CN113265040A - Conjugated organic microporous polymer and preparation method and application thereof - Google Patents
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Abstract
The invention belongs to the technical field of organic microporous polymers, and particularly relates to a conjugated organic microporous polymer and a preparation method and application thereof. The invention uses tetrabromo tetraphenyl methane and 4-formyl phenylboronic acid to react to generate tetraphenyl formaldehyde, then the tetraphenyl formaldehyde reacts with phloroglucinol to produce the novel conjugated organic microporous polymer material, the material has an amorphous structure, has good ultraviolet light absorption performance, has a flat spherical surface, and has important scientific value for the field of gas adsorption.
Description
Technical Field
The invention relates to the technical field of organic microporous polymers, in particular to a conjugated organic microporous polymer and a preparation method and application thereof.
Background
The organic microporous polymer is a spherical material with a pore structure. It has a number of advantages, such as: the composite material has the characteristics of large surface area, low skeleton density, high porosity, light weight, good thermal stability and the like, has good repairability, can regulate and control the pore size, is convenient to manufacture, and has wide application in the aspects of medicine, carbon dioxide adsorption, degradation catalysis and the like.
The advent of polyethylene conductive materials has raised the trend toward conjugated polymers, many of which have been synthesized and widely used. One class of polyethylene conductive materials is conjugated polymers having a specific microporous structure, which we refer to as conjugated microporous polymers having a specific microporous structure. Compared with the traditional conjugated polymer, the material has high specific surface area and microporosity, simultaneously has very good thermal stability, is insoluble in any acid, alkali and organic solvent under certain conditions, and has wide attention because the micropore size of the conjugated microporous polymer can be adjusted.
The conjugated organic microporous polymer is composed of a plurality of light elements, has the advantages of low skeleton density, large specific surface area, permanent open pore channel structure, stable physicochemical properties and the like, and can be widely used in the fields of selective separation, adsorption and storage of energy gas, capture of carbon dioxide, organic pollution control and the like. The conjugated organic microporous polymer has numerous synthetic methods and simple synthetic process, can be synthesized by various monomers, and can also achieve the function of adjusting the performance by modifying organic functional groups or changing the lengths of various chains, thereby achieving the purpose of specific synthesis.
Therefore, the research on the novel conjugated organic microporous polymer has important significance.
Disclosure of Invention
The invention aims to provide a conjugated organic microporous polymer and a preparation method and application thereof. The prepared conjugated organic microporous polymer has a novel structure and has important scientific value for the field of gas adsorption.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a conjugated organic microporous polymer, which comprises the following steps:
tetrabromo tetraphenyl methane, potassium carbonate, 4-formyl phenylboronic acid, tetrakis (triphenylphosphine) palladium and dioxane are mixed to carry out Suzuki coupling reaction, so as to obtain tetraphenyl formaldehyde;
and mixing the tetraphenylaldehyde, the phloroglucinol and the 1, 4-dioxane, and carrying out polymerization reaction to obtain the conjugated organic microporous polymer.
Preferably, the using amount ratio of the tetrabromotetraphenyl methane, the potassium carbonate, the 4-formylphenylboronic acid, the tetrakis (triphenylphosphine) palladium and the dioxane is 1.2477g, 2.0724g, 1.2571g, 0.2412g and 20-100 mL.
Preferably, the temperature of the Suzuki coupling reaction is 85 ℃ and the time is 72 hours.
Preferably, the Suzuki coupling reaction is carried out under nitrogen protection.
Preferably, after the Suzuki coupling reaction is completed, the method further comprises: and transferring the obtained reaction material into a mixed solution of concentrated hydrochloric acid and ice water, and then sequentially carrying out reduced pressure suction filtration, column chromatography separation, evaporation and drying to obtain the tetraphenylaldehyde.
Preferably, the dosage ratio of the tetraphenylaldehyde to the phloroglucinol to the 1, 4-dioxane is 0.2002g, 0.1362g and 5-50 mL.
Preferably, the temperature of the polymerization reaction is 220 ℃ and the time is 96 hours.
