CN110028640A - It is a kind of based on triphenylimidazolyl-phloroglucin porous polymer and its preparation method and application - Google Patents

Abstract

The present invention provides a porous polymer based on triphenylimidazole-phloroglucinol. The porous polymer is prepared by the following preparation method: firstly, terephthalaldehyde is protected by thioacetal, and a benzoin condensation reaction is carried out, After oxidation, 4,4-bis(1,3-dithiolanyl)bibenzoyl was obtained, then imidazole was formed into a ring, butyl was substituted for imidazole hydrogen, and 2,4,5-tris(4-formyl) was obtained by deprotection phenyl)-1-butyl-imidazole; then react 2,4,5-tris(4-formylphenyl)-1-butyl-imidazole with phloroglucinol to obtain triphenylimidazole-m- Porous polymer of pyrogallol. The porous polymer is a solid adsorbent with easy preparation, low cost and good adsorption effect, and the gas adsorption capacity is enhanced by enlarging the specific surface area of the polymer.

Description

A kind of porous polymer based on triphenylimidazole-phloroglucinol and preparation method thereof and use

technical field

The invention relates to a porous polymer and a preparation method thereof, in particular to a triphenylimidazole-phloroglucinol-based porous polymer for gas adsorption, a preparation method and application thereof, and belongs to the field of gas adsorbents.

Background technique

In recent years, global climate change caused by the greenhouse effect has gradually become an environmental issue that has attracted much attention. As the largest "contributor" to the greenhouse effect, carbon dioxide is increasing in the atmosphere and is exacerbating the deterioration of the global climate and ecology. . Carbon dioxide emissions are mainly caused by the burning of fossil fuels, so simply reducing carbon dioxide emissions is bound to have an impact on industrial development and social economy. Although countries have devoted themselves to the development of green energy and new energy, they have not yet reached the level of universal application. For my country, it is in the golden stage of economic development, and the development of industry will inevitably lead to an increase in carbon emissions. The development of carbon dioxide capture and storage (CCS) technology can not only reduce the impact on my country's economic development, but also achieve the purpose of reducing carbon dioxide gas emissions.

Carbon dioxide capture technologies mainly include liquid amine absorption, membrane separation and adsorption methods. At present, liquid amine solution is mainly used to absorb carbon dioxide. This method has high adsorption capacity, good selectivity and high efficiency, but there are still inherent shortcomings such as corrosion of equipment, difficult recovery, easy volatility, and poor cycle performance, which limit the Its further application in industry. Membrane separation technology has low efficiency and complicated operation, and this method is rarely used. In recent years, the continuously developed adsorption method uses solid adsorption materials to adsorb carbon dioxide, which has the advantages of high adsorption capacity, no corrosion, and low cost, which makes up for the shortcomings of the above two methods. Solid adsorbents are undoubtedly a good choice for capturing carbon dioxide, which converts carbon dioxide into solid form during the reaction process for easy storage, transportation and use. Fibers, ceramic materials, metal oxides, and porous materials have their own characteristics in adsorbing carbon dioxide. In general, there are the following problems. Materials with mature technology, wide sources, and easy synthesis generally have low adsorption capacity, and materials with high adsorption capacity are currently synthesized under harsh conditions, high energy consumption, high cost, and difficult to control the reaction process.

Porous materials widely exist in nature, for example, wood, sponge, natural zeolite, etc. are typical porous materials. Porous materials have the characteristics of large specific surface area, tunable pore size, and diverse structures. Therefore, it has broad application prospects in the fields of catalysis, adsorption, ion exchange, biomedicine, energy, environment, optoelectronic materials and so on.

After a lot of research, there are still some problems in the research field of carbon dioxide adsorption by solid adsorbents. At present, the use of polyamine-based amination reagents and methods such as increasing the specific surface area of the carrier can appropriately improve the adsorption capacity of adsorbing carbon dioxide, but the improvement effect is still It needs to be further improved; secondly, in the process of adsorbing carbon dioxide by solid adsorbents, the diffusion of carbon dioxide in the carrier pores is generally hindered, which reduces the adsorption capacity of adsorbents for carbon dioxide; moreover, the existing solid adsorbents are generally heat resistant. Poor, it is not enough to meet the use requirements under specific conditions (such as high temperature flue gas), which limits its application space. Therefore, the development of solid adsorbents with high heat resistance and strong carbon dioxide adsorption capacity is the focus of future research in this field.

SUMMARY OF THE INVENTION

Aiming at the problems of small specific surface area and weak adsorption capacity of the solid adsorbent used for adsorbing gas in the prior art, the present invention proposes a solid adsorbent that is easy to prepare, low cost, and has good adsorption effect. By expanding the specific surface area of the polymer to enhance the gas adsorption capacity. The invention develops and prepares a porous polymer based on triphenylimidazole-phloroglucinol, which has a larger specific surface area, and wherein active functional groups such as an imidazole ring can enhance the adsorption of carbon dioxide.

According to the first embodiment provided by the present invention, a porous polymer based on triphenylimidazole-phloroglucinol is provided.

A porous polymer based on triphenylimidazole-phloroglucinol, the porous polymer is prepared by the following preparation method: firstly, terephthalaldehyde is protected by thioacetal, subjected to benzoin condensation reaction, and obtained by oxidation 4,4-bis(1,3-dithiolanyl)bibenzoyl, then imidazole to form a ring, butyl to replace imidazole hydrogen, deprotection to obtain 2,4,5-tris(4-formylphenyl) -1-butyl-imidazole; 2,4,5-tris(4-formylphenyl)-1-butyl-imidazole is then reacted with phloroglucinol to obtain a triphenylimidazole-phloroglucinol-based of porous polymers.

The polymer has the following structural formula:

Preferably, the terephthalaldehyde is protected by thioacetal to react with thiol to obtain 4-(1,3-dithiolanyl)benzaldehyde.

Preferably, the benzoin condensation reaction is that 4-(1,3-dithiolanyl)benzaldehyde reacts with cyanate or vitamin B1 in an alcohol solution to obtain 1,2-bis(4-(1, 3-Dithiolanyl)phenyl)-2-hydroxyethanone.

