Organic porous polymer material and preparation method thereof

Abstract

The invention relates to an organic porous polymer material. The organic porous polymer material is synthesized from a trisail monomer and a tetramine monomer according to a certain molar ratio through a Schiff base reaction. The invention also relates to a preparation method of the porous polymer material. The porous polymer material prepared by the invention has excellent chemical stability, thermal stability, mechanical strength and good BET specific surface area, has a hydrophobic structural framework, contains alkaline N sites, and has a wide application prospect.

Description

Technical Field

[0001] The present invention relates to the technical field of porous materials, and particularly to an organic porous polymer material based on quinoxaline ring connection and a preparation method thereof. Background Art

[0002] Porous organic polymer materials are generally composed of light elements (such as carbon, hydrogen, oxygen, nitrogen, etc.), have the characteristics of low framework density and high specific surface area, and their polymer chains are connected by strong covalent bonds, having good thermal stability and chemical stability. Compared with inorganic porous materials (such as molecular sieves, inorganic-organic hybrid porous materials such as metal-organic frameworks, etc.), the great advantage of porous organic polymer materials is that the pore size and specific surface area of organic porous polymers can be adjusted by changing the functional groups and chain lengths of the structural molecules and different synthesis methods. At present, porous organic polymer materials have shown potential applications in the fields of gas storage and separation, heterogeneous catalysis, energy storage, etc.

[0003] Traditional polymerization methods for preparing porous organic polymer materials include coupling reactions, Schiff base reactions, Friedel-Crafts reactions, etc. Schiff base is a class of organic porous polymers with rich C=N structures, and due to its inherent high redox activity, rich specific surface area and excellent specific capacity, it is becoming an attractive research hotspot in the technical field of porous materials.

[0004] Therefore, it is necessary to construct quinoxaline-linked organic porous polymers through reversible Schiff base reactions and irreversible ring aromatization reactions, so that the synthesized organic porous polymer materials have a certain BET specific surface area, excellent chemical stability, thermal stability and mechanical strength. In this way, not only the diversity of the types of organic porous polymers is enriched, but also a new synthesis strategy is provided for the construction of organic porous polymers. Summary of the Invention

[0005] The present invention is made in view of the above problems, and its purpose is to provide an organic porous polymer material based on quinoxaline ring connection with a brand-new structure having a certain BET specific surface area, excellent chemical stability, thermal stability and mechanical strength.

[0006] To solve the above problems, the first aspect of the present invention provides an organic porous polymer material, and its chemical structure is as follows:

[0007]

[0008] Wherein Ar1 is selected from the following group:

[0009]

[0010] Wherein Ar2 is selected from the following group:

[0011]

[0012] Wherein X is selected from the following group:

[0013]

[0014] Wherein Y is selected from the following group:

[0015]

[0016] The second aspect of the present invention provides a method for preparing the organic porous polymer material as described in the first aspect, which includes:

[0017] Performing a polymerization reaction of a triacyl monomer and a tetraamine monomer in a solvent in the presence of an acidic catalyst to obtain the organic porous polymer material.

[0018] In one embodiment, the triacyl monomer is selected from the following group:

[0019]

[0020] Wherein Y is H, F, Cl, Br or I.

[0021] In one embodiment, the tetraamine monomer is selected from the following group:

[0022]

[0023] In one embodiment, the solvent is m-cresol, dimethyl sulfoxide or N-methylpyrrolidone.

[0024] In one embodiment, the acidic catalyst is formic acid, acetic acid or benzoic acid.

[0025] In one embodiment, the temperature of the polymerization reaction is 50°C - 120°C.

[0026] In one embodiment, the molar ratio of the triacyl monomer to the tetraamine monomer is 1:5 - 5:1, preferably 1:2 - 2:1, and more preferably 2:3.