Preferably, after the polymerization reaction is completed, the method further comprises: and carrying out reduced pressure suction filtration, first immersion cleaning, first suction filtration, second immersion cleaning, second suction filtration and drying on the obtained material in sequence to obtain the conjugated organic microporous polymer.
The invention provides the conjugated organic microporous polymer prepared by the preparation method in the technical scheme.
The invention provides application of the conjugated organic microporous polymer in the technical scheme in the field of gas adsorption.
The invention provides a conjugated organic microporous polymer and a preparation method and application thereof, wherein tetrabromo tetraphenyl methane and 4-formyl phenylboronic acid are reacted to generate tetraphenyl formaldehyde, and then the tetraphenyl formaldehyde and phloroglucinol are reacted to produce a novel conjugated organic microporous polymer material which has an amorphous structure, has good ultraviolet light absorption performance and a flat spherical surface.
Drawings
FIG. 1 is an infrared spectrum of tetraphenylaldehyde prepared in example 1;
FIG. 2 is a nuclear magnetic diagram of tetraphenylaldehyde prepared in example 1;
FIG. 3 is an infrared spectrum of tetraphenylaldehyde and ZC-CMP prepared in example 1;
FIG. 4 is a solid UV spectrum of tetraphenylaldehyde and ZC-CMP prepared in example 1;
FIG. 5 is a thermogravimetric and differential thermal profile of ZC-CMP prepared in example 1;
FIG. 6 is an XRD pattern of ZC-CMP prepared in example 1;
FIG. 7 is a scanning electron micrograph of ZC-CMP prepared in example 1 at different magnifications;
FIG. 8 is a graph of nitrogen adsorption performance of ZC-CMP prepared in example 1.
Detailed Description
The invention provides a preparation method of a conjugated organic microporous polymer, which comprises the following steps:
tetrabromo tetraphenyl methane, potassium carbonate, 4-formyl phenylboronic acid, tetrakis (triphenylphosphine) palladium and dioxane are mixed to carry out Suzuki coupling reaction, so as to obtain tetraphenyl formaldehyde;
and mixing the tetraphenylaldehyde, the phloroglucinol and the 1, 4-dioxane, and carrying out polymerization reaction to obtain the conjugated organic microporous polymer.
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
Tetrabromo tetraphenyl methane, potassium carbonate, 4-formyl phenylboronic acid, tetrakis (triphenylphosphine) palladium and dioxane are mixed to carry out Suzuki coupling reaction, so as to obtain tetraphenyl formaldehyde. The mixing process is not particularly limited in the present invention, and the raw materials can be uniformly mixed by selecting a process known to those skilled in the art.
In the invention, the dosage ratio of the tetrabromotetraphenyl methane, the potassium carbonate, the 4-formylphenylboronic acid, the tetrakis (triphenylphosphine) palladium and the dioxane is preferably 1.2477g, 2.0724g, 1.2571g, 0.2412g, and 20-100 mL; the potassium carbonate is preferably anhydrous potassium carbonate.
In the invention, the temperature of the Suzuki coupling reaction is preferably 80-120 ℃, more preferably 85-110 ℃, and the time is preferably 72 hours; the Suzuki coupling reaction is preferably carried out under the protection of nitrogen; the Suzuki coupling reaction is preferably carried out in a constant temperature oil bath.
In the present invention, after the Suzuki coupling reaction is completed, it preferably further includes: and transferring the obtained reaction material into a mixed solution of concentrated hydrochloric acid and ice water, stirring for 5min, and then sequentially carrying out reduced pressure suction filtration, column chromatography separation, evaporation and drying to obtain the tetraphenylaldehyde. In the invention, in the mixed liquid of concentrated hydrochloric acid and ice water, the mass concentration of the concentrated hydrochloric acid is preferably 3-10%; the invention neutralizes K in the reaction system by adding hydrochloric acid2CO3The Suzuki reaction was stopped. The suction filtration under reduced pressure is preferably carried out via a Buchner funnel. In the present invention, the reagent used for the column chromatography separation is preferably dichloromethane; the evaporation is preferably carried out by means of a rotary evaporator; the drying process is not particularly limited in the present invention, and a process known in the art may be selected.
