Polarity-staggered high-stability fluorine-rich porous super-crosslinked polymer and preparation method thereof

Abstract

The preparation method comprises the following steps: (1) sequentially adding 1-10% of a construction unit I, 5-25% of a catalyst and 60-85% of a dispersion medium into a container, slowly dropwise adding 1-10% of a construction unit II at the temperature of 0 DEG C under the protection of inert gas, and stirring at the temperature of 0 DEG C for 1-2 hours; then carrying out constant-temperature full reaction at room temperature; (2) after the reaction is finished, filtering, and sequentially washing with chloroform, distilled water, methanol, acetone, N, N-dimethylformamide and dimethyl sulfoxide; and (3) carrying out Soxhlet extraction by using tetrahydrofuran, and then carrying out vacuum drying on the product at 70 DEG C. According to the invention, the polarity-staggered high-stability fluorine-rich porous super-crosslinked polymer is prepared by adopting a normal-temperature one-step method, and the material has high BET surface area and pore volume and excellent chemical stability and thermal stability, and has potential application value in the aspects of adsorption, sewage treatment, catalysis, gas separation, gas storage and fluorescence sensing.

Description

Technical Field

[0001] The present invention belongs to the field of preparation of polymer materials, and particularly relates to a fluorine-rich porous hypercrosslinked polymer with polar alternation and high stability and a preparation method thereof. Background Art

[0002] Porous materials have a large specific surface area, a large pore volume, excellent thermal stability, and potential applications in adsorption, heavy metal sewage treatment, dye sewage treatment, industrial catalysis, gas purification, gas, and fluorescence sensing. In recent years, scientists have developed various organic or inorganic porous materials, and some of them have been industrialized.

[0003] Chinese Patent No. 104817461A discloses a method for preparing a dendritic porous polymer film, which is used as a fluorescence probe for detecting TNT gas, Fe 3+ and benzene gas, with high sensitivity, good repeatability, and strong practicability. Chinese Patent No. 104817461A discloses a method for preparing a nitrogen-containing tridentate ligand organic polymer material, which is a good adsorption material and catalyst support material, especially having good prospects in noble metal loading. US Patent No. 2015299380 - A1 discloses a method for preparing a soluble conjugated microporous polymer, the micropore volume of which is greater than 0.1 cm 3 / g, and the Brunauer - Emmett - Teller (BET) surface area is 500 m 2 / g, which has potential applications in catalysis, photocatalysis, supercapacitors, optoelectronic devices, electrode materials, gas separation and storage, etc. US Patent No. 2014066533 - A1 discloses a method for preparing a conjugated microporous macromolecular polymer, which can be doped with metal elements such as cobalt, zinc, copper, aluminum, chromium, etc.

[0004] Porous materials with polar alternation and high stability have excellent properties. The fluorine-containing group makes the material have a relatively high polarity and the alkyl chain group has a low polarity. Introducing the fluorine-containing group and the alkyl chain group into the material in an orderly manner endows the material with a polar alternating arrangement, making it have special properties. At present, there is no report on porous materials with polar alternation and high stability. Summary of the Invention

[0005] The purpose of the present invention is to provide a fluorine-rich porous hypercrosslinked polymer with polar alternation and high stability and a preparation method thereof, and directly synthesize a fluorine-rich porous hypercrosslinked polymer material with polar alternation and high stability by using an organic acid as a catalyst.

[0006] The technical solution adopted by the present invention: A fluorine-rich porous hypercrosslinked polymer with polar alternation and high stability, the structural formula of the product is as follows:

[0007]

[0008] R1 is an alkyl group or an alkoxy group, and R2 is an unsubstituted aromatic ring

[0009] The preparation method of the polar-interleaved highly stable fluorine-rich porous hypercrosslinked polymer provided by the present invention has the following reaction formula and steps:

[0010]

[0011] R1 is an alkyl group or an alkoxy group, and R2 is an unsubstituted aromatic ring

[0012] The method comprises the following steps:

[0013] (1) Add building block 1, catalyst, and dispersion medium into a container in sequence, wherein building block 1 is 1-10%, the catalyst is 5–25%, and the dispersion medium is 60–85%. Under the protection of inert gas, slowly drop 1-10% of building block 2 at 0 °C, and then react at a constant temperature for 72 h at room temperature;

[0014] (2) After the reaction is completed, filter, and wash four times with chloroform, distilled water, methanol, acetone, N,N-dimethylformamide, and dimethyl sulfoxide in sequence;

[0015] (3) Soxhlet extract with tetrahydrofuran for 48 h, and then vacuum dry the product at 70 °C for 24 h.

[0016] The building block 1 is one or any two of 1,3,5-triphenylbenzene, hexaphenylbenzene, tetraphenylmethane, and 1,3,5,7-tetraphenyladamantane.