[0027] The third aspect of the present invention provides a triacyl monomer, the chemical structure of which is as follows:

[0028]

[0029] The fourth aspect of the present invention provides a fluorinated triacyl monomer, the chemical structure of which is as follows:

[0030]

[0031] The beneficial technical effects of the present invention are as follows:

[0032] 1. Through the cycloaromatization reaction, quinoxaline rings are synthesized using aldehyde groups and amine monomers to achieve their efficient connection. This type of A2B2 bifunctional monomer exhibits similar chemical properties to traditional bifunctional monomers, thereby enhancing the chemical and thermodynamic stability of the material. The organic porous polymer material connected by quinoxaline rings provided by the present invention has excellent mechanical strength, thermal stability, and chemical stability.

[0033] 2. The reversibility of imine bonds is relatively strong, and organic porous polymers using them as linking units usually exhibit low chemical stability. However, by bridging aromatic amine groups and aromatic aldehyde groups through aromatic rings, the transformation of imine bonds into quinoline rings is achieved, reducing the reversibility of covalent bonds, thereby significantly enhancing the chemical stability of the material. In addition, this bridging method limits the rotational freedom of imine bonds and enhances the π-electron delocalization effect, contributing to the optimization of the electronic structure of the material.

[0034] 3. The preparation method of the quinoxaline ring-containing organic porous polymer material involved in the present invention results in an organic porous polymer material with a hydrophobic structural framework, excellent chemical stability, and basic N sites, having broad application prospects.

[0035] 4. The polymerization method of the present invention is simple and efficient. The Schiff base reaction has high reactivity and can proceed rapidly under appropriate catalytic conditions or solvent environments. Moreover, the reaction can be completed in a single step without by-products (only water is generated), which is environmentally friendly. It overcomes the problems of complex synthesis methods and high costs of existing organic porous polymers, and provides a porous polymer with a simple synthesis method, low production cost, and environmental friendliness, as well as its preparation method.

[0036] It should be understood that the content described in this part is not intended to identify the key or important features of the embodiments of the present disclosure, nor is it used to limit the scope of the present disclosure. Other features of the present disclosure will become easily understandable through the following description. Description of the Drawings

[0037] Figure 1 is the nuclear magnetic resonance spectrum of the triacyl monomer of Example 1 and the fluorine-containing triacyl monomer of Example 5.

[0038] Figure 2 is the infrared spectrum analysis chart of the organic porous polymer material of Example 1.

[0039] Figure 3 is the thermogravimetric analysis chart of the organic porous polymer material of Example 1.

[0040] Figure 4 is the tensile analysis chart of the organic porous polymer material of Example 1.

[0041] Figure 5It is the N2 adsorption / desorption analysis diagram of the organic porous polymer material of Example 1. Detailed implementation manners

[0042] Embodiments of the present disclosure will be described in more detail below. Although the present disclosure provides certain embodiments, it should be understood that the present disclosure can be implemented in various forms and should not be construed as limited to the embodiments set forth herein. Instead, these embodiments are provided to more thoroughly and completely understand the present disclosure. It should be understood that the drawings and embodiments of the present disclosure are only for exemplary purposes and are not used to limit the protection scope of the present disclosure.

[0043] The "range" in the present disclosure is defined in the form of a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of a particular range. The ranges defined in this way can include the end values or not include the end values, and can be combined arbitrarily, that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60 - 120 and 80 - 110 are listed for a specific parameter, it is understood that ranges of 60 - 110 and 80 - 120 are also contemplated. In addition, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, then the following ranges are all contemplated: 1 - 3, 1 - 4, 1 - 5, 2 - 3, 2 - 4, and 2 - 5. In the present disclosure, unless otherwise specified, the numerical range "a - b" represents an abbreviated representation of any real number combination between a and b, where a and b are both real numbers. For example, the numerical range "0 - 5" represents that all real numbers between "0 - 5" have been fully listed herein, and "0 - 5" is only an abbreviated representation of these numerical combinations. Additionally, when stating that a certain parameter is an integer ≥2, it is equivalent to disclosing that the parameter is, for example, the integer 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0044] The terms such as the first and the second used in the present disclosure are only for the purpose of clearly distinguishing each object and do not limit the size, quantity, or other order of the objects described. The directional terms indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, and are only for the purpose of facilitating the description of the present disclosure, rather than indicating or implying that the object referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be construed as a limitation to the present disclosure.

