymer prepared by the method has the characteristics of high specific surface area, good chemical stability and controllable structure, and the material can be applied to the fields of storage, transportation and the like of methane and other gases.)

1. A normal temperature rapid preparation method of a microporous organic polymer with high specific surface area is characterized in that: the preparation method adopts a Friedel-crafts reaction mode, selects materials to rapidly prepare the microporous organic polymer with high specific surface area under the normal temperature condition, and further increases the specific surface area along with the extension of reaction time.

2. The normal-temperature rapid preparation method of the microporous organic polymer with the high specific surface area according to claim 1 is characterized in that: the method comprises the following specific steps:

(1) weighing a certain amount of monomer a and a certain amount of anhydrous catalyst b;

(2) dissolving a monomer a in a certain amount of anhydrous organic solvent c to obtain a solution A, and dispersing a catalyst B in a certain amount of anhydrous organic solvent c to form a dispersion liquid B;

(3) adding the solution A into the dispersion liquid B, standing and reacting for a period of time in an open system, adding deionized water, stirring and terminating the reaction to obtain a reactant;

(4) transferring the reactant into a sample bottle, and washing the reactant;

(5) and (3) placing the washed reactant in a vacuum drying oven for drying for a period of time to obtain the microporous organic polymer.

3. The normal-temperature rapid preparation method of the microporous organic polymer with the high specific surface area according to claim 2 is characterized in that: the method is always completed at normal temperature.

4. The normal-temperature rapid preparation method of the microporous organic polymer with the high specific surface area according to claim 2 is characterized in that: in the step (1), the monomer a is one of 1, 4-dichlorobenzene, p-dichlorobenzyl, 4-dichlorobiphenyl and biphenyl dichlorobenzyl.

5. The normal-temperature rapid preparation method of the microporous organic polymer with the high specific surface area according to claim 2 is characterized in that: in the step (1), the catalyst b is one of anhydrous aluminum chloride, anhydrous zinc chloride, anhydrous ferric chloride, boron trifluoride and trifluoromethanesulfonic acid.

6. The normal-temperature rapid preparation method of the microporous organic polymer with the high specific surface area according to claim 2 is characterized in that: in the step (2), the anhydrous organic solvent c is one of chloroform, carbon tetrachloride, dichloromethane and dichloroethane.

7. The normal-temperature rapid preparation method of the microporous organic polymer with the high specific surface area according to claim 2 is characterized in that: the dosage of the monomer a is 50 mg-10 g, the dosage of the catalyst b is 50 mg-10 g, and the single dosage of the anhydrous organic solvent c in the step (1)/the step (2) is 1-100 mL.

8. The normal-temperature rapid preparation method of the microporous organic polymer with the high specific surface area according to claim 2 is characterized in that: in the step (3), the standing reaction temperature is 5-100 ℃, and the standing reaction time is 30s-30 min.

9. The normal-temperature rapid preparation method of the microporous organic polymer with the high specific surface area according to claim 2 is characterized in that: in the step (4), deionized water, absolute ethyl alcohol and tetrahydrofuran are sequentially used for washing reactants.

10. The normal-temperature rapid preparation method of the microporous organic polymer with the high specific surface area according to claim 2 is characterized in that: in the step (5), the drying temperature is 60-150 ℃, and the drying time is 2-30 h.

Technical Field

The invention relates to a preparation method of a polymer material with high specific surface area, and relates to a normal-temperature rapid preparation method of a microporous organic polymer with high specific surface area.

Background

Microporous Organic Polymers (MOPs) have been developed in recent decades, are novel porous materials assembled from organic molecular building blocks, and have the advantages of diverse synthetic methods, stable chemical and physical properties, and the like. The molecular chains of microporous organic polymers are composed mainly of lighter density elements such as: C. n, O, B, etc. Compared with the traditional microporous materials such as molecular sieve, active carbon, porous silicon and the like, the microporous organic polymer can control the pore size of the polymer through the type of a reaction monomer in a large range, and can achieve different functionalization purposes through different functional groups, so the microporous organic polymer has a very high application prospect.

Friedel-crafts reaction is a reaction that in the presence of Lewis acid such as anhydrous aluminum trichloride, aromatic hydrocarbon reacts with haloalkane to generate electrophilic substitution reaction on an aromatic ring, and hydrogen atoms of the electrophilic substitution reaction are substituted by alkyl to generate alkyl aromatic hydrocarbon. The Friedel-crafts reaction is one of the oldest and longest applied reactions so far, and is widely applied to the chemical industry fields of medicine, fuel, petroleum and the like. The preparation of the microporous organic polymer by using the Friedel-crafts reaction is a common chemical synthesis means, and the preparation of the microporous organic polymer by using the Friedel-crafts reaction at normal temperature can save energy consumption caused by synthesis to the greatest extent.

Disclosure of Invention

The invention aims to provide a more energy-saving and rapid synthesis mode for preparing a microporous organic polymer, the prepared microporous organic polymer has the characteristics of high specific surface area, excellent chemical stability, adjustable structure and the like, and the method is expected to realize large-scale, low-energy consumption and rapid synthesis of the microporous organic polymer.

