CN114276522B - Eutectic solvent modified acidic hydroxyl conjugated microporous polymer and preparation method thereof - Google Patents
Eutectic solvent modified acidic hydroxyl conjugated microporous polymer and preparation method thereof Download PDFInfo
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Abstract
The invention provides an acid hydroxyl conjugated microporous polymer modified by eutectic solvent and a preparation method thereof, and the preparation method mainly relates to a Sonogashira-Hagihara cross coupling chemistry catalyzed by tetra (triphenylphosphine) palladium and copper iodide and taking N, N-dimethylformamide and 2, 6-diisopropylaniline as reaction solvents. In addition, through modification of the eutectic solvent, a certain amount of nitrogen doping is carried out on the OH-CMP, so that the element types of the OH-CMP material are enriched, and the application of the OH-CMP as other composite materials can be improved. The preparation method has simple process and easily obtained raw materials, and the obtained DESs modified-OH functional group conjugated microporous polymer (DESs-OH-CMP) has high application value in the aspects of adsorption, electrochemistry and the like.
Description
Technical Field
The invention relates to the technical field of preparation of conjugated microporous polymers, in particular to an acid hydroxyl conjugated microporous polymer modified by a eutectic solvent and a preparation method thereof.
Background
Conjugated Microporous Polymers (CMPs) are a unique material. Conjugated microporous polymers have been an important class of microporous materials since the discovery in 2007. CMP is a unique microporous material, and only uses covalent bonds formed by light elements (carbon, hydrogen and the like) to combine pi-pi conjugation with a permanent microporous framework, so that CMPs have potential application prospects in the fields of gas adsorption and separation, chemical adsorption and encapsulation, heterogeneous catalysis, photooxidation reduction catalysis and the like. The broad range of synthetic building blocks and network formation reactions provides a large number of CMP's with different properties and structures. However, as the adsorbent, CMP has a general adsorption effect and adsorption selectivity. In addition, the elements of CMP are relatively single, and CMP materials are more limited in their application.
Disclosure of Invention
The invention aims to provide an acid hydroxyl conjugated microporous polymer modified by a eutectic solvent and a preparation method thereof, which are used for solving the problems that a CMP material is single and less in adsorption and extraction aspects in the prior art.
The technical scheme adopted by the invention is as follows: the eutectic solvent modified acidic hydroxyl conjugated microporous polymer is prepared by uniformly mixing a eutectic solvent and an acidic hydroxyl conjugated microporous polymer, heating at 70-90 ℃ for 6-10 hours, separating a solid-liquid mixture after the reaction is finished, and washing and drying the obtained solid to obtain the eutectic solvent modified acidic hydroxyl conjugated microporous polymer; wherein the eutectic solvent is ethylene glycol and choline chloride, phenol and choline chloride, urea and choline chloride or methylsulfonic acid and choline chloride; the structural formula of the acidic hydroxyl conjugated microporous polymer is shown as follows:
the molar ratio of the eutectic solvent to the acidic hydroxyl conjugated microporous polymer is 10-12:1.
The acidic hydroxyl conjugated microporous polymer is prepared by the following method:
placing 1,3, 5-triacetylene benzene, 2,4, 6-tribromoaniline, tetra (triphenylphosphine) palladium and copper iodide in a reaction vessel, adding N, N-dimethylformamide and 2, 6-diisopropylaniline, introducing circulating argon after air is removed, stirring the mixture for 20-28h under 70-90 ℃ oil bath, separating solid and liquid mixture after the reaction is finished, washing the obtained solid, extracting with methanol by Soxhlet, and drying to obtain the acidic hydroxyl conjugated microporous polymer.
The reaction formula for preparing the acidic hydroxyl conjugated microporous polymer is shown as follows:
the mass ratio of the 1,3, 5-triacetylene benzene to the 2,4, 6-tribromoaniline is 0.4-0.5:1; the mass ratio of the 1,3, 5-triacetylene benzene to the copper iodide is 7-9:1.
The mass ratio of the tetra (triphenylphosphine) palladium to the copper iodide is 5-7:1; the volume ratio of the solvent N, N-dimethylformamide to the 2, 6-diisopropylaniline is 1-2:1.
The preparation method of the acid hydroxyl conjugated microporous polymer modified by the eutectic solvent comprises the steps of uniformly mixing the eutectic solvent and the acid hydroxyl conjugated microporous polymer, heating at 70-90 ℃ for 6-10 hours, separating a solid-liquid mixture after the reaction is finished, and washing and drying the obtained solid to obtain the acid hydroxyl conjugated microporous polymer modified by the eutectic solvent; wherein the eutectic solvent is ethylene glycol and choline chloride, phenol and choline chloride, urea and choline chloride or methylsulfonic acid and choline chloride; the structural formula of the acidic hydroxyl conjugated microporous polymer is shown as follows:
the molar ratio of the eutectic solvent to the acidic hydroxyl conjugated microporous polymer is 10-12:1.