[0017] The building block 2 is one or any two of 4-(trifluoroacetyl)toluene, 3-(trifluoroacetyl)toluene, 1-(2,4-dimethoxyphenyl)-2,2,2-trifluoroethan-1-one, 1-(4-(tert-butyl)phenyl)-2,2,2-trifluoroethan-1-one, and 4'-methoxy-2,2,2-trifluoroacetone.

[0018] The catalyst is one or two of trifluoromethanesulfonic acid and trifluoroacetic acid.

[0019] The dispersion medium is one or any two of dichloromethane, chloroform, 1,2-dichloroethane, and o-dichlorobenzene.

[0020] The present invention uses a one-step method at room temperature to prepare a polar-interleaved highly stable fluorine-rich porous hypercrosslinked polymer. This material has a high BET surface area and pore volume, excellent chemical stability and thermal stability, and has potential application value in adsorption, sewage treatment, catalysis, gas separation, gas storage, and fluorescence sensing. Description of the Drawings

[0021] Figure 1Energy-dispersive spectroscopy of the porous hypercrosslinked polymer prepared in Example 1 of the present invention.

[0022] Figure 2 Scanning electron microscopy image of the porous hypercrosslinked polymer prepared in Example 2 of the present invention.

[0023] Figure 3 Infrared spectrum of the porous hypercrosslinked polymer prepared in Example 1 of the present invention.

[0024] Figure 4 X-ray diffraction pattern of the porous hypercrosslinked polymer prepared in Example 1 of the present invention.

[0025] Figure 5 Thermogravimetric curve of the porous hypercrosslinked polymer prepared in Example 1 of the present invention.

[0026] Figure 6 Nitrogen adsorption-desorption isotherm at 77K of the porous hypercrosslinked polymer prepared in Example 1 of the present invention. Detailed description of specific embodiments

[0027] The present invention will be described in detail below by way of specific examples, but the protection scope of the present invention is not limited. Unless otherwise specified, the experimental methods used in the embodiments of the present invention are conventional methods, and the experimental equipment, materials, reagents, etc. used can be purchased from chemical companies. The present invention will be further described in combination with specific experimental examples.

[0028] Example 1:

[0029] Under a nitrogen atmosphere, 1,3,5-triphenylbenzene (0.200 g, 0.653 mmol) and 4-(trifluoroacetyl)toluene (0.184 g) were dissolved in 10 ml of dry dichloromethane, and the system was cooled to 0 °C using an ice-water bath. 2.3 mL of trifluoromethanesulfonic acid was slowly added dropwise using a constant-pressure dropping funnel. After the addition was complete, the system was slowly warmed to room temperature, and the reaction was maintained for 72 hours. After the reaction was completed, the reaction system was poured into a mixed solution of ethanol and water, and the solid powder was obtained by suction filtration and washed with saturated sodium bicarbonate solution until neutral. Then, the solid powder was thoroughly washed successively with N,N-dimethylformamide, acetone, dichloromethane, methanol, and tetrahydrofuran. The product was extracted with tetrahydrofuran in a Soxhlet extractor for 24 h and dried under vacuum at 120 °C.

[0030] Example 2:

[0031] Under a nitrogen atmosphere, 1,3,5-triphenylbenzene (0.200 g, 0.653 mmol) and 4'-methoxy-2,2,2-trifluoroacetone (0.200 g) were dissolved in 10 mL of dry dichloromethane. The system was cooled to 0 °C using an ice-water bath. 2.3 mL of trifluoromethanesulfonic acid was slowly added dropwise using a constant-pressure dropping funnel. After the addition was complete, the system was slowly warmed to room temperature, and the reaction was maintained at this temperature for 72 hours. After the reaction was completed, the reaction system was poured into a mixed solution of ethanol and water, and the solid powder was obtained by suction filtration. It was washed with saturated sodium bicarbonate solution until neutral. Then, the solid powder was thoroughly washed successively with N,N-dimethylformamide, acetone, dichloromethane, methanol, and tetrahydrofuran. The product was extracted with tetrahydrofuran in a Soxhlet extractor for 24 h and dried under vacuum at 120 °C.

[0032] Example 3:

[0033] Under a nitrogen atmosphere, hexaphenylbenzene (0.300 g) and 4'-methoxy-2,2,2-trifluoroacetone (0.344 g) were dissolved in 10 mL of dry dichloromethane. The system was cooled to 0 °C using an ice-water bath. 2.3 mL of trifluoromethanesulfonic acid and 1 mL of trifluoroacetic acid were slowly added dropwise using a constant-pressure dropping funnel. After the addition was complete, the system was slowly warmed to room temperature, and the reaction was maintained at this temperature for 72 hours. After the reaction was completed, the reaction system was poured into a mixed solution of ethanol and water, and the solid powder was obtained by suction filtration. It was washed with saturated sodium bicarbonate solution until neutral. Then, the solid powder was thoroughly washed successively with N,N-dimethylformamide, acetone, dichloromethane, methanol, and tetrahydrofuran. The product was extracted with tetrahydrofuran in a Soxhlet extractor for 24 h and dried under vacuum at 120 °C.