In the present invention, the process of the Suzuki coupling reaction is as follows:
after the tetraphenylaldehyde is obtained, the tetraphenylaldehyde, the phloroglucinol and the 1, 4-dioxane are mixed and subjected to polymerization reaction to obtain the conjugated organic microporous polymer. In the invention, the dosage ratio of the tetraphenylaldehyde to the phloroglucinol to the 1, 4-dioxane is preferably 0.2002g, 0.1362g and 5-50 mL. The present invention preferably performs the mixing by ultrasonic treatment, so as to achieve uniform mixing, and the process of the ultrasonic treatment is not particularly limited, and may be a process well known in the art.
In the present invention, the polymerization reaction is preferably carried out at a temperature of 220 ℃ for a period of 96 hours. The polymerization reaction is preferably carried out in a reaction kettle with a polytetrafluoroethylene lining, nitrogen is preferably introduced into the polytetrafluoroethylene lining for 5min, then the reaction kettle is sealed, and then the reaction kettle is placed in a constant-temperature oven for polymerization reaction.
After the polymerization reaction is completed, it preferably further comprises: and carrying out reduced pressure suction filtration, first immersion cleaning, first suction filtration, second immersion cleaning, second suction filtration and drying on the obtained material in sequence to obtain the conjugated organic microporous polymer. Preferably, the vacuum filtration is carried out by adopting a Buchner funnel, then the obtained solid is subjected to first immersion cleaning for 24 hours by using acetone, the obtained solution is subjected to first suction filtration, then the obtained solid is subjected to second immersion cleaning for 24 hours by using dichloromethane, the obtained solution is subjected to second suction filtration, and the obtained solid is dried (vacuum dried) to obtain the conjugated organic microporous polymer which is marked as ZC-CMP. The vacuum drying process is not particularly limited in the present invention, and may be a process known to those skilled in the art.
In the present invention, the synthesis mechanism of the polymerization reaction is as follows:
the invention provides the conjugated organic microporous polymer prepared by the preparation method in the technical scheme. The conjugated organic microporous polymer is of an amorphous structure, has good ultraviolet light absorption performance, and has a flat spherical surface.
The invention provides application of the conjugated organic microporous polymer in the technical scheme in the field of gas adsorption. The method for applying the conjugated organic microporous polymer to the field of gas adsorption is not particularly limited, and a method well known to those skilled in the art can be selected.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
1) Preparation of tetraphenylaldehyde:
weighing 1.2477g of tetrabromobenzene methane, 2.0724g of anhydrous potassium carbonate, 1.2571g of 4-formylphenylboronic acid and 0.2412g of palladium, weighing 100mL of dioxane, adding the raw materials into a 250mL three-neck flask, vacuumizing the three-neck flask, protecting with nitrogen, heating the flask to 85 ℃ by using a constant-temperature oil bath kettle, carrying out Suzuki coupling reaction for 72h, pouring the obtained dark yellow green solution into a mixed solution of concentrated hydrochloric acid and ice water (the concentration of hydrochloric acid in the mixed solution is 10 percent), stirring for 5min, carrying out suction filtration under reduced pressure by using a Buchner funnel, dissolving the obtained yellow green solid into dichloromethane, carrying out column chromatography, evaporating the obtained light yellow solution by using a rotary evaporator, putting the obtained solid into an oven, and drying to obtain 0.4678g of light yellow powder, which is marked as X.
2) Preparation of conjugated organic microporous polymer:
mixing 0.2002g of tetraphenylmethylaldehyde, 0.1362g of phloroglucinol and 16mL of 1, 4-dioxane in a reaction kettle with a polytetrafluoroethylene lining, introducing nitrogen into the polytetrafluoroethylene lining for 5min, sealing the reaction kettle, placing the reaction kettle in a constant-temperature oven at 220 ℃ for reaction for 96h, performing reduced pressure suction filtration by using a Buchner funnel, performing immersion washing on the obtained solid for 24h by using acetone, performing suction filtration on the obtained solution, performing immersion washing on the solid obtained by suction filtration for 24h by using dichloromethane, performing suction filtration again, and drying the obtained solid by a vacuum drying method to obtain the conjugated organic microporous polymer, which is marked as ZC-CMP.
