CN115304748B - Preparation method of porous polymer material - Google Patents

Abstract

The invention discloses a preparation method of a porous polymer material, which comprises the following steps: and (3) taking the sodium-potassium alloy as a metal reducing agent, taking hexachloro-p-xylene as a precursor, stirring at room temperature, and finally preparing the porous polymer material by controlling the reaction time to adjust the pore channel structure of the porous polymer material. The preparation method provided by the invention has advanced process and accurate data, does not need additional template agent and high-temperature roasting, greatly shortens the preparation time and reduces the reaction energy consumption; the product obtained by the method is yellow powder, has a porous pore canal structure, the product yield is up to 81.2%, and the material can be used as CO after being modified by organic matters ₂ The cycloaddition catalyst is a very desirable method for preparing porous polymer materials.

Description

A kind of preparation method of porous polymer material

technical field

The disclosure of the invention relates to the technical field of preparation and application of porous materials, in particular to a preparation method of porous polymer materials.

Background technique

Porous polymer materials have the advantages of good structure adjustability, adsorption performance, high specific surface area and large pore volume, and have been widely used in the fields of adsorption, catalysis, and gas separation.

The synthesis method and process of the porous polymer material will directly affect the structural characteristics and properties of the material, and the selection of the synthesis method and template agent is the decisive factor, and the reaction temperature and reaction time also have an impact on the pore structure of the porous polymer material. important influence.

The template is the basic component of the preparation of porous polymer materials, and the precursor and the template form a porous structure through supramolecular force or chemical interaction. The structure and type of the template will affect the pore structure of the porous polymer material, so the selection and use of the template is very important.

In the process of synthesizing porous polymer materials with organic substances as precursors, most of them need to use soft templates or hard templates as structure-directing agents. Due to different chemical substances selected, different synthesis parameters, and differences in the synthesis process, the synthesis temperature ranges from 100°C to 200°C. °C, resulting in large differences in the chemical and physical properties of the obtained porous polymer materials, it is difficult to meet the requirements of synthetic substances, so that the application of such materials has been greatly limited.

Contents of the invention

In view of this, the disclosure of the present invention provides a preparation method of a porous polymer material, which provides a new reaction path for the preparation of a porous polymer material.

The technical solution provided by the present invention is specifically a preparation method of a porous polymer material, comprising: using sodium potassium alloy as a metal reducing agent, using hexachloro-p-xylene as a precursor, stirring at room temperature, and controlling the reaction The time reaches to adjust the pore structure of the porous polymer material, and the porous polymer material is finally prepared.

Further, the reactants included in the method are: metal sodium, metal potassium, hexachloro-p-xylene, tetrahydrofuran, ethanol, deionized water;

Its combined dosage is as follows: taking grams and milliliters as measurement units,

Including the following steps:

(1) Prepare sodium-potassium alloy: weigh 0.1g ± 0.01g of sodium metal, weigh 0.4g ± 0.02g of potassium metal, stir for 1 minute, and configure sodium-potassium alloy;

(2) Synthesis of porous polymer materials: under the protection of nitrogen, weigh 0.6g ± 0.02g of hexachloro-p-xylene, dissolve it in 10mL ± 0.5mL tetrahydrofuran, stir for 5 minutes, add the prepared sodium potassium alloy, and Stir and reduce, after reacting for 24 hours, add 20mL±1mL ethanol, continue to stir for 30 minutes, filter to obtain a solid, and obtain an intermediate product;

(3) Washing and suction filtration:

(4) Vacuum drying: after drying, it becomes a porous polymer material;

(5) Detection, analysis, and characterization: detection, analysis, and characterization of the morphology, composition, and chemical and physical properties of the prepared porous polymer material.

Further, the specific steps of step (3) washing and suction filtration are as follows: put the filtered product in a beaker, add 100 mL of deionized water, stir and wash for 5 minutes; place the washing liquid in the Buchner funnel of the suction filtration bottle , use a microporous filter membrane for suction filtration, retain the product filter cake on the filter membrane, pump the washing liquid into the filter bottle, wash and filter twice; add 100 mL of tetrahydrofuran, stir and wash for 5 minutes, wash and filter twice .

Further, the specific steps of step (4) vacuum drying are as follows: place the washed product filter cake in a glass container, and then place it in a vacuum drying oven for drying at a drying temperature of 50°C±1°C and a vacuum degree of 50Pa , drying time 10 hours.