Preferably, the oxidation is to react 1,2-bis(4-(1,3-dithiolanyl)phenyl)-2-hydroxyethanone with an oxidizing agent to obtain 4,4-bis(1,3 - dithiolanyl) bibenzoyl.

Preferably, the imidazole ring is formed by reacting 4,4-bis(1,3-dithiolanyl)bibenzoyl with 4-(1,3-dithiolanyl)benzaldehyde to obtain 2 ,4,5-Tris(4-(1,3-dithiolanyl)phenyl)-1H-imidazole.

Preferably, the butyl-substituted imidazole hydrogen is 2,4,5-tris(4-(1,3-dithiolanyl)phenyl)-1H-imidazole and a butyl-containing compound to react to obtain 2, 4,5-Tris(4-(1,3-dithiolanyl)phenyl)-1-butyl-imidazole.

Preferably, the deprotection is to react 2,4,5-tris(4-(1,3-dithiolanyl)phenyl)-1-butyl-imidazole with a metal complexing agent to obtain 2, 4,5-Tris(4-formylphenyl)-1-butyl-imidazole.

According to the second embodiment provided by the present invention, a preparation method of a porous polymer based on triphenylimidazole-phloroglucinol is provided.

A method for preparing a meta-triphenol imidazole ring-containing porous polymer or a method for preparing the triphenyl imidazole-phloroglucinol-based porous polymer described in the first embodiment, the method comprising the steps of:

(1) Preparation of catalyst: SiO ₂ is subjected to activation treatment, and then activated SiO ₂ is soaked in NaHSO ₄ to obtain a silica catalyst loaded with sodium bisulfate;

(2) Preparation of 2,4,5-tris(4-formylphenyl)-1-butyl-imidazole: firstly, terephthalaldehyde is protected by thioacetal, and benzoin condensation reaction is carried out, and 4, 4-bis(1,3-dithiolanyl)bibenzoyl, then imidazole to form a ring, butyl substituted imidazole hydrogen, deprotection treatment to obtain 2,4,5-tris(4-formylphenyl) )-1-butyl-imidazole;

(3) Synthesis of triphenylimidazole-phloroglucinol-based porous polymer: 2,4,5-tris(4-formylphenyl)-1-butyl-imidazole was dissolved in a solvent, in which Phloroglucinol is added and reacted to obtain a triphenylimidazole-phloroglucinol-based porous polymer.

Preferably, step (1) is specifically as follows: placing SiO ₂ in a muffle furnace for 1-4h (preferably 1.2- 3h, more preferably 1.5-2.5h), then the activated SiO ₂ is soaked in NaHSO ₄ for 12-48h (preferably 18-36h, more preferably 20-32h), filtered and dried (preferably by vacuum drying) , that is, the silica catalyst loaded with sodium bisulfate is obtained.

Preferably, the volume concentration of the NaHSO ₄ is 5-30%, preferably 6-25%, more preferably 8-20%; the mass ratio of the activated SiO ₂ to NaHSO ₄ is 1:2-20, preferably It is 1:4-18, more preferably 1:6-16.

Preferably, step (2) is specifically: the preparation of 2,4,5-tris(4-formylphenyl)-1-butyl-imidazole:

a. terephthalaldehyde is dissolved in organic solvent (preferably one or more in ethyl acetate, tetrahydrofuran, methylene dichloride), to wherein add the silicon dioxide of the supported sodium bisulfate prepared by step (1) catalyst, then add mercaptan (preferably one or more of ethanedithiol, methyl mercaptan, ethane mercaptan), stir to react (preferably at room temperature to react), separate (preferably adopt column chromatography) Separate, more preferably adopt the column chromatography that petroleum ether/ethyl acetate volume ratio is 10:1), obtain product 4-(1,3-dithiolanyl) benzaldehyde;

b. Dissolve 4-(1,3-dithiolanyl)benzaldehyde in a solvent (preferably ethanol solution, more preferably 70-99% ethanol solution, more preferably 80-98% ethanol solution) , then add cyanate or vitamin B1 (preferably NaCN) to it, heat (preferably heated to 50-75 ° C, more preferably heated to 55-70 ° C), react, wash (preferably use deionized water to wash ), separated (preferably by suction filtration), the solid was repeatedly washed (preferably washed twice with deionized water), recrystallized (preferably by absolute ethanol recrystallization) to obtain 1,2-two (4-(1,3 - dithiolanyl)phenyl)-2-hydroxyethanone;

c. Dissolve 1,2-bis(4-(1,3-dithiolanyl)phenyl)-2-hydroxyethanone in a solvent (preferably a mixture of glacial acetic acid and/or water, more preferably The volume ratio of glacial acetic acid and water is a mixed solution of 5-20:1), heating and dissolving (preferably heated to 80-160 ° C, more preferably 100-140 ° C), adding an oxidant (preferably FeCl ₃ ), carrying out Reaction, washing (preferably with deionized water washing), separation (preferably with suction filtration), column chromatography separation to obtain 4,4-bis(1,3-dithiolanyl)bibenzoyl;

d. Dissolve 4,4-bis(1,3-dithiolanyl)bibenzoyl and 4-(1,3-dithiolanyl)benzaldehyde in a solvent (preferably ammonium acetate is dissolved in acetic acid), react (preferably heated to 80-160°C in an inert gas, more preferably heated to 100-140°C), washed (preferably with cold water) to obtain 2,4,5- Tris(4-(1,3-Dithiolanyl)phenyl)-1H-imidazole;

e. Dissolve 2,4,5-tris(4-(1,3-dithiolanyl)phenyl)-1H-imidazole and a butyl-containing compound (preferably n-bromobutane) in a solvent (preferably TBAB, a mixed solution of sodium hydroxide and butanone), heated to reflux, and reacted to obtain 2,4,5-tris(4-(1,3-dithiolanyl)phenyl)-1-butyl - imidazole;

f. 2,4,5-tris(4-(1,3-dithiolanyl)phenyl)-1-butyl-imidazole, metal complexing agent (preferably mercuric oxide and/or mercuric nitrate) , the catalyst (preferably boron trifluoride ether and/or nitric acid) is dissolved in a solvent (preferably a mixed solution of THF and water, more preferably a mixed solution in which the volume ratio of THF/H ₂ O is 5-20:1) , heating (preferably heated to 50-100°C, more preferably 60-80°C), react, and separate (preferably by column chromatography) to obtain 2,4,5-tris(4-formylphenyl) -1-Butyl-imidazole.