The technical scheme of the invention comprises the following implementation steps:

the invention adopts a Friedel-crafts reaction mode, selects materials to rapidly prepare the microporous organic polymer with high specific surface area under the normal temperature condition, and further increases the specific surface area along with the extension of the reaction time.

The invention utilizes the high reactivity of Friedel-crafts reaction to realize the rapid preparation of the microporous organic polymer under the normal temperature condition. The microporous organic polymer prepared by the method has the characteristic of high specific surface area, and can be applied to the fields of storage, transportation and the like of gases such as methane and the like.

The method comprises the following specific steps:

(1) weighing a certain amount of monomer a and a certain amount of anhydrous catalyst b;

(2) dissolving a monomer a in a certain amount of anhydrous organic solvent c to obtain a solution A, and dispersing a catalyst B in a certain amount of anhydrous organic solvent c to form a dispersion liquid B;

(3) adding the solution A into the dispersion liquid B, standing and reacting for a period of time in an open system, and then quickly adding deionized water to stir and terminate the reaction to obtain a reactant;

(4) transferring the reactant to a 50mL sample bottle, and washing the reactant;

(5) and (3) placing the washed reactant in a vacuum drying oven for drying for a period of time to obtain the microporous organic polymer.

The method is always completed at normal temperature.

In the step (1), the monomer a is one of 1, 4-dichlorobenzene, p-dichlorobenzyl, 4-dichlorobiphenyl and biphenyl dichlorobenzyl, and can be a monomer for preparing a building block of a microporous organic polymer, such as chlorinated aromatic hydrocarbon, brominated aromatic hydrocarbon, iodo aromatic hydrocarbon and the like.

The preferable monomer a is one of 4, 4-dichlorobiphenyl and biphenyl dichlorobenzyl, and the monomer can greatly accelerate speed and has higher specific surface area.

In the step (1), the catalyst b is one of anhydrous aluminum chloride, anhydrous zinc chloride, anhydrous ferric chloride, boron trifluoride and trifluoromethanesulfonic acid.

In the step (2), the anhydrous organic solvent c is one of chloroform, carbon tetrachloride, dichloromethane and dichloroethane.

The dosage of the monomer a is 50 mg-10 g, the dosage of the catalyst b is 50 mg-10 g, and the single dosage of the anhydrous organic solvent c in the step (1)/the step (2) is 1-100 mL.

In the step (3), the standing reaction temperature is 5-100 ℃, and the standing reaction time is 30s-30 min.

For faster preparation, the preferred standing reaction time is 30s-10 min. Usually, the preparation time of the organic polymer is more than 10 hours, and some organic polymers need to be treated overnight, but the invention only needs 30s-10min to obtain products with excellent specific surface area effect.

In the step (4), deionized water, absolute ethyl alcohol and tetrahydrofuran are sequentially used for washing reactants.

In the step (5), the drying temperature is 60-150 ℃, and the drying time is 2-30 h.

The invention has the beneficial effects that:

the invention utilizes the high reactivity of the Friedel-crafts reaction to realize the rapid preparation of the microporous organic polymer (30s-30min) at normal temperature, and the prepared microporous organic polymer has the characteristic of high specific surface area, thereby obviously reducing the energy consumption in the synthesis process of the microporous organic polymer and preparing the microporous organic polymer with high specific surface area more economically and conveniently.

The microporous organic polymer prepared by the method has the characteristics of high specific surface area, good chemical stability and controllable structure, and the material is hopefully applied to the fields of storage, transportation and the like of gases such as methane and the like by utilizing the characteristics of the high specific surface area of the polymer.

The invention has the technical characteristics that:

(1) the economic efficiency is as follows: the material cost is low, and the synthesis cost is low;

(2) safety: the material is non-toxic, pollution-free, sanitary, safe, green and low-carbon;

(3) low energy consumption: the synthesis can be completed under the condition of normal temperature, and the reaction energy consumption is low;

(4) rapidity: the material can be synthesized for most part within 30s, and the specific surface area is as high as 945m²The specific surface area can reach 1700m along with the extension of the reaction time²/g；

(5) Stability: the material has excellent chemical stability and meets the use requirement;

(6) the structure is adjustable: the structure of the polymer can be adjusted, and different use requirements can be met.

Drawings

FIG. 1 shows a scanning electron micrograph of a microporous organic polymer in an example;

FIG. 2 shows a PXRD pattern of microporous organic polymers in an example;

FIG. 3 shows a Fourier transform infrared spectrum of a microporous organic polymer in an example;

FIG. 4 shows N of microporous organic Polymer in example₂Adsorption curve diagram;

FIG. 5 shows a pore size distribution plot of microporous organic polymers in examples.

Detailed Description

The present invention is further described below in conjunction with the following embodiments and the accompanying drawings, it being understood that the description of the figures and the following embodiments are only illustrative of the present invention and are not limiting.

The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.

Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.

The invention aims to provide a synthesis mode for rapidly preparing a microporous organic polymer under a normal temperature condition. The synthesis method has simple implementation process, and the prepared microporous organic polymer has the characteristics of high specific surface area, low synthesis cost and short synthesis time, and can realize large-scale production.