The preparation method of a porous polymer material provided by the invention has advanced technology, detailed and accurate data, no need for additional templating agent and high-temperature roasting, which greatly shortens the preparation time and reduces the energy consumption of the reaction; the product obtained by the method It is a yellow powder with a porous channel structure, and the product yield is as high as 81.2%. After the material is modified with organic matter, it can be used as a catalyst for the CO ₂ cycloaddition reaction, and it is an ideal method for preparing porous polymer materials.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the present disclosure.

Description of drawings

The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description serve to explain the principles of the invention.

In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings that need to be used in the description of the embodiments or the prior art. Obviously, for those of ordinary skill in the art, In other words, other drawings can also be obtained from these drawings on the premise of not paying creative work.

Figure 1 is a state diagram of the synthesis and preparation of porous polymer materials provided by the disclosed embodiments of the present invention;

Fig. 2 is the X-ray diffraction spectrum of the porous polymer material provided by the disclosed embodiments of the present invention;

Fig. 3 is the nitrogen adsorption and desorption curve diagram of the porous polymer body material provided by the disclosed embodiment of the present invention;

Fig. 4 is a transmission electron micrograph of the porous polymer material provided by the disclosed embodiment of the present invention.

Detailed ways

Reference will now be made in detail to the exemplary embodiments, examples of which are illustrated in the accompanying drawings. When the following description refers to the accompanying drawings, the same numerals in different drawings refer to the same or similar elements unless otherwise indicated. The implementations described in the following exemplary examples do not represent all implementations consistent with the present invention. Rather, they are merely examples of systems consistent with aspects of the invention as recited in the appended claims.

In order to solve the problem in the prior art, in the process of synthesizing porous polymer materials with organic substances as precursors, most of them need to use soft templates or hard templates as structure directing agents, and the chemical and physical properties of the obtained porous polymer materials are quite different. , It is difficult to meet the requirements of synthetic substances and other issues. This embodiment provides a novel metal reduction synthesis method, using sodium potassium alloy as a metal reducing agent, using hexachloro-p-xylene as a precursor, stirring at room temperature, Prepare the porous polymer material, adjust the pore structure of the porous polymer material by controlling the reaction time, and improve the chemical and physical properties. The material can be used as a catalyst for the CO ₂ cycloaddition reaction after being modified with organic matter.

Specifically, the chemical substances included in the method are: metal sodium, metal potassium, hexachloro-p-xylene, tetrahydrofuran, ethanol, deionized water;

Its combined dosage is as follows: taking grams and milliliters as measurement units,

The preparation method comprises the following steps:

(1) Prepare sodium-potassium alloy: weigh 0.1g ± 0.01g of sodium metal, weigh 0.4g ± 0.02g of potassium metal, stir for 1 minute, and configure sodium-potassium alloy;

(2) Synthesis of porous polymer materials: under the protection of nitrogen, weigh 0.6g ± 0.02g of hexachloro-p-xylene, dissolve it in 10mL ± 0.5mL tetrahydrofuran, stir for 5 minutes, add the prepared sodium potassium alloy, and Stir and reduce, after reacting for 24 hours, add 20mL±1mL ethanol, continue to stir for 30 minutes, filter to obtain a solid, and obtain an intermediate product;

(3) Washing and suction filtration:

(4) Vacuum drying: after drying, it becomes a porous polymer material;

(5) Detection, analysis, and characterization: detection, analysis, and characterization of the morphology, composition, and chemical and physical properties of the prepared porous polymer material.

Step (2) specifically includes as follows:

A. Prepare the mixed reaction mixture: weigh 0.6g±0.02g of hexachloro-p-xylene, 0.5g±0.03g of sodium potassium alloy, measure 10mL±0.5mL of tetrahydrofuran, and add them into a round bottom flask to form a mixed reaction solution;

B. Turn on the magnetic stirring, stir for 24 hours, and react the mixed reaction solution at room temperature.

C. After the reaction is completed, add 20mL ± 1mL ethanol, continue to stir at room temperature for 30 minutes, and stop stirring; suction filtration: put the reacted mixture in the Buchner funnel of the suction filter bottle, and perform suction filtration with a microporous filter membrane. The filter cake waste liquid remaining on the membrane is pumped into the filter bottle.