Preferably, step (3) is specifically: dissolving 2,4,5-tris(4-formylphenyl)-1-butyl-imidazole and phloroglucinol in a solvent (preferably 1,4-dioxo Hexane), heating and stirring to react (preferably heated to 50-90 ° C and stirring for 0.5-3 h), then placed in an autoclave, placed in an inert gas environment, and reacted at 180-280 ° C for 1-10d (preferably React 2-8d at 200-260°C), cool to room temperature, separate (preferably by suction filtration), wash (preferably wash with DMF), dry (preferably at 100-160°C under vacuum for 12-48h) to obtain Porous polymers based on triphenylimidazole-phloroglucinol.

Preferably, the mass concentration of 2,4,5-tris(4-formylphenyl)-1-butyl-imidazole dissolved in the solvent is 150-500g/L, preferably 180-400g/L; 2,4 , The molar ratio of 5-tris(4-formylphenyl)-1-butyl-imidazole to phloroglucinol is 1:1-4, preferably 1:1.2-3.

Preferably, in step a, the mass concentration of terephthalaldehyde dissolved in the solvent is 40-200 g/L, preferably 60-100 g/L.

Preferably, the mass ratio of the sodium bisulfate-loaded silica catalyst to terephthalaldehyde is 1:2-20, preferably 1:3-10.

Preferably, the mass ratio of thiol to terephthalaldehyde is 1:1-10, preferably 1:2-8.

Preferably, in step b, the mass concentration of 4-(1,3-dithiolanyl)benzaldehyde dissolved in the solvent is 50-500 g/L, preferably 80-400 g/L.

Preferably, the mass ratio of cyanate to 4-(1,3-dithiolanyl)benzaldehyde is 1:2-15, preferably 1:3-10.

Preferably, in step c, the mass concentration of 1,2-bis(4-(1,3-dithiolanyl)phenyl)-2-hydroxyethanone dissolved in the solvent is 40-200g/L, preferably It is 60-100g/L.

Preferably, the mass ratio of the oxidant to 1,2-bis(4-(1,3-dithiolanyl)phenyl)-2-hydroxyethanone is 1:0.5-5, preferably 1:0.8-2 .

Preferably, in step d, the molar ratio of 4,4-bis(1,3-dithiolanyl)bibenzoyl to 4-(1,3-dithiolanyl)benzaldehyde is 1:0.6 -2, preferably 1:0.8-1.5.

Preferably, the molar ratio of 4,4-bis(1,3-dithiolanyl)bibenzoyl to ammonium acetate is 1:5-20, preferably 1:8-15.

Preferably, in step e, the molar ratio of 2,4,5-tris(4-(1,3-dithiolanyl)phenyl)-1H-imidazole to the butyl-containing compound is 1:0.6-2, It is preferably 1:0.8-1.5.

Preferably, the mass concentration of 2,4,5-tris(4-(1,3-dithiolanyl)phenyl)-1H-imidazole dissolved in the solvent is 20-200g/L, preferably 40-100g /L.

Preferably, the volume ratio of sodium hydroxide and butanone is 1:1-3, preferably 1:1.2-2.5.

Preferably, the mass concentration of TBAB in the mixed solution is 1-20 g/L, preferably 30-15 g/L.

Preferably, in step f, the mass ratio of 2,4,5-tris(4-(1,3-dithiolanyl)phenyl)-1-butyl-imidazole to metal complexing agent is 1:0.8 -4, preferably 1:1-3.

Preferably, the mass ratio of 2,4,5-tris(4-(1,3-dithiolanyl)phenyl)-1-butyl-imidazole to the catalyst is 1:4-20, preferably 1:4: 5-10.

Preferably, the mass concentration of 2,4,5-tris(4-(1,3-dithiolanyl)phenyl)-1-butyl-imidazole dissolved in the solvent is 10-100g/L, preferably 12-80g/L.

According to the third embodiment provided by the present invention, there is provided the use of a triphenylimidazole-phloroglucinol-based porous polymer.

Triphenylimidazole-phloroglucinol-based porous polymer according to the first embodiment or triphenylimidazole-phloroglucinol-based porous polymer prepared according to the method described in the second embodiment The use of triphenylimidazole-phloroglucinol-based porous polymers for gas adsorption.

As a preference, porous polymers based on triphenylimidazole-phloroglucinol are used for _CO adsorption.

In the present invention, the reaction of terephthalaldehyde through thioacetal protection is as follows: terephthalaldehyde reacts with dithiol to obtain 4-(1,3-dithiolanyl)benzaldehyde. The purpose of this reaction is to protect the aldehyde group and prevent it from further reacting to produce a chain polymer.

In the present invention, the benzoin condensation reaction is that 4-(1,3-dithiolanyl)benzaldehyde reacts with cyanate in an alcohol solution to obtain 1,2-bis(4-(1,3-bis) thiolanyl)phenyl)-2-hydroxyethanone. The purpose of this reaction is to obtain the intermediate of benzoin.

The purpose of using cyanate is to act as a catalyst to promote the reaction.

In the present invention, the oxidation reaction is: 1,2-bis(4-(1,3-dithiolanyl)phenyl)-2-hydroxyethanone reacts with an oxidizing agent to obtain 4,4-bis(1 , 3-Dithiolanyl) bibenzoyl. The purpose of this reaction is to obtain an intermediate of benzil for the next step of imidazole ring formation.

The purpose of using the mixed solution of glacial acetic acid and/or water as the solvent is to dissolve all the reactants and the catalyst, and to speed up the reaction.

In the present invention, the imidazole ring-forming reaction is the reaction of 4,4-bis(1,3-dithiolanyl)bibenzoyl and 4-(1,3-dithiolanyl)benzaldehyde to obtain 2,4,5-Tris(4-(1,3-dithiolanyl)phenyl)-1H-imidazole. The purpose of this reaction is to form an intermediate of the imidazole ring.

The purpose of using the mixed solution of ammonium acetate dissolved in acetic acid is that ammonium acetate acts as a reactant to react with an aldehyde group to form an imidazole ring.