The acidic hydroxyl conjugated microporous polymer is prepared by the following method;
placing 1,3, 5-triacetyl benzene, 2,4, 6-tribromoaniline, tetra (triphenylphosphine) palladium and copper iodide in a reaction vessel, adding N, N-dimethylformamide and 2, 6-diisopropylaniline, introducing circulating argon after air is removed, stirring the mixture for 20-28h under 70-90 ℃ oil bath, separating solid and liquid mixture after the reaction is finished, washing the obtained solid, performing Soxhlet extraction on methanol, and drying to obtain the acidic hydroxyl conjugated microporous polymer; the reaction formula for preparing the acidic hydroxyl conjugated microporous polymer is shown as follows:
the mass ratio of the 1,3, 5-triacetylene benzene to the 2,4, 6-tribromoaniline is 0.4-0.5:1; the mass ratio of the 1,3, 5-triacetylene benzene to the copper iodide is 7-9:1; the mass ratio of the tetra (triphenylphosphine) palladium to the copper iodide is 5-7:1; the volume ratio of the solvent N, N-dimethylformamide to the 2, 6-diisopropylaniline is 1-2:1.
The preparation method mainly relates to a Sonogashira-Hagihara cross-coupling chemistry which takes tetra (triphenylphosphine) palladium and copper iodide as a reaction solvent and takes N, N-Dimethylformamide (DMF) and 2, 6-Diisopropylaniline (DIPA). OH-CMP was synthesized.
In addition, through the modification of the eutectic solvent (Deep Eutectic Solvents), a certain amount of nitrogen doping is carried out on the OH-CMP, so that the element types of the OH-CMP material are enriched, and the application of the OH-CMP as other composite materials, such as the application of electrochemical materials and the like, can be improved.
The preparation method has simple process and easily available raw materials, and the prepared OH-CMP improves the selectivity of the CMP as an adsorbent. And the OH-CMP is multi-element doped by modification of DESs. The obtained DESs modified-OH functional group conjugated microporous polymer (DESs-OH-CMP) has high adsorption, electrochemistry and other application values.
The beneficial effects of the invention are as follows:
1) The invention provides a method for synthesizing a conjugated microporous polymer containing acidic hydroxyl by selecting functional groups from a reaction monomer, which provides a new way for improving the adsorption selectivity of a conjugated microporous polymer material;
2) The acidic hydroxyl conjugated microporous polymer is obtained by modifying with different eutectic solvents, and the characterization data prove that the modification of the eutectic solvents carries out multi-element doping on the acidic hydroxyl conjugated microporous polymer; the element types of the acidic hydroxyl conjugated microporous polymer are increased, and the application value of the acidic hydroxyl conjugated microporous polymer is improved.
Drawings
FIG. 1 is a scanning electron microscope image of OH-CMP of the present invention.
FIG. 2 is an infrared view of OH-CMP of the present invention.
FIG. 3 is a graph showing the adsorption and desorption of OH-CMP according to the present invention.
FIG. 4 is an X-ray diffraction pattern of OH-CMP of the present invention.
FIG. 5 is a thermogravimetric analysis of OH-CMP of the present invention.
FIG. 6 is a scanning electron microscope image of DESs-OH-CMP of the invention.
FIG. 7 is an infrared plot of DESs-OH-CMP of the invention.
FIG. 8 is a graph of the adsorption and desorption profile of DESs-OH-CMP of the present invention.
Detailed Description
The invention will be described in detail with reference to the following specific examples, in which reagents and procedures not mentioned are carried out as usual in the art.
Example 1:
preparation steps of OH-CMP: 1,3, 5-Triacetylenyl (181.60 mg), 2,4, 6-tribromophenol (400.00 mg), tetrakis (triphenylphosphine) palladium (139.73 mg) and copper iodide (23.00 mg) were placed in a 25.00 mL three-neck round bottom flask, 6.00 mL DMF and 6.00 mL DIPA were added, and after removal of air, recycle argon was introduced. The mixture was stirred at 80 ℃ in an oil bath for about 24h, after the reaction, the solid-liquid mixture was suction-filtered, the upper layer solid was taken out, and the mixture was washed with dichloromethane and methanol solvent by filtration for several times, respectively, to remove unreacted monomers and catalyst. Finally, soxhlet extraction with methanol was carried out for 3 days, and the resulting product was dried at 100℃for 24 hours until the weight was constant. The resulting product was characterized and the results are shown in FIGS. 1-5.
