Porous polymer and preparation method thereof
By using CuCl and DMF in air for coupling reaction, monomers with terminal alkynyl groups or alkyl silyl alkynyl are prepared, which solves the complex and cost-effective problems of organic porous polymer synthesis method, and achieves low cost and simplicity The process of porous polymer preparation is suitable for industrial production and reduces the impact on the environment.
Patent Information
- Application Number
- CN202411486250.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-23
- Publication Date
- 2024-12-31
AI Technical Summary
The existing organic porous polymer synthesis methods are costly, complex and difficult to achieve industrial production, and the synthesis process has an impact on the environment.
CuCl as the coupling agent and DMF as the solvent, and the coupling reaction uses monomers with terminal alkynyl groups or alkyl silyl alkynyl as raw materials to prepare porous polymers in air, avoiding the use of expensive organic phosphine and metal catalysts. , simplify the process flow.
It realizes low-cost and simple operational porous polymer preparation, is suitable for industrial production, and reduces the impact on the environment.
Smart Images
Figure CN119219897A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the field of polymerization technology, and in particular relates to a porous polymer and a preparation method thereof. Background Art
[0002] Organic porous polymers are widely used in gas storage, separation, water treatment, catalysis and other fields due to their large specific surface area, adjustable pore size and diverse synthesis methods. Traditional polymerization methods include coupling reactions (such as Suzuki cross-coupling reaction, Yamamoto, Sonogashira-Hagihara, Buchwald-Hartwig, Heck coupling reaction), Schiff base reaction, Friedel-Crafts reaction, cyclotrimerization reaction and oxidative polymerization. With the continuous progress in the field of scientific research, the synthesis methods of organic porous polymers have made significant breakthroughs. In addition to traditional synthesis routes, a series of innovative alternative methods such as ion thermal reaction, microwave radiation reaction and electrochemical method have gradually emerged.
[0003] However, organic porous polymers may face challenges in terms of cost, stability, and recyclability in practical applications. How to overcome these challenges, develop simple polymerization methods, and achieve large-scale application of microporous polymers is an urgent problem to be solved. In addition, the chemical reagents and solvents that may be used in the synthesis process will also have a certain impact on the environment. Therefore, its environmental friendliness needs to be fully considered during the research and development process. Summary of the invention
[0004] In view of the shortcomings of the prior art, the technical problem to be solved by the present invention is to overcome the problems of high cost, complex preparation method and difficulty in industrial production in the existing organic porous polymer synthesis method, and to propose a porous polymer with low cost and simple preparation method and its preparation method.
[0005] In order to solve the technical problem, the technical solution adopted by the present invention is:
[0006] The invention provides a method for preparing a porous polymer, comprising: using CuCl as a coupling agent, DMF as a solvent, a monomer with a terminal acetylenic group or a monomer containing an alkylsilylacetylenic group as a raw material, and utilizing a coupling reaction to prepare the porous polymer.
[0007] Preferably, when the monomer 1,3,5-triynylbenzene having a terminal alkynyl group is used as the raw material, the preparation reaction process of the porous polymer is:
[0008]
[0009] Preferably, when 1,3,5-triynylbenzene, a monomer having a terminal alkynyl group, is used as a raw material, the preparation process of the porous polymer comprises:
[0010] In a dry round-bottom bottle, add 0.7-1.1 g of 4-9 mmol 1,3,5-triynylbenzene, 1.6-2.0 g of 16-20 mmol CuCl, and 10-50 mL of dry DMF, heat the mixture to 50-70° C., stir in air for 12-40 h, filter after the reaction is completed, wash, perform Soxhlet extraction with water and ethanol as solvents, and vacuum dry to obtain the porous polymer.
[0011] Preferably, 0.9 g of 6 mmol 1,3,5-triynylbenzene and 1.8 g of 18 mmol CuCl are added to a dry round-bottom flask, 30 mL of dry DMF is added, the mixture is heated to 60 ° C, stirred in air for 36 hours, filtered after the reaction is completed, the obtained solid is dispersed in 40 mL of 3M hydrochloric acid, stirred for 1 hour, filtered, this step is repeated 3 times, the obtained solid is dispersed in a saturated aqueous solution of sodium thiosulfate, stirred for 1 hour, filtered, this step is repeated 3 times, Soxhlet extraction is performed with water and ethanol as solvents for 36 hours, and the polymer is dried in a vacuum drying oven to obtain.
