Polyamine type porous polymer as well as preparation method and application thereof

Abstract

The invention discloses a polyamine type porous polymer as well as a preparation method and application thereof, and belongs to the technical field of synthesis of porous organic polymers. The specific method comprises the following steps: dispersing beta-mercaptoethylamine, a photoinitiator and a porous framework polymer with carbon-carbon double bond connection in a polar organic solvent; under the ultraviolet light initiation condition, the photoinitiator excites beta-mercaptoethylamine to generate sulfydryl free radicals, and the sulfydryl free radicals and the porous framework polymer with carbon-carbon double bond connection are subjected to an addition reaction; and washing and drying the product after the addition reaction to obtain the amino-modified polyamine porous polymer. The preparation method provided by the invention is rapid in reaction, extremely high in reactant utilization rate and simple in post-treatment, and the prepared polyamine type porous polymer has rich adsorption sites, good stability and excellent carbon dioxide adsorption performance, and can be applied to the field of carbon capture and the like.

Description

Technical Field

[0001] The present invention belongs to the technical field of porous organic polymer synthesis, and in particular relates to a polyamine-type porous polymer, a preparation method and application thereof. Background Art

[0002] The widespread use of fossil fuels has significantly increased carbon dioxide emissions, exacerbating climate change. Reducing carbon dioxide emissions has become an urgent task to prevent irreversible impacts on the atmospheric environment. In this context, developing efficient and cost-effective carbon dioxide adsorption technologies has become a key approach to addressing this issue.

[0003] Covalent organic framework materials (COFs) are crystalline materials connected by covalent bonds. They have the characteristics of high specific surface area, stable pore structure, low skeleton density and ordered channel system. They have shown great application potential in the fields of gas storage, catalysis, sensing and separation. Since the chemical and structural properties of COF materials can be flexibly controlled, they have attracted widespread attention in carbon dioxide capture and storage. By adjusting the structure and functional groups of COF, it can be made to efficiently adsorb carbon dioxide through physical or chemical means. In order to improve the adsorption capacity of carbon dioxide and effectively separate carbon dioxide from gas mixtures, it is necessary to introduce stronger chemical adsorption sites into COF materials to enhance their capture efficiency. The synthesis of covalent organic framework materials with higher carbon dioxide adsorption capacity has important application prospects and is expected to promote this material to become the next generation of high-efficiency carbon dioxide adsorbents and achieve wider industrial applications. Summary of the Invention

[0004] The purpose of the present invention is to solve the deficiencies in the prior art and provide a polyamine-type porous polymer, a preparation method and applications thereof.

[0005] The specific technical solutions adopted in the present invention are as follows:

[0006] In a first aspect, the present invention provides a method for preparing a polyamine-type porous polymer, comprising dispersing β-mercaptoethylamine, a photoinitiator, and a porous framework polymer having carbon-carbon double bonds in a polar organic solvent; under ultraviolet light initiation conditions, the photoinitiator excites the β-mercaptoethylamine to generate thiol free radicals, which react with the porous framework polymer having carbon-carbon double bonds through addition reaction; and washing and drying the product after the addition reaction to obtain a polyamine-modified porous polymer.

[0007] Preferably, the preparation method of the porous framework polymer having carbon-carbon double bonds is as follows:

[0008] 2,4,6-trimethyl-1,3,5-triazine, an aldehyde compound and benzoic anhydride are mixed and heated to perform a polymerization reaction to obtain a crude product; the crude product is washed to remove unreacted compounds and then dried to obtain a porous framework polymer with carbon-carbon double bonds; the aldehyde compound has two or more aldehyde sites that can react with the 2,4,6-trimethyl-1,3,5-triazine.

[0009] Furthermore, the aldehyde compound adopts one of the following chemical structural formulas:

[0010]

[0011] Furthermore, the aldehyde compound is 1,3,5-benzenetricarboxaldehyde, 1,3,5-tris(4-formylphenyl)benzene or 4,4',4"-[benzene-1,3,5-triyltris(acetylene-2,1-diyl)]tribenzaldehyde.

[0012] Furthermore, the molar ratio of the 2,4,6-trimethyl-1,3,5-triazine, the aldehyde compound and the benzoic anhydride is 1:1:4; the temperature range of the polymerization reaction is 150° C. to 200° C., and the reaction time is 72 to 120 hours.