The purpose of the reaction in an inert gas is to prevent oxidation of the aldehyde group.

In the present invention, 2,4,5-tris(4-(1,3-dithiolanyl)phenyl)-1H-imidazole is reacted with a butyl-containing compound. 2,4,5-Tris(4-formylphenyl)-1-butyl-imidazole was substituted with butyl at the imidazole hydrogen due to 2,4,5-tris(4-formylphenyl)-1H-imidazole It has poor solubility and is difficult to separate and purify. Therefore, it is considered to replace the hydrogen on imidazole, but when short alkane chains such as methyl and ethyl are connected, the solubility is still relatively poor. In addition, considering that the too long alkyl chain may affect the specific surface area of the polymer, the butyl group is selected to replace the hydrogen on the imidazole ring.

The reaction adopts the mixed solution of TBAB, sodium hydroxide and butanone as the solvent; the function of TBAB is to act as a phase transfer catalyst.

The role of sodium hydroxide is to act as a base remover to carry out a substitution reaction with hydrogen on imidazole.

The role of butanone is as a reaction solvent.

In the present invention, the deprotection reaction is as follows: 2,4,5-tris(4-(1,3-dithiolanyl)phenyl)-1-butyl-imidazole is reacted with a metal complexing agent to obtain 2,4,5-Tris(4-formylphenyl)-1-butyl-imidazole. This reaction is a phase transfer catalytic reaction.

The role of the metal complexing agent is to form a complex with the deprotected ethanedithiol to make the reaction proceed in the positive direction.

The function of using boron trifluoride ether is to lower the reaction temperature and promote the reaction.

In the present invention, the catalyst is first treated, the SiO ₂ is subjected to activation treatment, and then the activated SiO ₂ is soaked in NaHSO ₄ . The purpose of this treatment is to support _NaHSO4 on _SiO2 .

The reason for choosing NaHSO ₄ is its simple availability and high catalytic efficiency.

In the present invention, the purpose of selecting 1,4-dioxane as the solvent in step (3) is because the solution has a pore-forming effect, which is beneficial to increase the specific surface area of the polymer.

In step (3), firstly stir at 50-90°C for 0.5-3h, because the reaction is a solvothermal reaction, and no stirring is required after putting it into the autoclave. In order to make the reaction uniform, it must be stirred at 50-90°C After 0.5-3h, all the reactants were dissolved and then transferred to the autoclave.

The specific surface area of the porous polymer based on triphenylimidazole-phloroglucinol prepared by the present invention is 978 m ² /g. The porous polymer based on triphenylimidazole-phloroglucinol synthesized in the present invention has an adsorption capacity of 3.99 mmol/g for carbon dioxide at 0° C., and an adsorption capacity of 2.79 mmol/g for carbon dioxide at room temperature.

Compared with the prior art, the technical scheme provided by the present invention has the following beneficial technical effects:

1. The synthesis of the polymer monomer 2,4,5-tris(4-formylphenyl)-1-butyl-imidazole provided by the present invention and the formation of a porous polymer with phloroglucinol are the first time.

2. The porous polymer based on triphenylimidazole-phloroglucinol prepared by the present invention has a larger specific surface area and has certain advantages in gas adsorption.

3. The porous polymer based on triphenylimidazole-phloroglucinol prepared by the present invention has active functional groups such as imidazole ring and a large number of hydroxyl groups, which are helpful for the adsorption of carbon dioxide.

Description of drawings

Figure 1 is a synthesis diagram of the present invention for preparing 2,4,5-tris(4-formylphenyl)-1butyl-imidazole.

FIG. 2 is a nuclear magnetic characterization diagram of 2,4,5-tris(4-formylphenyl)-1butyl-imidazole prepared in Example 1 of the present invention.

Figure 3 is a synthesis diagram of the present invention for preparing a porous polymer based on triphenylimidazole-phloroglucinol.

4 is the nitrogen adsorption and desorption curve of the porous polymer based on triphenylimidazole-phloroglucinol prepared in Example 3 of the present invention.

5 is a pore size distribution diagram of the triphenylimidazole-phloroglucinol-based porous polymer prepared in Example 3 of the present invention.

6 is the _CO adsorption curve of the triphenylimidazole-phloroglucinol-based porous polymer at 273K in Example 3 of the present invention.

7 is the _CO adsorption curve of the triphenylimidazole-phloroglucinol-based porous polymer at 298K in Example 3 of the present invention.

Detailed ways

The technical solutions of the present invention are illustrated below with examples, and the scope of the claimed protection of the present invention includes but is not limited to the following examples.

According to embodiments provided by the present invention, a porous polymer based on triphenylimidazole-phloroglucinol is provided.

A porous polymer based on triphenylimidazole-phloroglucinol, the polymer is prepared by the following preparation method: firstly, terephthalaldehyde is protected by thioacetal, subjected to benzoin condensation reaction, and oxidized to obtain 4 ,4-bis(1,3-dithiolanyl)bibenzoyl, and then imidazole to form a ring, butyl substituted imidazole hydrogen, deprotection to obtain 2,4,5-tris(4-formylphenyl)- 1-butyl-imidazole; 2,4,5-tris(4-formylphenyl)-1-butyl-imidazole is then reacted with phloroglucinol to obtain triphenylimidazole-phloroglucinol-based Porous polymer.

Preferably, the terephthalaldehyde is protected by thioacetal to react with dithiol to obtain 4-(1,3-dithiolanyl)benzaldehyde.

Preferably, the benzoin condensation reaction is that 4-(1,3-dithiolanyl)benzaldehyde reacts with cyanate in an alcohol solution to obtain 1,2-bis(4-(1,3-bis(1,3-dithiocyanate) thiolanyl)phenyl)-2-hydroxyethanone.

Preferably, the oxidation is to react 1,2-bis(4-(1,3-dithiolanyl)phenyl)-2-hydroxyethanone with an oxidizing agent to obtain 4,4-bis(1,3 - dithiolanyl) bibenzoyl.

Preferably, the imidazole ring is formed by reacting 4,4-bis(1,3-dithiolanyl)bibenzoyl with 4-(1,3-dithiolanyl)benzaldehyde to obtain 2 ,4,5-Tris(4-(1,3-dithiolanyl)phenyl)-1H-imidazole.