[0012] Preferably, when the monomer 1,4-bis(trimethylsilyl)-1,3-butadiyne containing alkylsilylalkyne is used as the raw material, the preparation reaction process of the porous polymer is:
[0013]
[0014] Preferably, when the monomer 1,4-bis(trimethylsilyl)-1,3-butadiyne containing alkylsilylalkyne is used as the raw material, the preparation process of the porous polymer comprises:
[0015] 0.2-0.5 g of 1-3 mmol 1,4-bis(trimethylsilyl)-1,3-butadiyne, 0.5-0.9 g of 2-6 mmol CuCl and 18-22 mL of dry DMF are added into a dry round-bottom bottle, the mixture is heated to 50-70° C., stirred in air for 12-40 h, filtered after the reaction is completed, the obtained solid is dispersed in a saturated aqueous solution of sodium thiosulfate, stirred, filtered, Soxhlet extracted with water and ethanol as solvents, and vacuum dried to obtain the porous polymer.
[0016] Preferably, 0.39 g of 2 mmol 1,4-bis(trimethylsilyl)-1,3-butadiyne, 0.7 g of 4 mmol CuCl and 20 mL of dry DMF are added to a dry round-bottom flask, the mixture is heated to 60° C., stirred in air for 36 h, filtered after the reaction is completed, and the obtained solid is dispersed in a saturated aqueous solution of sodium thiosulfate, stirred for 1 h, and filtered. This step is repeated 3 times, and Soxhlet extraction is performed with water and ethanol as solvents for 36 h, and dried in a vacuum drying oven to obtain the porous polymer.
[0017] Another aspect of the present invention provides a porous polymer prepared by the method for preparing a porous polymer described in any of the above technical solutions.
[0018] Preferably, when the porous polymer is Polymer 1, the specific surface area of the porous polymer is 406 m 2 / g, and the micropore diameter is 0.8nm.
[0019] Preferably, when the porous polymer is Polymer 2, the specific surface area of the porous polymer is 700 m 2 / g, and the micropore diameter is 0.6nm.
[0020] Compared with the prior art, the present invention has the following beneficial effects:
[0021] The present invention provides a method for preparing a porous polymer, which does not use expensive organic phosphine, nitrogen ligands and metal catalysts, does not require a harsh anhydrous and oxygen-free environment, and successfully prepares an organic porous polymer in the air. The method has the characteristics of simple operation, low cost and being conducive to industrial production. BRIEF DESCRIPTION OF THE DRAWINGS
[0022] Figure 1 is a scanning electron microscope photograph of Polymer 2 of the present invention;
[0023] Figure 2 Polymer 2 and the hydrogen storage performance of Polymer 2 under different lithium doping conditions (10 bar, 77 K). DETAILED DESCRIPTION
[0024] The technical scheme in the specific embodiment of the present invention is described in detail and completely below. Obviously, the described embodiment is only a part of the specific implementation of the overall technical scheme of the present invention, rather than all implementations. Based on the overall concept of the present invention, all other embodiments obtained by ordinary technicians in this field fall within the scope of protection of the present invention.
[0025] The present invention provides a method for preparing a porous polymer, comprising: using CuCl as a coupling agent, DMF as a solvent, using a monomer having a terminal acetylenic group or a monomer containing an alkylsilylacetylenic group as a raw material, and using a coupling reaction to prepare the porous polymer. The preparation method does not use expensive organic phosphine, nitrogen ligands and metal catalysts, does not require a harsh environment without water and oxygen, and successfully prepares an organic porous polymer in the air, and has the characteristics of simple operation, low cost, and being conducive to industrial production.
[0026] In a preferred embodiment, when the monomer 1,3,5-triynylbenzene having a terminal alkynyl group is used as a raw material, the preparation reaction process of the porous polymer is:
[0027]
[0028] In a preferred embodiment, when the monomer 1,3,5-triynylbenzene having a terminal alkynyl group is used as the raw material, the preparation process of the porous polymer includes: adding 0.7-1.1g of 1,3,5-triynylbenzene with a concentration of 4-9mmol, 1.6-2.0g of CuCl with a concentration of 16-20mmol into a dry round-bottom bottle, adding 10-50mL of dry DMF, heating the mixture to 50-70°C, stirring in the air for 12-40h, filtering after the reaction is completed, washing, Soxhlet extraction with water and ethanol as solvents, and vacuum drying to obtain the porous polymer.
[0029] In a preferred embodiment, 0.9 g of 6 mmol 1,3,5-triynylbenzene and 1.8 g of 18 mmol CuCl were added to a dry round-bottom flask, and 30 mL of dry DMF was added. The mixture was heated to 60° C. and stirred in air for 36 h. After the reaction was completed, the mixture was filtered. The obtained solid was dispersed in 40 mL of 3M hydrochloric acid, stirred for 1 h, and filtered. This step was repeated 3 times. The obtained solid was dispersed in a saturated aqueous solution of sodium thiosulfate, stirred for 1 h, and filtered. This step was repeated 3 times. Soxhlet extraction was performed with water and ethanol as solvents for 36 hours, and the polymer was dried in a vacuum oven to obtain a polymer.