[0013] Furthermore, the crude product is soaked in a mixed solution of methanol and 1M NaOH solution in a volume ratio of 1:1 for 24 hours to remove 2,4,6-trimethyl-1,3,5-triazine, aldehyde compounds and benzoic anhydride that do not participate in the reaction; the soaked product is washed with methanol and tetrahydrofuran solution in turn to remove residual alkaline substances and then dried to obtain a porous framework polymer with carbon-carbon double bonds.

[0014] Preferably, the mass ratio of the β-mercaptoethylamine, the photoinitiator and the porous framework polymer having carbon-carbon double bonds is (5-50): (0.1-1): 1; preferably, the photoinitiator is benzoin dimethyl ether, isopropylthioxanthone or camphorquinone; preferably, the polar organic solvent is tetrahydrofuran, acetone, dichloromethane or chloroform.

[0015] Preferably, the addition reaction temperature is controlled at 20-25° C., and the reaction time is 0.5-12 h. The product obtained by the addition reaction is washed with methanol and tetrahydrofuran solution in sequence and then dried.

[0016] In a second aspect, the present invention provides a polyamine-type porous polymer obtained by the preparation method described in the first aspect.

[0017] In a third aspect, the present invention provides a use of the polyamine-type porous polymer described in the second aspect as a carbon dioxide gas adsorption material.

[0018] Compared with the prior art, the present invention has the following beneficial effects:

[0019] Compared to existing CO2 adsorption materials, this method boasts a high number of open polyamine sites, extremely high reaction utilization, rapid reaction time, and simple post-processing, resulting in excellent CO2 adsorption potential. Compared to other physical modification methods involving impregnation of porous materials with amines, it offers greater recycling potential. Furthermore, this method can modify all covalent organic framework materials with carbon-carbon double bonds, demonstrating a certain degree of universality. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is a comparison chart of the carbon dioxide adsorption-desorption performance of the polyamine-type porous polymer prepared in Example 1 before and after amino group modification, where the circles and triangles are the materials before and after amino group modification, respectively, the solid area represents the carbon dioxide adsorption curve, and the hollow area represents the carbon dioxide desorption curve;

[0021] Figure 2 This is a comparison chart of the carbon dioxide adsorption-desorption performance of the polyamine-type porous polymer prepared in Example 2 before and after amino group modification, where the circles and triangles are the materials before and after amino group modification, respectively, the solid area represents the carbon dioxide adsorption curve, and the hollow area represents the carbon dioxide desorption curve;

[0022] Figure 3 This is a comparison chart of the carbon dioxide adsorption-desorption performance of the polyamine-type porous polymer prepared in Example 3 before and after modification with amino groups, where the circles and triangles represent the materials before and after amino group modification, respectively, the solid area represents the carbon dioxide adsorption curve, and the hollow area represents the carbon dioxide desorption curve. DETAILED DESCRIPTION

[0023] The present invention will be further described and illustrated below in conjunction with the accompanying drawings and specific embodiments. Those skilled in the art can refer to the content of the present invention and optimize the relevant experimental parameters according to the actual experimental environment. It should be noted that the following is only a preferred embodiment of the present invention. For those skilled in the art, without departing from the principles of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be regarded as the scope of protection of the present invention. The synthetic route and method of the present invention have been described in detail through preferred implementation cases. These descriptions are only exemplary descriptions and do not constitute a limitation on the scope of the present invention. It is obvious that those skilled in the relevant art can make appropriate changes and combinations to the methods described in the present invention without departing from the content and scope of the present invention to implement the relevant technology of the present invention. The present invention will be further described and illustrated below in conjunction with the accompanying drawings and specific embodiments. The technical features of each embodiment of the present invention can be combined accordingly without conflicting with each other.

[0024] Example 1

[0025] In this example, 2,4,6-trimethyl-1,3,5-triazine, 1,3,5-benzenetricarboxaldehyde, and benzoic anhydride were used to prepare a porous framework polymer TMT-TFB-COF with carbon-carbon double bonds. Subsequently, an addition reaction was carried out under photoinitiation conditions to modify a large number of amino groups on the framework material to obtain a polyamine-type porous polymer. The preparation method is as follows:

[0026] (1) Preparation of porous framework polymers with carbon-carbon double bonds

[0027] In a 10mL ampoule, 0.020g of 2,4,6-trimethyl-1,3,5-triazine, 0.026g of 1,3,5-benzenetricarboxaldehyde, and 0.15g of benzoic anhydride were added sequentially. The ampoule was sealed and heated in an oven at 180°C for 72 hours for melt polymerization to obtain a crude product. The crude product was then soaked in a mixture of 20mL of methanol and 20mL of 1M NaOH solution for 24 hours to remove organic matter that did not participate in the polymerization reaction. The crude product was then filtered, ground, and washed with methanol and tetrahydrofuran to remove the sodium hydroxide. Finally, it was dried to obtain a porous framework polymer TMT-TFB-COF material with carbon-carbon double bonds.