Preferably, the butyl-substituted imidazole hydrogen is 2,4,5-tris(4-(1,3-dithiolanyl)phenyl)-1H-imidazole and a butyl-containing compound to react to obtain 2, 4,5-Tris(4-(1,3-dithiolanyl)phenyl)-1-butyl-imidazole.

Preferably, the deprotection is the reaction of 2,4,5-tris(4-(1,3-dithiolanyl)phenyl)-1H-imidazole with a metal complexing agent to obtain 2,4,5 -Tris(4-formylphenyl)-1H-imidazole.

Example 1

A preparation method of a porous polymer based on triphenylimidazole-phloroglucinol, the method comprises the following steps:

(1) Preparation of catalyst: SiO ₂ is subjected to activation treatment, and then activated SiO ₂ is soaked in NaHSO ₄ to obtain a silica catalyst loaded with sodium bisulfate;

(2) Preparation of 2,4,5-tris(4-formylphenyl)-1-butyl-imidazole: firstly, terephthalaldehyde is protected by thioacetal, and benzoin condensation reaction is carried out, and 4, 4-bis(1,3-dithiolanyl)bibenzoyl, then imidazole to form a ring, butyl substituted imidazole hydrogen, deprotection treatment to obtain 2,4,5-tris(4-formylphenyl) )-1-butyl-imidazole;

(3) Synthesis of triphenylimidazole-phloroglucinol-based porous polymer: 2,4,5-tris(4-formylphenyl)-1-butyl-imidazole was dissolved in a solvent, in which Phloroglucinol is added and reacted to obtain a triphenylimidazole-phloroglucinol-based porous polymer.

Example 2

A preparation method of a porous polymer based on triphenylimidazole-phloroglucinol, the method comprises the following steps:

(1) Preparation of catalyst: take 100g SiO ₂ and place it in a muffle furnace for activation at 200°C for 2h, then pour the activated SiO ₂ into 10% NaHSO ₄ solution and soak it for 24h, finally filter it with suction, and dry it to obtain Silica catalyst loaded with sodium bisulfate;

(2) Preparation of 2,4,5-tris(4-formylphenyl)-1-butyl-imidazole:

a. Dissolve 1g of terephthalaldehyde in 10ml of methylene chloride, add 0.2g of the supported sodium bisulfate catalyst prepared in step (1) to it, then slowly drop 0.35g of ethylene glycol while stirring Thiol, stir the reaction at room temperature, spin dry the solvent after the reaction is complete, and separate the product by column chromatography (petroleum ether/ethyl acetate (10:1)) to obtain the product 4-(1,3-dithiolanyl)benzene formaldehyde;

b. Dissolve 2g of 4-(1,3-dithiolanyl)benzaldehyde in 10ml of 95% ethanol solution, add 0.4g of NaCN to it, heat to about 65°C, pour the reacted liquid into 200ml of deionized water was washed, and the solid was obtained by suction filtration, and the washing was repeated twice to obtain a crude product; the crude product was recrystallized twice in absolute ethanol to obtain 1,2-bis(4-(1,3-dithiolanyl) phenyl)-2-hydroxyethanone;

c. Add 10ml of glacial acetic acid and 1ml of water to a 100ml round-bottomed flask, add 1g of 1,2-bis(4-(1,3-dithiolanyl)phenyl)-2-hydroxyethanone to it, heat it To 120 ℃, after it is completely dissolved, add 1g FeCl ₃ , pour 50ml of deionized water into the reaction solution after the reaction is completed, and suction filtration to obtain a solid crude product; the crude product is separated by column chromatography to obtain 4,4-di( 1,3-Dithiolanyl)bibenzoyl;

d. 1 g (2.4 mmol) 4,4-bis(1,3-dithiolanyl)bibenzoyl, 0.5 g (2.4 mmol) 4-(1,3-dithiolanyl)benzaldehyde and 1.85g (24mmol) of ammonium acetate was dissolved in the acetic acid solution, the reaction was heated to 110 ° C under inert gas to reflux, the reaction solution was poured into cold water and washed twice to obtain 2,4,5-tris(4-(1,3 - dithiolanyl)phenyl)-1H-imidazole;

e. 3g 2,4,5-tris(4-(1,3-dithiolanyl)phenyl)-1H-imidazole (4.93mmol), 6.7g (4.93mmol) n-bromobutane, 0.5g TBAB It was added to a solution containing 20ml of 50% sodium hydroxide and 40ml of butanone, heated to reflux, and reacted to obtain 2,4,5-tris(4-(1,3-dithiolanyl)phenyl)-1 -Butyl-imidazole;

f. Take 1g of 2,4,5-tris(4-(1,3-dithiolanyl)phenyl)-1-butyl-imidazole and add 1.3g HgO, 7.5ml BF ₃ -diethyl ether, 20ml (tetrahydrofuran: Water V:V 9:1) solvent; react at 70°C, and column chromatography obtains the target product 2,4,5-tris(4-formylphenyl)-1-butyl-imidazole.

(3) Synthesis of triphenylimidazole-phloroglucinol-based porous polymer: 0.504 g (4 mmol) of phloroglucinol and 0.873 g (2 mmol) of 2,4,5-trismol were added to a 10 ml round-bottomed flask (4-Formylphenyl)-1-butyl-imidazole was added to 5 ml of 1,4-dioxane; the mixture was kept stirring at 70°C for 1 hour, then the resulting yellow solution was transferred to a Teflon-lined high pressure In the kettle, the reaction was carried out at 220°C for 4 days under an inert gas; after cooling to room temperature, a dark red solid was obtained by suction filtration, which was washed twice with DMF and acetone respectively, and then vacuum-dried at 120°C for 24h. Yield 94%.