The examples of the invention are as follows:

example 1

Firstly, 251mg of monomer biphenyl dichlorobenzyl is weighed and transferred to a 30mL transparent sample bottle, and 1.5mL of anhydrous dichloromethane is added to dissolve the monomer; 162mg of catalyst anhydrous ferric chloride was weighed, transferred to a 30mL transparent sample bottle, and 1mL of anhydrous dichloromethane was added to prepare a dispersion. Then, the biphenyl dichlorobenzyl solution is added into the catalyst dispersion liquid, and after the biphenyl dichlorobenzyl solution is left to stand for reaction for 30s, 20mL of deionized water is rapidly added to stop the reaction. The reaction product was transferred to a 50mL transparent sample bottle, and the product was washed with deionized water, absolute ethanol, and tetrahydrofuran, respectively. And collecting the cleaned solid product, and drying the solid product in a vacuum drying oven at 120 ℃ for 10 hours to obtain the target microporous organic polymer.

The scanning electron microscope image of the prepared microporous organic polymer is shown in the attached figure 1, and the material is seen to be in a block shape. Polycrystalline X-ray diffraction (PXRD) testing was performed on the material, as shown in figure 2, and it can be seen that the material is in a partially ordered state. Meanwhile, Fourier transform infrared spectrum test is carried out on the material, and the test result is shown in figure 3. The specific surface area and pores of the conjugated microporous polymer were then testedPorosity, measured by nitrogen adsorption at 77K, the specific surface area and pore size of the samples were evaluated by the Brunauer-Emmett-Teller (BET) method. As shown in FIG. 4, the specific surface area of the conjugated microporous polymer was 945m, which was measured as the reaction time of 30s²In terms of/g, the nitrogen adsorption isotherm of the material is at a lower relative pressure (P/P)₀<0.1) a sharp rise occurs, indicating that the material is predominantly microporous. Pore size analysis was performed using the non-localized density functional theory (NLDFT) and the pore size distribution of the material was predominantly below 2nm as shown in figure 5.

As can be seen from the test results, the specific surface area of the conjugated microporous polymer was as high as 945m at a reaction time of only 30s²And the reaction is carried out at normal temperature, so that the energy consumption of the reaction is greatly reduced. The method is expected to be used for large-scale production and is put into practical application.

Example 2

Firstly, 251mg of monomer biphenyl dichlorobenzyl is weighed and transferred to a 30mL transparent sample bottle, and 1.5mL of anhydrous dichloromethane is added to dissolve the monomer; 132. mu.L of the catalyst trifluoromethanesulfonic acid was weighed, transferred to a 30mL transparent sample bottle, and 1mL of anhydrous dichloromethane was added to prepare a dispersion. And then adding the biphenyl dichlorobenzyl solution into the catalyst dispersion liquid, and quickly adding 20mL of deionized water to terminate the reaction after 5min of open standing reaction. The reaction product was transferred to a 50mL transparent sample bottle, and the product was washed with deionized water, absolute ethanol, and tetrahydrofuran, respectively. And collecting the cleaned solid product, and drying the solid product in a vacuum drying oven at 120 ℃ for 10 hours to obtain the target microporous organic polymer.

Example 3

Firstly, 251mg of monomer biphenyl dichlorobenzyl is weighed and transferred to a 30mL transparent sample bottle, and 1.5mL of anhydrous dichloromethane is added to dissolve the monomer; 162mg of catalyst anhydrous ferric chloride was weighed, transferred to a 30mL transparent sample bottle, and 1mL of anhydrous dichloromethane was added to prepare a dispersion. And then adding the biphenyl dichlorobenzyl solution into the catalyst dispersion liquid, and adding 20mL of deionized water to terminate the reaction after the biphenyl dichlorobenzyl solution is subjected to open standing reaction for 30 min. The reaction product was transferred to a 50mL transparent sample bottle, and the product was washed with deionized water, absolute ethanol, and tetrahydrofuran, respectively. And then collecting the cleaned solid product, and placing the solid product in a vacuum drying oven to dry for 10 hours at the temperature of 120 ℃ to obtain the target microporous organic polymer.

Example 4

Firstly, 251mg of monomer biphenyl dichlorobenzyl is weighed and transferred to a 30mL transparent sample bottle, and 5mL of anhydrous dichloromethane is added to dissolve the monomer; 162mg of catalyst anhydrous ferric chloride was weighed, transferred to a 30mL transparent sample bottle, and 5mL of anhydrous dichloromethane was added to prepare a dispersion. And then adding the biphenyl dichlorobenzyl solution into the catalyst dispersion liquid, and adding 20mL of deionized water to terminate the reaction after the biphenyl dichlorobenzyl solution is subjected to open standing reaction for 30 min. The reaction product was transferred to a 50mL transparent sample bottle, and the product was washed with deionized water, absolute ethanol, and tetrahydrofuran, respectively. And collecting the cleaned solid product, and drying the solid product in a vacuum drying oven at 120 ℃ for 10 hours to obtain the target microporous organic polymer.