[0028] The chemical structure of 1,3,5-benzenetricarboxaldehyde is:

[0029] (2) Preparation of polyamine-type porous polymers

[0030] The photoinitiator benzoin dimethyl ether, an excess of β-mercaptoethylamine, and the TMT-TFB-COF material obtained in step (1) are dispersed in a tetrahydrofuran solution and subjected to an addition reaction under ultraviolet irradiation. The mass ratio of β-mercaptoethylamine, benzoin dimethyl ether, and TMT-TFB-COF material is 10:0.1:1.

[0031] The addition reaction was carried out at room temperature (20-25° C.) for 12 hours. The product obtained by the addition reaction was washed with methanol and tetrahydrofuran solution in sequence and then dried to obtain a polyamine-type porous polymer TMT-TFB-COF-NH2.

[0032] The TMT-TFB-COF and TMT-TFB-COF-NH2 prepared in this example were subjected to carbon dioxide adsorption tests at 298K. The results are as follows: Figure 1As shown. Both TMT-TFB-COF and TMT-TFB-COF-NH2 showed carbon dioxide absorption performance, and the desorption curves were very close to the adsorption curves, proving that the adsorption process was reversible in all cases. It is worth noting that after a large number of amino group modifications, TMT-TFB-COF-NH2 showed better CO2 adsorption performance. At 298K, the maximum CO2 adsorption capacity of TMT-TFB-COF-NH2 was 2.8mmol g -1 At 298 K, the maximum CO2 adsorption capacity of TMT-TFB-COF was 1.9 mmol g -1 This means that the carbon dioxide adsorption level of TMT-TFB-COF-NH2 modified with a large number of amino groups is almost 1.5 times that of the unmodified TMT-TFPEB-COF.

[0033] Through the preparation method of the polyamine-type porous polymer provided by the present invention, the polyamine-type porous polymer TMT-TFB-COF-NH2 generated by the reaction of TMT-TFB-COF and β-mercaptoethylamine in this embodiment has a high carbon dioxide adsorption level and has great application potential in carbon dioxide adsorption.

[0034] Example 2

[0035] In this example, 2,4,6-trimethyl-1,3,5-triazine, 1,3,5-tris(4-formylphenyl)benzene, and benzoic anhydride were used to prepare a porous framework polymer TMT-TFPB-COF with carbon-carbon double bonds. Subsequently, an addition reaction was carried out under photoinitiation conditions to modify a large number of amino groups on the framework material to obtain a polyamine-type porous polymer. The preparation method is as follows:

[0036] (1) Preparation of porous framework polymers with carbon-carbon double bonds

[0037] In a 10mL ampoule, 0.020g of 2,4,6-trimethyl-1,3,5-triazine, 0.063g of 1,3,5-tris(4-formylphenyl)benzene, and 0.15g of benzoic anhydride were added sequentially. The ampoule was sealed and heated in an oven at 180°C for 72 hours for melt polymerization to obtain a crude product. The crude product was then soaked in a mixture of 20mL of methanol and 20mL of 1M NaOH solution for 24 hours to remove organic matter that did not participate in the polymerization reaction. The crude product was then filtered, ground, and washed with methanol and tetrahydrofuran to remove the sodium hydroxide. Finally, it was dried to obtain a porous framework polymer TMT-TFPB-COF material with carbon-carbon double bonds.

[0038] The chemical formula of 1,3,5-tris(4-formylphenyl)benzene is:

[0039] (2) Preparation of polyamine-type porous polymers

[0040] The photoinitiator benzoin dimethyl ether, an excess of β-mercaptoethylamine, and the TMT-TFPB-COF material obtained in step (1) are dispersed in a tetrahydrofuran solution and subjected to an addition reaction under ultraviolet irradiation. The mass ratio of β-mercaptoethylamine, benzoin dimethyl ether, and TMT-TFPB-COF material is 10:0.1:1.