[0030] In a preferred embodiment, when the monomer 1,4-bis(trimethylsilyl)-1,3-butadiyne containing alkylsilylalkyne is used as the raw material, the preparation reaction process of the porous polymer is:
[0031]
[0032] In a preferred embodiment, when the monomer 1,4-bis(trimethylsilyl)-1,3-butadiyne containing alkylsilyl alkyne is used as the raw material, the preparation process of the porous polymer includes: adding 0.2-0.5g of 1-3mmol of 1,4-bis(trimethylsilyl)-1,3-butadiyne, 0.5-0.9g of CuCl with a concentration of 2-6mmol and 18-22mL of dry DMF into a dry round-bottom bottle, heating the mixture to 50-70°C, stirring in air for 12-40h, filtering after the reaction is completed, dispersing the obtained solid in a saturated aqueous solution of sodium thiosulfate, stirring, filtering, Soxhlet extraction with water and ethanol as solvents, and vacuum drying to obtain the porous polymer.
[0033] In a preferred embodiment, 0.39 g of 2 mmol 1,4-bis(trimethylsilyl)-1,3-butadiyne, 0.7 g of 4 mmol CuCl and 20 mL of dry DMF are added to a dry round-bottom flask, the mixture is heated to 60° C., stirred in air for 36 h, filtered after the reaction is completed, and the obtained solid is dispersed in a saturated aqueous solution of sodium thiosulfate, stirred for 1 h, and filtered. This step is repeated 3 times, and Soxhlet extraction is performed with water and ethanol as solvents for 36 h, and dried in a vacuum oven to obtain the porous polymer.
[0034] Regarding the above Polymer 1 and Polymer 2, it should be noted that, as in the above synthesis route, Polymer 1 is formed by coupling 1,3,5-triynylbenzene. Because the material is insoluble, its molecular weight and molecular weight distribution cannot be tested. At the same time, the preparation of conjugated microporous polymers under anhydrous and oxygen-free conditions using 1,3,5-triynylbenzene as a functional monomer has been widely reported in the literature (LiA, LuR F, WangY, Wang X, Han KL, Deng WQ. Lithium-Doped Conjugated Microporous Polymers for Reversible Hydrogen Storage, Angew Chem, 2010, 49, 3330-3333.), and the reaction formula is as follows:
[0035]
[0036] The specific surface area of Polymer 1 was measured by a surface area analyzer and was approximately 406 m 2 / g, and the micropore size is 0.8nm. Polymer 2 is formed by coupling with 1,3-butadiynyl, and its molecular weight and molecular weight distribution cannot be tested because the material is insoluble. Figure 1 This is a scanning electron microscope image of Polymer 2. The specific surface area of Polymer 2 measured by the surface area analyzer is about 700m2 / g, and the micropore size is 0.6nm. In view of the porous structure of Polymer 2, its storage capacity for hydrogen was studied; in order to further optimize the hydrogen storage performance of Polymer 2, the hydrogen storage performance of lithium-doped Polymer 2 was studied (such as Figure 2 As shown), under the conditions of 10 bar and 77 K, when the lithium doping amount is 1wt%, the hydrogen storage capacity reaches 1.46wt%, which is 20.6% higher than that of the undoped material.
[0037] Another aspect of the present invention provides a porous polymer prepared by the method for preparing a porous polymer described in any of the above technical solutions.
[0038] In a preferred embodiment, when the porous polymer is Polymer 1, the specific surface area of the porous polymer is 406 m 2 / g, and the micropore diameter is 0.8nm.
[0039] In a preferred embodiment, when the porous polymer is Polymer 2, the specific surface area of the porous polymer is 700 m 2 / g, and the micropore diameter is 0.6nm.
[0040] In order to more clearly and in detail introduce the porous polymer and the preparation method thereof provided by the embodiments of the present invention, they will be described below in conjunction with specific embodiments.
[0041] Example 1
[0042] Synthesis of Polymer 1
[0043] Add 1,3,5-triynylbenzene (0.9 g, 6 mmol), CuCl (1.8 g, 18 mmol) and dry DMF (30 mL) to a dry round-bottom flask, heat the mixture to 60 ° C, and stir in air for 36 hours. After the reaction is completed, filter and disperse the obtained solid in 40 mL of hydrochloric acid (3M), stir for 1 hour, filter, and repeat this step 3 times. Disperse the obtained solid in a saturated aqueous solution of sodium thiosulfate, stir for 1 hour, filter, and repeat this step 3 times. Soxhlet extraction is performed with water and ethanol as solvents for 36 hours, and dried in a vacuum oven to obtain a polymer.
[0044] The performance test of the prepared Polymer 1 showed that the specific surface area was 406 m 2 / g, and the micropore diameter is 0.8nm.