Performance testing and characterization
1) Infrared spectroscopy was performed on compound X prepared in example 1, and the results are shown in FIG. 1.
As can be seen from the figure, 3068.24cm-1The peak at (A) is a characteristic peak of-C-H on the benzene ring, 1490.97cm-1And 1401.72cm-1The peak at (a) indicates that the skeleton-C ═ C of the benzene ring, and thus indicates the presence of the benzene ring. 1772.58cm-1And 1716.64cm-1Is the peak of aldehyde group, 580cm in the figure-1No large peak appears at the left and right, which indicates that the bromine radical is completely absent and the reaction is complete. Taken together, the compound can be demonstrated to be tetraphenylaldehyde.
2) Nuclear magnetic characterization was performed on compound X prepared in example 1, and the results are shown in fig. 2.
As a result of analysis from the figure, peaks were observed in the vicinity of 0ppm, 1.6ppm, 5.2ppm, 7.1ppm and 10ppm, proton peaks on the benzene ring were 7.04ppm and 7.09ppm, proton peaks on the aldehyde group were 7.87ppm, proton peaks on formaldehyde were 10.05ppm, and other peaks were impurity peaks and solvent peaks. Therefore, the product is the tetraphenylaldehyde.
3) Infrared spectroscopy was performed on ZC-CMP prepared in example 1 and compared with the infrared spectrum of tetraphenylaldehyde, the results are shown in FIG. 3, in which the upper side represents tetraphenylaldehyde and the lower side represents ZC-CMP.
As judged by the graph analysis, the height was 3278.98cm-1Is a-C-H characteristic peak on a benzene ring, 1614.41cm-1And 1487.11cm-1The peak at (a) demonstrates a backbone of a benzene ring-C ═ C, indicating the presence of a benzene ring; 1720cm-1The peak at the aldehyde group had completely disappeared. In addition, according to 3682.57cm-1The existence of hydroxyl can be judged by the absorption peak. Therefore, the product can be judged to be ZC-CMP.
4) Solid UV tests were performed on the tetraphenylaldehyde and ZC-CMP prepared in example 1, and the results are shown in FIG. 4.
Comparing ZC-CMP with tetraphenylaldehyde, the absorbance of the tetraphenylaldehyde is rapidly reduced at 360nm, ZC-CMP is unchanged, ZC-CMP begins to slowly reduce to 500nm, the product on the surface has better ultraviolet absorption performance, and the absorption wavelength of ZC-CMP is 360-500 nm.
5) The results of thermogravimetric testing of ZC-CMP prepared in example 1 are shown in FIG. 5, where the thermogravimetric curve describes the change in sample mass with increasing temperature; the differential thermal profile describes the heat absorption and release conditions that accompany the change in mass of the sample.
From the figure, it can be calculated that the final weight loss rate of ZC-CMP is 59.8%, the mass of the product gradually decreases with increasing temperature. The weight loss speed is relatively slow between 100 ℃ and 200 ℃, which indicates that the product contains a certain amount of moisture, the moisture is slowly removed along with the temperature rise, and the mass reduction speed is slow, which indicates that the substance is relatively stable in the temperature range. With the further increase of the temperature, the mass reduction speed is increased between 200 and 300 ℃, which shows that the product has structural collapse and the mass is rapidly reduced.
6) XRD diffraction test was performed on ZC-CMP prepared in example 1, and the results are shown in FIG. 6.
The crystal structure of the product can be observed through XRD diffraction, the peak shape of the crystal structure is not sharp and narrow or is obviously outstanding, and the compound is seen to be an amorphous structure.