[0034] Example 4:

[0035] Under a nitrogen atmosphere, tetraphenylmethane (0.200 g) and 1-(4-(tert-butyl)phenyl)-2,2,2-trifluoroethan-1-one (0.287 g) were dissolved in 10 mL of dry dichloromethane. The system was cooled to 0 °C using an ice-water bath. 2.3 mL of trifluoromethanesulfonic acid was slowly added dropwise using a constant-pressure dropping funnel. After the addition was complete, the system was slowly warmed to room temperature, and the reaction was maintained at this temperature for 72 hours. After the reaction was completed, the reaction system was poured into a mixed solution of ethanol and water, and the solid powder was obtained by suction filtration. It was washed with saturated sodium bicarbonate solution until neutral. Then, the solid powder was thoroughly washed successively with N,N-dimethylformamide, acetone, dichloromethane, methanol, and tetrahydrofuran. The product was extracted with tetrahydrofuran in a Soxhlet extractor for 24 h and dried under vacuum at 120 °C.

[0036] Example 5:

[0037] Under a nitrogen atmosphere, 1,3,5,7-tetraphenyladamantane (0.200 g) and 1-(4-(tert-butyl)phenyl)-2,2,2-trifluoroethan-1-one (0.209 g) were dissolved in 10 mL of dry chloroform. The system was cooled to 0 °C using an ice-water bath. 2.3 mL of trifluoromethanesulfonic acid was slowly added dropwise using a constant-pressure dropping funnel. After the addition was complete, the system was slowly warmed to room temperature and the reaction was maintained at this temperature for 72 hours. After the reaction was completed, the reaction system was poured into a mixed solution of ethanol and water, and the solid powder was obtained by suction filtration and washed with saturated sodium bicarbonate solution until neutral. Then, the solid powder was thoroughly washed successively with N,N-dimethylformamide, acetone, dichloromethane, methanol, and tetrahydrofuran. The product was extracted with tetrahydrofuran in a Soxhlet extractor for 24 h and dried under vacuum at 120 °C.

[0038] Example 6:

[0039] At 0 °C in an ice-water bath and 1 bar, using a gas adsorption instrument, the propane gas adsorption capacity of the solid powder product of Example 1 was measured to be 82 cm 3 / g.

[0040] In summary, the above examples are only preferred examples of the present invention and are not intended to limit the present invention. Any person skilled in the art can make some changes or modifications to equivalent embodiments with equivalent changes within the scope of the technical solution of the present invention by using the disclosed technical content. However, any simple modification made to the above examples based on the technical essence of the present invention without departing from the technical solution of the present invention still falls within the scope of the technical solution of the present invention.

Claims

1. A fluorine-rich porous hypercrosslinked polymer with polar alternation, characterized in that The structural formula of the porous hypercrosslinked polymer is as follows: R1 is an alkyl group or an alkoxy group, and R2 is an unsubstituted aromatic ring.

2. The preparation method of the porous polymer rich in hydroxyl groups and secondary amino groups according to claim 1, characterized in that, The reaction formula and steps are as follows: R1 is an alkyl group or an alkoxy group, and R2 is an unsubstituted aromatic ring (1) Add building block one, catalyst, and dispersion medium into a container in sequence. Among them, building block one accounts for 1-10%, the catalyst accounts for 5–25%, and the dispersion medium accounts for 60–85%. Under the protection of an inert gas, slowly dropwise add 1-10% of building block two at 0 °C, and then react at a constant temperature at room temperature for a sufficient time; (2) After the reaction is completed, filter and wash successively with chloroform, distilled water, methanol, acetone, N,N-dimethylformamide, and dimethyl sulfoxide; (3) Perform Soxhlet extraction with tetrahydrofuran, and then vacuum dry the product at 70 °C.

3. The preparation method of the polarity-interleaved highly stable fluorine-rich porous hypercrosslinked polymer according to claim 2, characterized in that The building block one is one or any two of 1,3,5-triphenylbenzene, hexaphenylbenzene, tetraphenylmethane, and 1,3,5,7-tetraphenyladamantane.

4. The preparation method of the fluorine-rich porous hypercrosslinked polymer with polar interlacing according to claim 2, characterized in that, The building block two is one or any two of 4-(trifluoroacetyl)toluene, 3-(trifluoroacetyl)toluene, 1-(2,4-dimethoxyphenyl)-2,2,2-trifluoroethan-1-one, 1-(4-(tert-butyl)phenyl)-2,2,2-trifluoroethan-1-one, and 4'-methoxy-2,2,2-trifluoroacetone.

5. The preparation method of the fluorine-rich porous hypercrosslinked polymer with polar alternation according to claim 2, characterized in that, The catalyst is one or two of trifluoromethanesulfonic acid and trifluoroacetic acid.

6. The preparation method of the polarity-interleaved highly stable fluorine-rich porous hypercrosslinked polymer according to claim 2, characterized in that, The dispersion medium is one or any two of dichloromethane, chloroform, 1,2-dichloroethane, and o-dichlorobenzene.

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