[0041] The addition reaction was carried out at room temperature (20-25° C.) for 12 hours. The product obtained by the addition reaction was washed with methanol and tetrahydrofuran solution in sequence and then dried to obtain a polyamine-type porous polymer TMT-TFPB-COF-NH2.

[0042] The TMT-TFPB-COF and TMT-TFPB-COF-NH2 prepared in this example were subjected to carbon dioxide adsorption tests at 298K. The results are as follows: Figure 2 As shown. Both TMT-TFPB-COF and TMT-TFPB-COF-NH2 showed carbon dioxide absorption performance, and the desorption curves were very close to the adsorption curves, proving that the adsorption process was reversible in all cases. It is worth noting that after a large number of amino group modifications, TMT-TFPB-COF-NH2 showed better CO2 adsorption performance. At 298K, the maximum CO2 adsorption capacity of TMT-TFPB-COF-NH2 was 2.2mmol g -1 At 298 K, the maximum CO2 adsorption capacity of TMT-TFPB-COF was 0.9 mmol g -1 This means that the carbon dioxide adsorption level of TMT-TFPB-COF-NH2 modified with a large number of amino groups is almost twice that of the unmodified TMT-TFPB-COF.

[0043] Through the preparation method of the polyamine-type porous polymer provided by the present invention, the polyamine-type porous polymer TMT-TFPB-COF-NH2 generated by the reaction of TMT-TFPB-COF and β-mercaptoethylamine in this embodiment has a high carbon dioxide adsorption level and has great application potential in carbon dioxide adsorption.

[0044] Example 3

[0045] In this example, 2,4,6-trimethyl-1,3,5-triazine, 4,4',4"-[benzene-1,3,5-triyltris(acetylene-2,1-diyl)]tribenzaldehyde and benzoic anhydride were used to prepare a porous framework polymer TMT-TFPEB-COF with carbon-carbon double bonds. Subsequently, an addition reaction was carried out under photoinitiation conditions to modify a large number of amino groups on the framework material to obtain a polyamine-type porous polymer. The preparation method is as follows:

[0046] (1) Preparation of porous framework polymers with carbon-carbon double bonds

[0047] In a 10mL ampoule, 0.020g of 2,4,6-trimethyl-1,3,5-triazine, 0.090g of 4,4',4"-[benzene-1,3,5-triyltris(acetylene-2,1-diyl)]tribenzaldehyde, and 0.15g of benzoic anhydride were mixed in sequence. The ampoule was sealed and heated in an oven at 180°C for 72 hours to allow melt polymerization to obtain a crude product. The crude product was then soaked in a mixture of 20mL of methanol and 20mL of 1M NaOH solution for 24 hours to remove organic matter that did not participate in the polymerization reaction. The product was then filtered, ground, and washed with methanol and tetrahydrofuran to remove the sodium hydroxide. Finally, it was dried to obtain a porous framework polymer TMT-TFPEB-COF material with carbon-carbon double bonds.

[0048] The chemical structure of 4,4',4"-[benzene-1,3,5-triyltris(acetylene-2,1-diyl)]tribenzaldehyde is:

[0049]

[0050] (2) Preparation of polyamine-type porous polymers

[0051] The photoinitiator benzoin dimethyl ether, an excess of β-mercaptoethylamine, and the TMT-TFPEB-COF material obtained in step (1) are dispersed in a tetrahydrofuran solution and subjected to an addition reaction under ultraviolet irradiation. The mass ratio of β-mercaptoethylamine, benzoin dimethyl ether, and TMT-TFPEB-COF material is 10:0.1:1.

[0052] The addition reaction was carried out at room temperature (20-25° C.) for 12 hours. The product obtained by the addition reaction was washed with methanol and tetrahydrofuran solution in sequence and then dried to obtain a polyamine-type porous polymer TMT-TFPEB-COF-NH2.