[0045] If there is no special instruction, all the implementation manners and optional implementation manners of the present disclosure can be combined with each other to form a new technical solution.

[0046] Unless otherwise specified, all steps of the present disclosure can be carried out in sequence or randomly, preferably in sequence. For example, the method includes steps (a) and (b), which means that the method may include steps (a) and (b) carried out in sequence, or may also include steps (b) and (a) carried out in sequence. For example, when it is mentioned that the method may further include step (c), it means that step (c) can be added to the method in any order. For example, the method may include steps (a), (b) and (c), or may also include steps (a), (c) and (b), or may also include steps (c), (a) and (b), etc.

[0047] Unless otherwise specified, the terms "comprising", "including", "having", "containing" or any other variation thereof as used in the present disclosure are intended to cover non-exclusive inclusion.

[0048] Unless otherwise specified, the indefinite articles "a" and "an" before an element or component in the present disclosure do not limit the number requirement (i.e., the number of occurrences) of the element or component. Therefore, "a" or "an" should be interpreted as including one or at least one, and the singular form of an element or component also includes the plural form, unless the quantity is clearly intended to limit the singular form.

[0049] As mentioned above, there is an urgent need in the prior art to synthesize novel organic porous polymer materials with a certain BET specific surface area, excellent chemical stability, thermal stability and mechanical strength.

[0050] Organic porous polymer material

[0051] To at least partially solve one or more of the above problems and other potential problems, the first exemplary embodiment of the present disclosure provides an organic porous polymer material, the chemical structure of which is as follows:

[0052]

[0053] Wherein Ar1 is selected from the following group:

[0054] Wherein Ar2 is selected from the following group:

[0055] Wherein X is selected from the following group:

[0056]

[0057] Wherein Y is selected from the following group:

[0058]

[0059] Method for preparing organic porous polymer material

[0060] To at least partially address one or more of the above problems and other potential problems, a second exemplary embodiment of the present disclosure provides a method for preparing an organic porous polymer material as described in the first exemplary embodiment, which includes:

[0061] In the presence of an acidic catalyst, subjecting a triacyl monomer and a tetraamine monomer to a polymerization reaction in a solvent to obtain the organic porous polymer material.

[0062] In one embodiment, the triacyl monomer is selected from the group consisting of:

[0063]

[0064] wherein Y is H, F, Cl, Br or I.

[0065] In one embodiment, the tetraamine monomer is selected from the group consisting of:

[0066]

[0067] In one embodiment, the solvent is m-cresol, dimethyl sulfoxide or N-methylpyrrolidone.

[0068] In one embodiment, the acidic catalyst is formic acid, acetic acid or benzoic acid.

[0069] In one embodiment, the temperature of the polymerization reaction is 50°C - 120°C.

[0070] In one embodiment, the molar ratio of the triacyl monomer to the tetraamine monomer is 1:5 - 5:1, preferably 1:2 - 2:1, and more preferably 2:3.

[0071] Monomer

[0072] To at least partially address one or more of the above problems and other potential problems, a third exemplary embodiment of the present disclosure provides a triacyl monomer having the following chemical structure:

[0073]

[0074] To at least partially address one or more of the above problems and other potential problems, a fourth exemplary embodiment of the present disclosure provides a fluorinated triacyl monomer having the following chemical structure:

[0075]

[0076] Hereinafter, embodiments of the present disclosure will be described. The embodiments described below are exemplary and are only used to explain the present disclosure, and should not be construed as a limitation to the present disclosure. For those without specific technical or conditions noted in the embodiments, the techniques or conditions described in the literature in this field or according to the product specifications are followed. Those reagents or instruments without the manufacturer noted are all conventional products that can be obtained through commercial purchase.