[0045] Example 2
[0046] Synthesis of Polymer 2
[0047] Add 1,4-bis(trimethylsilyl)-1,3-butadiyne (0.39 g, 2 mmol), CuCl (0.7 g, 4 mmol) and dry DMF (20 mL) to a dry round-bottomed bottle, heat the mixture to 60°C, and stir in air for 36 h. After the reaction is complete, filter and disperse the obtained solid in a saturated aqueous solution of sodium thiosulfate, stir for 1 h, and filter. Repeat this step 3 times. Perform Soxhlet extraction with water and ethanol as solvents for 36 h and dry in a vacuum oven.
[0048] The performance test of the prepared Polymer 2 showed that the specific surface area was 700 m 2 / g, and the micropore diameter is 0.6nm.
Claims
1. A method for preparing a porous polymer, characterized in that: include: The porous polymer is prepared by using CuCl as a coupling agent, DMF as a solvent, a monomer having a terminal acetylenic group or a monomer containing an alkylsilylacetylenic group as a raw material, and a coupling reaction.
2. The method for preparing a porous polymer according to claim 1, characterized in that: When the monomer 1,3,5-triynylbenzene having a terminal alkynyl group is used as a raw material, the preparation reaction process of the porous polymer is:
3. The method for preparing a porous polymer according to claim 2, characterized in that: When 1,3,5-triynylbenzene, a monomer having a terminal alkynyl group, is used as a raw material, the preparation process of the porous polymer includes: In a dry round-bottom bottle, add 0.7-1.1 g of 4-9 mmol 1,3,5-triynylbenzene, 1.6-2.0 g of 16-20 mmol CuCl, and 10-50 mL of dry DMF, heat the mixture to 50-70° C., stir in air for 12-40 h, filter after the reaction is completed, wash, perform Soxhlet extraction with water and ethanol as solvents, and vacuum dry to obtain the porous polymer.
4. The method for preparing a porous polymer according to claim 3, characterized in that: In a dry round-bottom flask, add 0.9 g of 6 mmol 1,3,5-triynylbenzene and 1.8 g of 18 mmol CuCl, add 30 mL of dry DMF, heat the mixture to 60 ° C, stir in air for 36 hours, filter after the reaction is completed, disperse the obtained solid in 40 mL of 3M hydrochloric acid, stir for 1 hour, filter, repeat this step 3 times, disperse the obtained solid in a saturated aqueous solution of sodium thiosulfate, stir for 1 hour, filter, repeat this step 3 times, perform Soxhlet extraction with water and ethanol as solvents for 36 hours, and dry in a vacuum oven to obtain a polymer.
5. The method for preparing a porous polymer according to claim 1, characterized in that: When the monomer 1,4-bis(trimethylsilyl)-1,3-butadiyne containing alkylsilyl alkyne is used as the raw material, the preparation reaction process of the porous polymer is as follows:
6. The method for preparing a porous polymer according to claim 5, characterized in that: When the monomer 1,4-bis(trimethylsilyl)-1,3-butadiyne containing alkylsilyl alkyne is used as the raw material, the preparation process of the porous polymer includes: 0.2-0.5 g of 1-3 mmol 1,4-bis(trimethylsilyl)-1,3-butadiyne, 0.5-0.9 g of 2-6 mmol CuCl and 18-22 mL of dry DMF are added into a dry round-bottom bottle, the mixture is heated to 50-70° C., stirred in air for 12-40 h, filtered after the reaction is completed, the obtained solid is dispersed in a saturated aqueous solution of sodium thiosulfate, stirred, filtered, Soxhlet extracted with water and ethanol as solvents, and vacuum dried to obtain the porous polymer.
7. The method for preparing a porous polymer according to claim 6, characterized in that: 0.39 g of 2 mmol 1,4-bis(trimethylsilyl)-1,3-butadiyne, 0.7 g of 4 mmol CuCl and 20 mL of dry DMF were added into a dry round-bottom flask, the mixture was heated to 60°C, stirred in air for 36 h, filtered after the reaction was completed, the obtained solid was dispersed in a saturated aqueous solution of sodium thiosulfate, stirred for 1 h, filtered, this step was repeated 3 times, Soxhlet extraction was performed with water and ethanol as solvents for 36 h, and dried in a vacuum oven to obtain the porous polymer.
8. The porous polymer prepared according to the method for preparing a porous polymer according to any one of claims 1 to 7.
9. The porous polymer according to claim 8, characterized in that When the porous polymer is Polymer 1, the specific surface area of the porous polymer is 406 m 2 / g, and the micropore diameter is 0.8nm.
10. The porous polymer according to claim 8, characterized in that When the porous polymer is Polymer 2, the specific surface area of the porous polymer is 700 m 2 / g, and the micropore diameter is 0.6nm.