[0053] The TMT-TFPEB-COF and TMT-TFPEB-COF-NH2 prepared in this example were subjected to carbon dioxide adsorption tests at 298K. The results are as follows: Figure 3As shown. Both TMT-TFPEB-COF and TMT-TFPEB-COF-NH2 showed carbon dioxide absorption performance, and the desorption curves were very close to the adsorption curves, proving that the adsorption process was reversible in all cases. It is worth noting that after a large number of amino group modifications, TMT-TFPEB-COF-NH2 showed better CO2 adsorption performance. At 298K, the maximum CO2 adsorption capacity of TMT-TFPEB-COF-NH2 was 1.4mmol g -1 At 298 K, the maximum CO2 adsorption capacity of TMT-TFPEB-COF is 0.6 mmol g -1 This means that the carbon dioxide adsorption level of TMT-TFPEB-COF-NH2 modified with a large number of amino groups is almost twice that of the unmodified TMT-TFPEB-COF.

[0054] Through the preparation method of the polyamine-type porous polymer provided by the present invention, TMT-TFPEB-COF-NH2 generated by the reaction of TMT-TFPEB-COF and β-mercaptoethylamine in this embodiment has a high carbon dioxide adsorption level and has great application potential in carbon dioxide adsorption.

[0055] The embodiment described above is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Persons skilled in the art may make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, any technical solution obtained by equivalent substitution or equivalent transformation falls within the scope of protection of the present invention.

Claims

1. A method for preparing a polyamine-type porous polymer, characterized in that: β-mercaptoethylamine, a photoinitiator, and a porous framework polymer with carbon-carbon double bonds are dispersed in a polar organic solvent; under ultraviolet light initiation conditions, the photoinitiator excites the β-mercaptoethylamine to generate thiol free radicals, which then undergo an addition reaction with the porous framework polymer with carbon-carbon double bonds; the product after the addition reaction is washed and dried to obtain a polyamine-modified porous polymer.

2. The method for preparing a polyamine-type porous polymer according to claim 1, wherein: The preparation method of the porous framework polymer having carbon-carbon double bonds is as follows: 2,4,6-trimethyl-1,3,5-triazine, an aldehyde compound and benzoic anhydride are mixed and heated to perform a polymerization reaction to obtain a crude product; the crude product is washed to remove unreacted compounds and then dried to obtain a porous framework polymer with carbon-carbon double bonds; the aldehyde compound has two or more aldehyde sites that can react with the 2,4,6-trimethyl-1,3,5-triazine.

3. The method for preparing a polyamine-type porous polymer according to claim 2, wherein: The aldehyde compound adopts one of the following chemical structural formulas:

4. The method for preparing a polyamine-type porous polymer according to claim 3, wherein: The aldehyde compound is 1,3,5-benzenetricarboxaldehyde, 1,3,5-tris(4-formylphenyl)benzene or 4,4',4"-[benzene-1,3,5-triyltris(acetylene-2,1-diyl)]tribenzaldehyde.

5. The method for preparing a polyamine-type porous polymer according to claim 2, wherein: The molar ratio of the 2,4,6-trimethyl-1,3,5-triazine, the aldehyde compound and the benzoic anhydride is 1:1:4; the temperature range of the polymerization reaction is 150° C. to 200° C., and the reaction time is 72 to 120 hours.

6. The method for preparing a polyamine-type porous polymer according to claim 2, wherein: The crude product is soaked in a mixed solution of methanol and 1M NaOH solution in a volume ratio of 1:1 for 24 hours to remove 2,4,6-trimethyl-1,3,5-triazine, aldehyde compounds and benzoic anhydride that have not participated in the reaction; the soaked product is washed with methanol and tetrahydrofuran solution in sequence to remove residual alkaline substances and then dried to obtain a porous framework polymer with carbon-carbon double bonds.

7. The method for preparing a polyamine-type porous polymer according to claim 1, wherein: The mass ratio of the β-mercaptoethylamine, the photoinitiator and the porous framework polymer having carbon-carbon double bonds is (5-50): (0.1-1): 1; preferably, the photoinitiator is benzoin dimethyl ether, isopropylthioxanthone or camphorquinone; preferably, the polar organic solvent is tetrahydrofuran, acetone, dichloromethane or chloroform.

8. The method for preparing a polyamine-type porous polymer according to claim 1, wherein: The addition reaction temperature is controlled at 20-25° C., and the reaction time is 0.5-12 h. The product obtained by the addition reaction is washed with methanol and tetrahydrofuran solution in sequence and then dried.

9. A polyamine-type porous polymer obtained by the preparation method according to any one of claims 1 to 8.

10. Use of the polyamine-type porous polymer according to claim 9 as a carbon dioxide gas adsorbent material.

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