[0077] Example 1

[0078] Synthesis of triacyl monomer

[0079] Specific synthesis method:

[0080] (1) Using 1,3,5-triphenylbenzene and phenylacetyl chloride as reaction raw materials, anhydrous aluminum chloride as a catalyst (molar ratio 1:3.05:3.10), and dichloromethane as a solvent (the solid content of the reaction system is 35%); under a nitrogen atmosphere, react at an ice bath for 24 h;

[0081] (2) Pour the solution obtained in step (1) into an aqueous hydrochloric acid solution with a mass fraction of 10%, stir and then filter. Wash the filter cake with deionized water until neutral, dry it, then pour the crude product into acetone and heat it until completely dissolved, and then cool to precipitate the product. Collect the product and dry it;

[0082] (3) Using the product obtained in step (2) as a raw material, pour it into DMSO (the solid content of the reaction system is 25%) and stir until completely dissolved. Then add copper bromide (the molar amount of copper bromide used is in a ratio of 3.05:1 to the molar amount of the product obtained in step (2)) as a catalyst. Heat the reaction system to 80 °C and react for 24 h. Then pour the reaction solution into an aqueous hydrochloric acid solution with a mass fraction of 10%, stir and then filter. Wash the filter cake with deionized water until neutral, dry it, pour it into acetone to dissolve, filter to obtain the filtrate, pour the filtrate into an aqueous hydrochloric acid solution, stir and then filter to obtain the filter cake, and then wash it with deionized water until neutral, dry it and collect the product to obtain the triacyl monomer, and its chemical structural formula is as follows:

[0083]

[0084] Using the above triacyl monomer and tetraamine monomer as reaction raw materials, add them to m-cresol (the solid content of the reaction system is 1%) and stir to dissolve according to a molar ratio of 2:3. Add acetic acid (the molar amount of acetic acid used is in a ratio of 2:1 to the molar amount of the tetraamine monomer) as a catalyst. The reaction temperature is 70 °C and the reaction is carried out for 48 h. After the reaction is completed, pour it into a methanol solution to precipitate, and then filter and dry the obtained product to prepare an organic porous polymer material based on quinoxaline ring connection. The tetraamine monomer used in the above reaction is The structural formula of the obtained organic porous polymer material is:

[0085]

[0086] Example 2

[0087] Using the triacyl monomer used in Example 1 and the tetraamine monomer used in Example 1 as reaction raw materials, they were added to NMP (the solid content of the reaction system was 0.8%) in a molar ratio of 2:3 and stirred to dissolve. Formic acid (the molar ratio of the amount of formic acid used to the amount of tetraamine monomer used was 2:1) was added as a catalyst. The reaction temperature was 120 °C, and the reaction was carried out for 24 h. After the reaction, it was poured into a methanol solution to precipitate, and then the obtained product was filtered and dried to prepare an organic porous polymer material based on quinoxaline ring connection.

[0088] Example 3

[0089] Using the triacyl monomer used in Example 1 and the tetraamine monomer used in Example 1 as reaction raw materials, they were added to DMSO (the solid content of the reaction system was 0.8%) in a molar ratio of 2:3 and stirred to dissolve. Acetic acid (the molar ratio of the amount of acetic acid used to the amount of tetraamine monomer used was 2:1) was added as a catalyst. The reaction temperature was 50 °C, and the reaction was carried out for 72 h. After the reaction, it was poured into a methanol solution to precipitate, and then the obtained product was filtered and dried to prepare an organic porous polymer material based on quinoxaline ring connection.

[0090] Example 4

[0091] Using the triacyl monomer used in Example 1 and the tetraamine monomer used in Example 1 as reaction raw materials, they were added to m-cresol (the solid content of the reaction system was 1%) in a molar ratio of 2:3 and stirred to dissolve. Formic acid (the molar ratio of the amount of formic acid used to the amount of tetraamine monomer used was 2:1) was added as a catalyst. The reaction temperature was 100 °C, and the reaction was carried out for 48 h. After the reaction, it was poured into a methanol solution to precipitate, and then the obtained product was filtered and dried to prepare an organic porous polymer material based on quinoxaline ring connection.