The specific steps of the above step (3) washing and suction filtration are: place the filtered product in a beaker, add 100 mL of deionized water, stir and wash for 5 minutes; place the washing liquid in the Buchner funnel of the suction filtration bottle, The filter membrane is subjected to suction filtration, the product filter cake is retained on the filter membrane, the washing solution is pumped into the filter bottle, washing and suction filtration are performed twice; 100 mL of tetrahydrofuran is added, stirred and washed for 5 minutes, washing and suction filtration are performed twice.

The specific steps of the above step (4) vacuum drying are: place the washed product filter cake in a glass container, and then place it in a vacuum drying oven for drying. The drying temperature is 50°C ± 1°C, the vacuum degree is 50Pa, and the drying time is 10°C. Hour.

The porous polymer material prepared by the above preparation method can be used as a catalyst for the _CO2 cycloaddition reaction after being modified with an organic substance.

As shown in Figure 1, it is a state diagram for the synthesis and preparation of porous polymer materials. As shown in the figure, the positions of each part must be correct, proportioned according to the amount, and operated in sequence; the amount of the chemical substances used in the preparation is determined according to the preset range. , in units of grams and milliliters.

The synthesis of the porous polymer material is carried out in a glass round bottom flask, and is completed under stirring conditions at room temperature;

The stirrer is rectangular, and the round-bottomed flask 2 is fixed on the fixed rod 4 of the stirring table 3 by using the iron clip 1. The magnetic stirrer 5 is placed at the bottom of the conical flask, and the mouth of the conical flask is sealed with a plastic rubber stopper 6. A display screen 8, an indicator light 9, a power switch 10, and a speed controller 11 are arranged on the stirrer seat 7.

The present invention will be further explained below in conjunction with specific examples, but it is not intended to limit the protection scope of the present invention.

The preparation method is as follows:

(1) Selected chemical substances and materials

The chemical substances and materials used in the preparation should be carefully selected and their quality and purity should be controlled:

(2) Preparation of sodium potassium alloy

Weigh 0.1g±0.01g of sodium metal and 0.4g±0.02g of potassium metal, stir for 1 minute, and configure it into a sodium-potassium alloy;

(3) Synthesis of porous polymer materials

The synthesis of the porous polymer material is carried out under the protection of nitrogen, stirring and reducing at room temperature, and then filtering to obtain a solid.

① Prepare mixed reaction mixture

Weigh 0.6g±0.02g of hexachloro-p-xylene, 0.1g±0.01g of sodium potassium alloy, and measure 10mL±0.5mL of tetrahydrofuran;

Add to a round bottom flask to form a mixed reaction solution;

② Turn on the magnetic stirring, stir for 24 hours, mix the reaction solution for reaction,

③After the reaction is completed, add 20mL±1mL ethanol and continue stirring for 30 minutes, then stop stirring;

(4) suction filtration

Place the reacted mixture in the Buchner funnel of the suction filter bottle, and carry out suction filtration with a microporous filter membrane, retain the product filter cake on the filter membrane, and pump the waste liquid into the filter bottle;

(5) Washing and suction filtration

Put the filtered product in a beaker, add 100 mL of deionized water, stir and wash for 5 minutes;

Place the washing solution in the Buchner funnel of the suction filter bottle, and perform suction filtration with a microporous filter membrane, retain the product filter cake on the filter membrane, and pump the washing solution into the filter bottle;

Washing and suction filtration are carried out twice;

Put the product filter cake in a beaker, add 100 mL of deionized water, stir and wash for 5 minutes;

Add 100 mL of ethanol, stir and wash for 5 minutes,

Washing and suction filtration were performed twice.

(6) vacuum drying

Put the washed product filter cake in a glass container, and then put it in a vacuum drying oven for drying, the drying temperature is 50°C±1°C, the vacuum degree is 50Pa, and the drying time is 10h;

Porous polymer material after drying;

(7) Detection, analysis, characterization

Detect, analyze, and characterize the morphology, composition, and chemical and physical properties of the prepared porous polymer material;

The structural analysis of the material was carried out with an X-ray diffractometer; the result is shown in Figure 2, which is the X-ray diffraction pattern of the porous polymer material, and it can be seen in Figure 2 that the obtained material has an amorphous crystal structure.