7) The results of the scanning electron microscope test on ZC-CMP prepared in example 1 are shown in FIG. 7.
Wherein, the left figure is a 10 μm topography, the right figure is a 5 μm topography, the left figure shows that the product presents a certain coral shape, and the right figure shows that the surface of the product is a relatively smooth flat sphere shape.
8) The nitrogen adsorption test was performed on the ZC-CMP prepared in example 1, and the results are shown in FIG. 8.
Wherein, the left side is a nitrogen adsorption-desorption isotherm, and the right side is a pore size distribution diagram, and the left graph shows that the curve shows a gradual rising trend and the desorption curve has a hysteresis phenomenon, which indicates that the material has a mesoporous structure. The reason for the presence of mesoporous structures is due to the loosely stacked nanofiber structure of the polymer and its swelling effect at low temperatures. The specific surface area of ZC-CMP calculated according to the BET theory is 621m2·g-1Total volume of 0.34cm3·g-1. The pore size distribution of the material was calculated to be 2.87nm according to the non-density functional theory (NLDFT). The above data indicate that ZC-CMP has some adsorption to nitrogen.
The embodiments show that the invention provides a conjugated organic microporous polymer, a preparation method and an application thereof, wherein tetrabromo tetraphenyl methane and 4-formyl phenylboronic acid react to generate tetraphenyl formaldehyde, and then the tetraphenyl formaldehyde reacts with phloroglucinol to produce a novel conjugated organic microporous polymer material which has an amorphous structure, has good ultraviolet light absorption performance, and has a flat spherical surface.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A method for preparing a conjugated organic microporous polymer, comprising the steps of:
tetrabromo tetraphenyl methane, potassium carbonate, 4-formyl phenylboronic acid, tetrakis (triphenylphosphine) palladium and dioxane are mixed to carry out Suzuki coupling reaction, so as to obtain tetraphenyl formaldehyde;
and mixing the tetraphenylaldehyde, the phloroglucinol and the 1, 4-dioxane, and carrying out polymerization reaction to obtain the conjugated organic microporous polymer.
2. The preparation method of claim 1, wherein the using amount ratio of tetrabromotetraphenyl methane, potassium carbonate, 4-formylphenylboronic acid, tetrakis (triphenylphosphine) palladium and dioxane is 1.2477g, 2.0724g, 1.2571g, 0.2412g, and 20-100 mL.
3. The method of claim 1, wherein the temperature of the Suzuki coupling reaction is 85 ℃ and the time is 72 hours.
4. The method of claim 1, wherein the Suzuki coupling reaction is performed under nitrogen protection.
5. The method of claim 3 or 4, further comprising, after the Suzuki coupling reaction is completed: and transferring the obtained reaction material into a mixed solution of concentrated hydrochloric acid and ice water, and then sequentially carrying out reduced pressure suction filtration, column chromatography separation, evaporation and drying to obtain the tetraphenylaldehyde.
6. The preparation method of claim 1, wherein the amount ratio of the tetraphenylaldehyde to the phloroglucinol to the 1, 4-dioxane is 0.2002 g/0.1362 g/5-50 mL.
7. The method according to claim 1, wherein the polymerization reaction is carried out at a temperature of 220 ℃ for a period of 96 hours.
8. The method according to claim 6 or 7, further comprising, after completion of the polymerization reaction: and carrying out reduced pressure suction filtration, first immersion cleaning, first suction filtration, second immersion cleaning, second suction filtration and drying on the obtained material in sequence to obtain the conjugated organic microporous polymer.
9. The conjugated microporous organic polymer prepared by the method of any one of claims 1 to 8.
10. Use of the conjugated organic microporous polymer according to claim 9 in the field of gas adsorption.
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| CN113603845A (en) * | 2021-08-27 | 2021-11-05 | 台州学院 | Hydroxyl-containing porous covalent organic framework material and preparation method and application thereof |
| CN113603845B (en) * | 2021-08-27 | 2023-07-21 | 台州学院 | Hydroxyl-containing porous covalent organic framework material and preparation method and application thereof |
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