[0092] Example 5

[0093] Synthesis of fluorinated triacyl monomer

[0094] Specific synthesis method:

[0095] (1) Using 1,3,5-triphenylbenzene and p-fluorophenylacetyl chloride as reaction raw materials, anhydrous aluminum chloride as a catalyst (molar ratio 1:3.05:3.10), and dichloromethane as a solvent (the solid content of the reaction system was 35%); under a nitrogen atmosphere, the reaction was carried out in an ice bath for 24 h;

[0096] (2) Pour the solution obtained in step (1) into 10% hydrochloric acid aqueous solution, stir and then filter. Wash the filter cake with deionized water until neutral, dry it, pour the crude product into acetone, heat it until completely dissolved, then cool to precipitate the product, collect the product and dry it;

[0097] (3) Take the product obtained in step (2) as the raw material, pour it into DMSO (the solid content of the reaction system is 25%) and stir until completely dissolved. Then add copper bromide (the molar dosage ratio of copper bromide to the product obtained in step (2) is 3.05:1) as the catalyst, heat the reaction system to 80 °C and react for 24 h. Then pour the reaction solution into 10% hydrochloric acid aqueous solution, stir and then filter. Wash the filter cake with deionized water until neutral, dry it, pour it into acetone to dissolve, filter to obtain the filtrate, pour the filtrate into hydrochloric acid aqueous solution, stir and then filter to obtain the filter cake, and then wash it with deionized water until neutral, dry it and collect the product;

[0098] The structural formula of the obtained fluorinated triacyl monomer is as follows:

[0099]

[0100] As a representative example, the performance of the organic porous polymer material prepared in Example 1 was tested.

[0101] Test results

[0102] The test results are as Figure 3 、 4 and Figure 5 show that it can be clearly seen that the synthesized organic porous polymer material based on quinoxaline ring connection has excellent chemical stability, thermal stability (the thermal weight loss temperature is higher than 500 °C), mechanical strength (the tensile strength is greater than 80 MPa), and has a certain BET specific surface area, thus achieving obvious beneficial technical effects.

[0103] The foregoing examples are merely illustrative and are used to explain some features of the present disclosure. The appended claims are intended to claim the broadest scope conceivable, and the embodiments presented herein are merely illustrative of selected implementations from all possible combinations of embodiments. Thus, the applicant's intention is that the appended claims not be limited by the selection of examples that illustrate the features of the present application. As used in the claims, the term "comprising" and its semantic variants also logically include different and varying terms, such as but not limited to "consisting essentially of" or "consisting of". When numerical ranges are provided, those ranges also include sub-ranges therebetween. Variations within these ranges will also be apparent to those skilled in the art and should not be considered dedicated to the public, and such variations should, where possible, be construed as being covered by the appended claims. Moreover, technological advancements will form possible equivalents or sub-substitutions that are not currently contemplated due to the imprecision of language expression, and such variations should, where possible, be construed as being covered by the appended claims.

Claims

1. An organic porous polymer material, with its chemical structure as follows: wherein Ar1 is selected from the following group: wherein Ar2 is selected from the following group: wherein X is selected from the following group: wherein Y is selected from the following group:

2. A method for preparing the organic porous polymer material as claimed in claim 1, which comprises: carrying out a polymerization reaction between a triacyl monomer and a tetraamine monomer in a solvent in the presence of an acidic catalyst to obtain the organic porous polymer material.

3. The method according to claim 2, wherein the triacyl monomer is selected from the following group: wherein Y is H, F, Cl, Br or I.

4. The method according to claim 2, wherein the tetraamine monomer is selected from the following group:

5. The method according to claim 2, wherein the solvent is m-cresol, dimethyl sulfoxide or N-methylpyrrolidone.

6. The method according to claim 2, wherein the acidic catalyst is formic acid, acetic acid or benzoic acid.

7. The method according to claim 2, wherein the temperature of the polymerization reaction is 50°C - 120°C.

8. The method according to claim 2, wherein the molar ratio of the triacyl monomer to the tetraamine monomer is 1:5 - 5:1, preferably 1:2 - 2:1, more preferably 2:

3.

9. A triacyl monomer, with its chemical structure as follows:

10. A fluorinated triacyl monomer, with its chemical structure as follows:

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