Example 3

A preparation method of a porous polymer based on triphenylimidazole-phloroglucinol, the method comprises the following steps:

(1) Preparation of catalyst: take 100g _SiO2 and put it in a muffle furnace for activation at 200 °C for 2h, then pour the activated _SiO2 into 10% _NaHSO4 solution and soak it for 24h to ensure that _NaHSO4 is adsorbed on _SiO2 , finally filtered through a Buchner funnel, transferred to a drying oven at 60°C, and dried to obtain a sodium bisulfate-loaded silica catalyst;

(2) Preparation of 2,4,5-tris(4-formylphenyl)-1-butyl-imidazole:

a. Add 1g (7.5mmol) terephthalaldehyde, 10ml anhydrous dichloromethane, 0.2g sodium bisulfate-loaded silica catalyst to the 25ml round-bottomed flask, then slowly drop 0.7g (7.5g) while stirring mmol) 1,2-ethanedithiol, the reaction was stirred at room temperature, and after the reaction was completed, the product 4-(1,3-dithiopentane) was separated by column chromatography (petroleum ether/ethyl acetate (8:1)) Cyclo)benzaldehyde 1.2g, yield 75%;

b. Dissolve 2g 4-(1,3-dithiolanyl)benzaldehyde (9.5mmol) in 20ml 95% ethanol solution, add 0.23g NaCN (5%mmol) to it, heat to 65°C , pour the reacted liquid into 200ml of deionized water and wash, suction filtration to obtain a solid, repeat the washing twice to obtain a crude product, and the crude product is recrystallized twice through absolute ethanol to obtain 1,2-bis(4-(1,3 -Dithiolanyl)phenyl)-2-hydroxyethanone 1.89g, yield 94.7%;

c. Add 10ml of glacial acetic acid and 1ml of water to a 100ml round-bottomed flask, take 1g (2.4mmol) of 1,2-bis(4-(1,3-dithiolanyl)phenyl)-2-hydroxyethanone Add it, heat to 120°C, add 1.2g (7.2mmol) FeCl ₃ after it is completely dissolved, then pour 50ml of deionized water into the reaction solution, suction filtration to obtain a solid crude product, and the crude product is separated by column chromatography (Petroleum ether/dichloromethane (2:1)) to obtain the product 4,4-bis(1,3-dithiolanyl)bibenzoyl 0.5g, with a yield of 50%;

d. 1g (2.4mmol) 4,4-bis(1,3-dithiolanyl)bibenzoyl, 0.5g (2.4mmol) 4-(1,3-dithiolanyl)benzaldehyde and 1.85g (24mmol) of ammonium acetate were dissolved in acetic acid solution, heated to 110 ℃ reflux in inert gas, the reaction solution was poured into cold water and washed twice, the resulting crude product was 2,4,5-tri(4-( 1,3-Dithiolanyl)phenyl)-1H-imidazole;

e. 3g 2,4,5-tris(4-(1,3-dithiolanyl)phenyl)-1-butyl-imidazole (4.93mmol), 6.7g (4.93mmol) n-bromobutane , 0.5g of TBAB was added to a mixed solution containing 20ml of 50% sodium hydroxide and 40ml of butanone, heated to reflux, to obtain 2,4,5-tris(4-(1,3-dithiolanyl)phenyl) )-1-butyl-imidazole;

f. Take 1g of 2,4,5-tris(4-(1,3-dithiolanyl)phenyl)-1-butyl-imidazole and add 1.3g HgO, 7.5ml BF ₃ -diethyl ether, 20ml THF/H ₂ In a mixed solution solvent with a volume ratio of O of 9:1, react at 70 °C, and column chromatography obtains 2,4,5-tris(4-formylphenyl)-1-butanyl-imidazole;

NMR characterization of 2,4,5-tris(4-formylphenyl)-1-butanyl-imidazole, ¹ H NMR (400MHz, Chloroform-d)δ10.14(s,1H), 10.12(s ,1H),9.94(s,1H),8.08–8.03(m,4H),7.93(d,J=7.8Hz,2H),7.74(dd,J=8.3,1.4Hz,2H),7.66–7.61( m, 4H), 4.01(t, J=7.6Hz, 2H), 1.32(t, J=7.5Hz, 2H), 0.98(q, J=7.4Hz, 2H), 0.62(t, J=7.3Hz, 3H).

(3) Synthesis of triphenylimidazole-phloroglucinol-based porous polymer: 2,4,5-tris(4-formylphenyl)-1-butylimidazole (218 mg, 0.5 mmol) and m The mixture of phloroglucinol (126mg 1mmol) was dissolved in 5ml 1,4-dioxane, the resulting reaction solution was first placed at 70°C and stirred for 1h, after obtaining a clear reaction solution, it was transferred to the autoclave, and continued to the Nitrogen was introduced to remove oxygen. After the oxygen removal was completed, it was sealed and transferred to 220°C to react for 96 hours. After cooling to room temperature, a reddish-brown solid precipitate was obtained. The unreacted monomers and oligomers wrapped by the polymer were washed with DMF. Then, it was washed several times with dichloromethane, water, THF, ethanol and acetone, respectively, to exchange DMF and 1,4-dioxane, and finally vacuum-dried at 120 °C overnight to obtain a compound based on m-triphenol. Porous polymer of imidazole rings in 88% yield.

Example 4

Example 3 was repeated, except that the solvent in step (2) was tetrahydrofuran, and the thiol was methyl mercaptan.

Example 5

Example 3 was repeated except that NaCN was replaced with vitamin B1 in step (3).

Example 6

Example 3 was repeated except that in step (7), mercuric nitrate was used to replace mercuric oxide, and nitric acid was used to replace boron trifluoride-diethyl ether.

The specific surface area of the triphenylimidazole-phloroglucinol-based porous polymer prepared in Example 1 of the present invention may be 978 m ² /g. The results are shown in Figure 4.

The benzoxazole polymer POF-3 formed by the polymerization of tris(4-formylphenyl)amine and phloroglucinol has a carbon dioxide adsorption of only 2.84 mmol/g at 0 °C, and a carbon dioxide adsorption of only 1.5 at room temperature. mmol/g, while the porous polymer based on triphenylimidazole-phloroglucinol synthesized by the present invention has 3.99 mmol/g of carbon dioxide adsorption at 0 ° C, and 2.79 mmol/g of carbon dioxide adsorption at room temperature, higher than POF-3 polymer. The result is shown in Figure 6-7.