The pore structure analysis of the material was carried out with a nitrogen physical adsorption instrument; as shown in Figure 3, it is a nitrogen adsorption and desorption curve of the porous polymer material. It can be seen from the figure that the obtained porous polymer material has a porous pore structure.

The microstructure analysis of the material was carried out with a transmission electron microscope; the results are shown in Figure 4, which is a transmission electron microscope photo of the porous polymer material. It can be seen from the figure that the obtained porous polymer material has a channel structure. All the above-mentioned figures were processed with the material studio software program;

The conclusion is that the porous polymer material synthesized at room temperature is a yellow powder, the material has a mesoporous channel structure, and the product yield is 81.2%.

(8) Product storage

The prepared porous polymer material is stored in a brown transparent glass container, sealed and protected from light, waterproof, moisture-proof, sun-proof, acid, alkali and salt erosion, storage temperature 20°C ± 2°C, relative humidity ≤ 10%.

Other embodiments of the invention will be readily apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. This application is intended to cover any modification, use or adaptation of the present invention, these modifications, uses or adaptations follow the general principles of the present invention and include common knowledge or conventional technical means in the technical field not disclosed in the present invention . The specification and examples are to be considered exemplary only, with the true scope and spirit of the invention indicated by the appended claims.

It should be understood that the present invention is not limited to the precise constructions which have been described above and shown in the accompanying drawings, and various modifications and changes may be made without departing from the scope thereof. The scope of the invention is limited only by the appended claims.

Claims (3)

1. A method of preparing a porous polymeric material comprising: taking sodium-potassium alloy as a metal reducing agent, taking hexachloro-p-xylene as a precursor, stirring at room temperature, and finally preparing the porous polymer material by controlling the reaction time to adjust the pore channel structure of the porous polymer material;

the preparation method comprises the following reactants: metal sodium, metal potassium, hexachloro-para-xylene, tetrahydrofuran, ethanol and deionized water;

the combined dosage is as follows: taking g and ml as the measurement units,

sodium metal: na 0.1 g.+ -. 0.01g

Metal potassium: k0.4 g.+ -. 0.02g

Hexachloroparaxylene C ₈ H ₄ Cl ₆ 0.6g ± 0.02g

Tetrahydrofuran C ₄ H ₈ O 10 mL± 0.5mL

Ethanol: c (C) ₂ H ₅ OH 20 mL± 1mL

Deionized water: h ₂ O 300 mL± 10mL

Tetrahydrofuran C ₄ H ₈ O 100 mL±1mL

The method comprises the following steps:

(1) Preparing a sodium-potassium alloy: weighing 0.1 g+/-0.01 g of metallic sodium, weighing 0.4 g+/-0.02 g of metallic potassium, and stirring for 1 minute to prepare a sodium-potassium alloy;

(2) Synthetic porous polymeric material: under the protection of nitrogen, weighing 0.6 g+/-0.02 g of hexachloro paraxylene, dissolving in 10 mL+/-0.5 mL of tetrahydrofuran, stirring for 5 minutes, adding the prepared sodium-potassium alloy, stirring and reducing at room temperature, reacting for 24 hours, adding 20 mL+/-1 mL of ethanol, continuously stirring for 30 minutes, and filtering to obtain a solid to obtain an intermediate product;

(3) Washing and suction filtration:

(4) Vacuum drying: drying to obtain porous polymer material;

(5) Detection, analysis, characterization: and detecting, analyzing and characterizing the appearance, the components and the chemical and physical properties of the prepared porous polymer material.

2. The method for preparing a porous polymer material according to claim 1, wherein the specific steps of washing and suction filtration in the step (3) are as follows: placing the filtered product in a beaker, adding 100mL of deionized water, stirring and washing for 5 minutes; placing the washing liquid in a Buchner funnel of a suction filtration bottle, performing suction filtration by using a microporous filter membrane, reserving a product filter cake on the filter membrane, and performing washing and suction filtration for 2 times; 100mL of tetrahydrofuran was added thereto, followed by washing with stirring for 5 minutes, followed by washing and suction filtration 2 times.

3. The method for preparing a porous polymer material according to claim 1, wherein the step (4) of vacuum drying comprises the specific steps of: placing the washed product filter cake into a glass container, and then placing into a vacuum drying oven for drying at a drying temperature of 50 DEG C ^o C ± 1 ^o C, the vacuum degree is 50Pa, and the drying time is 10 hours.

Images