DESs-OH-CMP preparation steps: the eutectic solvent based on the alcoholic hydroxyl group consists of glycol and choline chloride in a molar ratio of 1:3, mixing and heating at 80 ℃; DESs (ethylene glycol: choline chloride) to OH-CMP in a molar ratio of 10: heating 8h at 80 ℃, filtering the solid-liquid mixture after the reaction is finished, taking the upper layer of solid, washing the upper layer of solid with purified water for multiple times, and vacuum drying 6 h at 80 ℃ to obtain the DESs (ethylene glycol: choline chloride) -OH-CMP material. Scanning electron microscopy, infrared, BET characterization was then performed. The results are shown in the graphs or curves labeled 1 in FIGS. 6 and 7.
Example 2:
the OH-CMP preparation procedure was the same as in example 1.
The phenolic hydroxyl-based eutectic solvent consists of phenol and choline chloride in a molar ratio of 1:2, mixing and heating at 80 ℃; DESs (phenol: choline chloride) to OH-CMP molar ratio 10:1 heating 8h at 80 ℃, filtering, washing, and vacuum drying 6 h at 80 ℃ to obtain DESs (phenol: choline chloride) -OH-CMP material. Scanning electron microscopy, infrared, BET characterization was then performed. The results are shown in the graphs or curves labeled 2 in fig. 6 and 7.
Example 3:
the OH-CMP preparation procedure was the same as in example 1.
Amide-based eutectic solvents consist of urea and choline chloride in a molar ratio of 1:2, mixing and heating at 80 ℃; DESs (Urea: choline chloride) to OH-CMP molar ratio 10:1 heating 8h at 80 ℃, filtering, washing, and vacuum drying 6 h at 80 ℃ to obtain DESs (urea: choline chloride) -OH-CMP material. Scanning electron microscopy, infrared, BET characterization was then performed. The results are shown in figures 6 and 7 with the reference number 3.
Example 4:
the OH-CMP preparation procedure was the same as in example 1.
The sulfonic group-based eutectic solvent consists of methylsulfonic acid and choline chloride in a molar ratio of 1:2, mixing and heating at 80 ℃; DESs (methylsulfonic acid: choline chloride) to OH-CMP molar ratio 10:1 heating 8h at 80 ℃, filtering, washing, and vacuum drying 6 h at 80 ℃ to obtain DESs (methylsulfonic acid: choline chloride) -OH-CMP material. Scanning electron microscopy, infrared, BET characterization was then performed. The results are shown in figures 6 and 7, numbered 4, or curves.
Example 5:
analysis of DESs modified OH-CMP by BET method was performed as follows: the empty tube was weighed and recorded first, then 0.1 g of OH-CMP and 0.1 g of DESs-OH-CMP, respectively, prepared in example 1, were placed in the tube, and the tube weight after placing the samples was weighed and recorded. And after weighing, sequentially installing the sample tubes. After the sample tube is assembled, vacuum pumping is started. After the vacuum pumping is completed and the heating window appears, changing the pressure in the pretreatment parameters to 10 MPa, setting the furnace temperature, opening a heating switch, and manually lifting the furnace. After heating, a prompt window is automatically popped up, after the temperature of the sample tube is reduced to room temperature for 2 seconds, a liquid nitrogen tank is arranged, a foam pad is covered, the liquid nitrogen tank automatically rises about 5 minutes, and adsorption and desorption curve measurement is started (12-24 hours). After the measurement is finished, a weight window of the input sample is popped up, the liquid nitrogen tank automatically falls down, and the residual liquid nitrogen is poured back. And taking down the OH-CMP and DESs-OH-CMP samples.
The nitrogen adsorption-desorption curve results of fig. 3 and 8 show that the OH-CMP material belongs to the type I and type II isotherm composite composition because the OH-CMP material has a very significant adsorption amount at the low end of P/P0, which is related to the micropore filling of the OH-CMP material, belonging to the activated carbon type material containing narrow slit holes. However, after modification by DESs, DESs-OH-CMP materials belong to gas adsorption generated by non-porous or macroporous materials, because type II isotherms reflect unrestricted single-layer-multi-layer adsorption, which is complete and ends; this portion of the curve is a more gradual curve, indicating a superposition of the monolayer coverage and the onset of multilayer adsorption. When P/p0=1, no plateau has been formed yet, adsorption has not reached saturation, and the thickness of the multi-layered adsorption seems to increase without limitation.