Claims (10)

1. a kind of based on triphenylimidazolyl-phloroglucin porous polymer, which is by following preparation method Prepared: terephthalaldehyde is protected by mercaptal first, carries out benzoic conden-sation reaction, obtains 4,4- bis- through oxidation (1,3- dithiolane base) dibenzoyl, then imidazoles cyclization, butyl substituted imidazole hydrogen, deprotection obtain 2,4,5- tri- (4- formyls Base phenyl) -1- butyl-imidazolium；Again by 2,4,5- tri- (4- Fonnylphenyl) -1- butyl-imidazoliums and phloroglucinol reaction, obtain Based on triphenylimidazolyl-phloroglucin porous polymer.

2. according to claim 1 based on triphenylimidazolyl-phloroglucin porous polymer, it is characterised in that: described Terephthalaldehyde is reacted for terephthalaldehyde with mercaptan by mercaptal protection, obtains 4- (1,3- dithiolane base) benzene first Aldehyde；And/or

Benzoic conden-sation reaction be 4- (1,3- dithiolane base) benzaldehyde in alcoholic solution with cyanate or vitamin B1 It is reacted, obtains 1,2- bis- (4- (1,3- dithiolane base) phenyl) -2- hydroxyethanone.

3. according to claim 1 or 2 based on triphenylimidazolyl-phloroglucin porous polymer, it is characterised in that: institute It states and is oxidized to 1,2- bis- (4- (1,3- dithiolane base) phenyl) -2- hydroxyethanone and is reacted with oxidant, obtain 4,4- bis- (1,3- dithiolane base) dibenzoyl；And/or

The imidazoles cyclization be (the 1,3- dithiolane base) dibenzoyl of 4,4- bis- and 4- (1,3- dithiolane base) benzaldehyde into Row reaction, obtains 2,4,5- tri- (4- (1,3- dithiolane base) phenyl) -1H- imidazoles.

4. according to any one of claim 1-3 based on triphenylimidazolyl-phloroglucin porous polymer, feature Be: the butyl substituted imidazole hydrogen is (4- (1,3- dithiolane base) the phenyl) -1H- imidazoles of 2,4,5- tri- and chemical combination containing butyl Object is reacted, and 2,4,5- tri- (4- (1,3- dithiolane base) phenyl) -1- butyl-imidazolium is obtained；And/or

The deprotection is that (4- (1,3- dithiolane base) the phenyl) -1- butyl-imidazolium of 2,4,5- tri- and metal chelating agent carry out Reaction obtains 2,4,5- tri- (4- Fonnylphenyl) -1- butyl-imidazolium.

5. a kind of prepare based in the poromeric method of triphenylimidazolyl-phloroglucin or preparation claim 1-4 Based on the poromeric method of triphenylimidazolyl-phloroglucin described in one, method includes the following steps:

(1) preparation of catalyst: by SiO₂By being activated, then by activated SiO₂Using NaHSO₄It impregnates to get negative Carry the SiO 2 catalyst of sodium bisulfate；

(2) preparation of 2,4,5- tri- (4- Fonnylphenyl) -1- butyl-imidazolium: terephthalaldehyde is protected by mercaptal first Shield carries out benzoic conden-sation reaction, obtains 4,4- bis- (1,3- dithiolane base) dibenzoyl, then imidazoles cyclization, fourth through oxidation Base substituted imidazole hydrogen, is handled by deprotection, obtains 2,4,5- tri- (4- Fonnylphenyl) -1- butyl-imidazolium；

(3) based on the poromeric synthesis of triphenylimidazolyl-phloroglucin: by 2,4,5- tri- (4- Fonnylphenyl) -1- Butyl-imidazolium is dissolved in solvent, and phloroglucin is added wherein, is reacted, and is obtained based on triphenylimidazolyl-phloroglucin Porous polymer.

6. method according to claim 5, it is characterised in that: step (1) specifically: by SiO₂It is placed in Muffle furnace and passes through 150-300 DEG C (preferably 160-280 DEG C, more preferably 180-240 DEG C) activation processing 1-4h (preferably 1.2-3h, more preferably For 1.5-2.5h), then by activated SiO₂Using NaHSO₄Impregnate 12-48h (preferably 18-36h, more preferably 20- 32h), it filters, dry (preferably using vacuum drying) is to get the SiO 2 catalyst of load sodium bisulfate；And/or

The NaHSO₄Volumetric concentration be 5-30%, preferably 6-25%, more preferably 8-20%；Activated SiO₂With NaHSO₄Mass ratio be 1:2-20, preferably 1:4-18, more preferably 1:6-16.

7. the method according to claim 5 or 6, it is characterised in that: step (2) specifically: 2,4,5- tri- (4- formoxyls Phenyl) -1- butyl-imidazolium preparation:

A. terephthalaldehyde is dissolved in organic solvent (preferably one of ethyl acetate, tetrahydrofuran, methylene chloride or more Kind) in, it is charged with the SiO 2 catalyst of the load sodium bisulfate of step (1) preparation, mercaptan then is added (preferably One of methyl mercaptan, ethyl mercaptan, dithioglycol are a variety of), stirring is reacted and (is preferably stirred at room temperature and is reacted), Separation (preferably uses column chromatography for separation, more preferably use petrol ether/ethyl acetate volume ratio for the column chromatography for separation of 10:1), obtains To product 4- (1,3- dithiolane base) benzaldehyde；

B. by 4- (1,3- dithiolane base) benzaldehyde be dissolved in solvent (preferably ethanol solution, further preferably 70-99%'s Ethanol solution, the more preferably ethanol solution of 80-98%) in, then it is charged with cyanate or vitamin B1 (preferably NaCN), (being preferably heated to 50-75 DEG C, be further preferably heated to 55-70 DEG C) is heated, is reacted, washing is (preferably Adopt and be washed with deionized), solid repeated washing (is preferably adopted and is washed with deionized two by separation (preferably using suction filtration) It is secondary), recrystallization (is preferably recrystallized using dehydrated alcohol), and 1,2- bis- (4- (1,3- dithiolane base) phenyl) -2- hydroxyl is obtained Ethyl ketone；

C. 1,2- bis- (4- (1,3- dithiolane base) phenyl) -2- hydroxyethanone is dissolved in solvent (preferably glacial acetic acid and/or water Mixed liquor, further preferably the volume ratio of glacial acetic acid and water be 5-20:1 mixed liquor) in, dissolve by heating (preferably plus Heat is to 80-160 DEG C, and further preferably 100-140 DEG C), oxidant (preferably FeCl is added₃), it is reacted, is washed (excellent Choosing, which is adopted, to be washed with deionized), separation (preferably using suction filtration), column chromatography for separation obtains 4,4- bis- (1,3- dithiolane base) Dibenzoyl；

D. (the 1,3- dithiolane base) dibenzoyl of 4,4- bis- is dissolved in solvent with 4- (1,3- dithiolane base) benzaldehyde (excellent It is selected as the mixed solution that ammonium acetate is dissolved in acetic acid), it is reacted and (is preferably heated to 80-160 DEG C in inert gas to carry out instead Answer, be further preferably heated to 100-140 DEG C), washing (is preferably washed using cold water), and 2,4,5- tri- (4- (1,3- bis- are obtained Thiophane base) phenyl) -1H- imidazoles；

E. by (4- (1,3- dithiolane base) the phenyl) -1H- imidazoles of 2,4,5- tri-, (be preferably positive bromine fourth with butyl is contained Alkane) it is dissolved in solvent (mixed solution of preferably TBAB, sodium hydroxide and butanone), it is heated to reflux, is reacted, obtain 2,4, 5- tri- (4- (1,3- dithiolane base) phenyl) -1- butyl-imidazolium；

F. by 2,4,5- tri- (4- (1,3- dithiolane base) phenyl) -1- butyl-imidazolium, metal chelating agent (preferably mercury oxide And/or mercuric nitrate), catalyst (preferably boron trifluoride ether and/or nitric acid) be dissolved in the solvent (mixing of preferably THF and water Solution, further preferably THF/H₂The volume ratio of O is the mixed solution of 5-20:1) in, heating (is preferably heated to 50-100 DEG C, further preferably 60-80 DEG C), it is reacted, separation (preferably uses column chromatography for separation), obtains (the 4- formyl of 2,4,5- tri- Base phenyl) -1- butyl-imidazolium.

8. the method according to any one of claim 5-7, it is characterised in that: step (3) specifically: by 2,4,5- tri- (4- Fonnylphenyl) -1- butyl-imidazolium and phloroglucin are dissolved in solvent (preferably Isosorbide-5-Nitrae-dioxane), heating stirring into Row reaction (being preferably heated to 50-90 DEG C of stirring 0.5-3h), is subsequently placed in autoclave, is placed in inert gas environment and exists, 1-10d (preferably reacting 2-8d at 200-260 DEG C) is reacted at 180-280 DEG C, is cooled to room temperature, separation is (preferably using pumping Filter separation), washing (is preferably washed using DMF), and dry (being preferably dried in vacuo 12-48h at 100-160 DEG C) is based on Triphenylimidazolyl-phloroglucin porous polymer；

Preferably, it is 150- that 2,4,5- tri- (4- Fonnylphenyl) -1- butyl-imidazoliums, which are dissolved in the mass concentration in solvent, 500g/L, preferably 180-400g/L；The molar ratio of 2,4,5- tri- (4- Fonnylphenyl) -1- butyl-imidazolium and phloroglucin For 1:1-4, preferably 1:1.2-3.

9. method according to claim 7, it is characterised in that: in step a, terephthalaldehyde is dissolved in organic solvent Mass concentration is 40-200g/L, preferably 60-100g/L；Load the SiO 2 catalyst and terephthalaldehyde of sodium bisulfate Mass ratio be 1:2-20, preferably 1:3-10；The mass ratio of mercaptan and terephthalaldehyde is 1:1-10, preferably 1:2-8；

In step b, it is 50-500g/L, preferably 80- that 4- (1,3- dithiolane base) benzaldehyde, which is dissolved in the mass concentration in solvent, 400g/L；The mass ratio of cyanate and 4- (1,3- dithiolane base) benzaldehyde is 1:2-15, preferably 1:3-10；

In step c, 1,2- bis- (4- (1,3- dithiolane base) phenyl) -2- hydroxyethanone is dissolved in the mass concentration in solvent and is 40-200g/L, preferably 60-100g/L；Oxidant and 1,2- bis- (4- (1,3- dithiolane base) phenyl) -2- hydroxyethanone Mass ratio is 1:0.5-5, preferably 1:0.8-2；

In step d, the molar ratio of 4,4- bis- (1,3- dithiolane base) dibenzoyls and 4- (1,3- dithiolane base) benzaldehyde For 1:0.6-2, preferably 1:0.8-1.5；The molar ratio of (the 1,3- dithiolane base) dibenzoyl of 4,4- bis- and ammonium acetate is 1: 5-20, preferably 1:8-15；

In step e, 2,4,5- tri- (4- (1,3- dithiolane base) phenyl) -1H- imidazoles are with the molar ratio containing butyl 1:0.6-2 preferably 1:0.8-1.5；2,4,5- tri- (4- (1,3- dithiolane base) phenyl) -1H- imidazoles is dissolved in solvent Mass concentration is 20-200g/L, preferably 40-100g/L；The volume ratio of sodium hydroxide and butanone be 1:1-3, preferably 1: 1.2-2.5；Mass concentration of the TBAB in mixed solution is 1-20g/L, preferably 30-15g/L；

In step f, the mass ratio of 2,4,5- tri- (4- (1,3- dithiolane base) phenyl) -1- butyl-imidazoliums and metal chelating agent For 1:0.8-4, preferably 1:1-3；(4- (1,3- dithiolane base) the phenyl) -1- butyl-imidazolium of 2,4,5- tri- and catalyst Mass ratio is 1:4-20, preferably 1:5-10；2,4,5- tri- (4- (1,3- dithiolane base) phenyl) -1- butyl-imidazolium is dissolved in Mass concentration in solvent is 10-100g/L, preferably 12-80g/L.

10. according to claim 1 described in any one of -4 based on triphenylimidazolyl-phloroglucin porous polymer or according to The preparation of any one of claim 5-9 the method based on the poromeric purposes of triphenylimidazolyl-phloroglucin, will It is used for gas absorption based on triphenylimidazolyl-phloroglucin porous polymer, will preferably be based on triphenylimidazolyl-phloroglucin Porous polymer be used for CO₂Absorption.