Claims (7)
1. The acid hydroxyl conjugated microporous polymer modified by the eutectic solvent is characterized in that the eutectic solvent and the acid hydroxyl conjugated microporous polymer are uniformly mixed, then the mixture is heated for 6 to 10 hours at the temperature of 70 to 90 ℃, after the reaction is finished, the solid-liquid mixture is separated, and the obtained solid is washed and dried to obtain the acid hydroxyl conjugated microporous polymer modified by the eutectic solvent; wherein the eutectic solvent is ethylene glycol and choline chloride, phenol and choline chloride, urea and choline chloride or methylsulfonic acid and choline chloride;
the acidic hydroxyl conjugated microporous polymer is prepared by the following method:
placing 1,3, 5-triacetylene benzene, 2,4, 6-tribromoaniline, tetra (triphenylphosphine) palladium and copper iodide in a reaction vessel, adding N, N-dimethylformamide and 2, 6-diisopropylaniline, introducing circulating argon after air is removed, stirring the mixture for 20-28h under 70-90 ℃ oil bath, separating solid and liquid mixture after the reaction is finished, washing the obtained solid, extracting with methanol by Soxhlet, and drying to obtain the acidic hydroxyl conjugated microporous polymer.
2. The eutectic solvent modified acidic hydroxyl conjugated microporous polymer of claim 1, wherein the molar ratio of the eutectic solvent to the acidic hydroxyl conjugated microporous polymer is 10-12:1.
3. The eutectic solvent modified acidic hydroxyl conjugated microporous polymer according to claim 1, wherein the mass ratio of 1,3, 5-triacetoxybenzene to 2,4, 6-tribromoaniline used is 0.4-0.5:1; the mass ratio of the 1,3, 5-triacetylene benzene to the copper iodide is 7-9:1.
4. The eutectic solvent modified acidic hydroxyl conjugated microporous polymer of claim 1, wherein the mass ratio of tetrakis (triphenylphosphine) palladium to copper iodide is 5-7:1; the volume ratio of the solvent N, N-dimethylformamide to the 2, 6-diisopropylaniline is 1-2:1.
5. A preparation method of an acid hydroxyl conjugated microporous polymer modified by a eutectic solvent is characterized in that the eutectic solvent and the acid hydroxyl conjugated microporous polymer are uniformly mixed, then the mixture is heated for 6 to 10 hours at the temperature of 70 to 90 ℃, after the reaction is finished, a solid-liquid mixture is separated, and the obtained solid is washed and dried to obtain the acid hydroxyl conjugated microporous polymer modified by the eutectic solvent; wherein the eutectic solvent is ethylene glycol and choline chloride, phenol and choline chloride, urea and choline chloride or methylsulfonic acid and choline chloride;
the acidic hydroxyl conjugated microporous polymer is prepared by the following method:
placing 1,3, 5-triacetylene benzene, 2,4, 6-tribromoaniline, tetra (triphenylphosphine) palladium and copper iodide in a reaction vessel, adding N, N-dimethylformamide and 2, 6-diisopropylaniline, introducing circulating argon after air is removed, stirring the mixture for 20-28h under 70-90 ℃ oil bath, separating solid and liquid mixture after the reaction is finished, washing the obtained solid, extracting with methanol by Soxhlet, and drying to obtain the acidic hydroxyl conjugated microporous polymer.
6. The method of claim 5, wherein the molar ratio of the eutectic solvent to the acidic hydroxyl conjugated microporous polymer is 10-12:1.
7. The process according to claim 5, wherein the mass ratio of 1,3, 5-triacetoxybenzene to 2,4, 6-tribromoaniline is 0.4-0.5:1; the mass ratio of the 1,3, 5-triacetylene benzene to the copper iodide is 7-9:1; the mass ratio of the tetra (triphenylphosphine) palladium to the copper iodide is 5-7:1; the volume ratio of the solvent N, N-dimethylformamide to the 2, 6-diisopropylaniline is 1-2:1.
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| CN103242557A (en) * | 2013-05-03 | 2013-08-14 | 大连理工大学 | Elastic hydrophobic material and synthetic method as well as application thereof |
| CN107312172A (en) * | 2017-07-06 | 2017-11-03 | 中北大学 | A kind of preparation method of micro-nano structure polyaniline material |
| CN108878911A (en) * | 2018-06-19 | 2018-11-23 | 广西师范大学 | A kind of nitrogen-doped carbon nanometer pipe load Pt catalyst and the preparation method and application thereof based on eutectic solvent |
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