CN114789045B - Organic porous material for separating and purifying electron special gas and preparation method thereof - Google Patents
Organic porous material for separating and purifying electron special gas and preparation method thereof Download PDFInfo
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- 239000011148 porous material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 43
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 20
- 239000011737 fluorine Substances 0.000 claims abstract description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 5
- 239000013354 porous framework Substances 0.000 claims abstract description 5
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 3
- 238000005695 dehalogenation reaction Methods 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 34
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- 238000000944 Soxhlet extraction Methods 0.000 claims description 16
- 239000012065 filter cake Substances 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- SDXUIOOHCIQXRP-UHFFFAOYSA-N 1,2,4,5-tetrafluorobenzene Chemical compound FC1=CC(F)=C(F)C=C1F SDXUIOOHCIQXRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000000967 suction filtration Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000000746 purification Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 7
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical group [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- -1 tri-tert-butylphosphine tetrafluoroborate Chemical group 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 2
- 230000002209 hydrophobic effect Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000011259 mixed solution Substances 0.000 description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000000843 powder Substances 0.000 description 7
- 238000011010 flushing procedure Methods 0.000 description 6
- 229910018503 SF6 Inorganic materials 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000013308 plastic optical fiber Substances 0.000 description 5
- 239000013309 porous organic framework Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 5
- 229960000909 sulfur hexafluoride Drugs 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- QKCGXXHCELUCKW-UHFFFAOYSA-N n-[4-[4-(dinaphthalen-2-ylamino)phenyl]phenyl]-n-naphthalen-2-ylnaphthalen-2-amine Chemical compound C1=CC=CC2=CC(N(C=3C=CC(=CC=3)C=3C=CC(=CC=3)N(C=3C=C4C=CC=CC4=CC=3)C=3C=C4C=CC=CC4=CC=3)C3=CC4=CC=CC=C4C=C3)=CC=C21 QKCGXXHCELUCKW-UHFFFAOYSA-N 0.000 description 3
- 238000001020 plasma etching Methods 0.000 description 3
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005441 electronic device fabrication Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28071—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
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- Engineering & Computer Science (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an organic porous material for electronic special gas adsorption separation and a preparation method thereof, and a fluorine-containing organic porous framework material product connected by carbon-carbon bonds is obtained according to an arene dehalogenation reaction principle. The material prepared by the invention has the characteristics of organic nano-pore structure and strong hydrophobic property, and has obvious adsorption effect on electron gas.
Description
Technical Field
The invention belongs to the field of preparation of organic porous framework materials, and particularly relates to an organic porous material for separation and purification of electron specific gas and a preparation method thereof.
Background
Global semiconductor market sales in 2020 will reach 4400 billions of dollars, 6.8% increase over 2019, and 2021 is expected to achieve a 10.9% two digit increase. Fluorinated electron specialty gases (F-gas) are critical to current semiconductor manufacturing because they have unique chemical reactivity in terms of plasma etching and cleaning, and other alternatives are not duplicated at present. For example NF 3 、CF 4 And SF (sulfur hexafluoride) 6 Wafer plasma etching and chemical vapor deposition chamber plasma cleaning are widely used in integrated circuit, solar cell and electronic device fabrication. Currently, in the electronic gas market, fluorine-containing electronic special gas accounts for about 30% of the total gas consumption in the semiconductor industry. Due to its strong Global Warming Potential (GWP)And very long atmospheric lifetimes, most countries have strict controls on the use of fluorine-containing gases and environmental emissions. 1997, kyoto protocol CF 4 And SF (sulfur hexafluoride) 6 The fluorine-containing gas is greenhouse gas, the temperature rising range of the fluorine-containing gas is about 2000 times of that of carbon dioxide, and the fluorine-containing gas stays in the atmosphere for up to 3000 years. NF (NF) 3 Greenhouse gases are also listed by the united nations environment university in 2008 and can remain in the atmosphere for 550 years. The european meeting passed a legal draft requiring the use of fluorinated gases to be phased out in the european union, aiming at reducing their use in the european union by 80% by 2030. Currently, the use and cleaning of these fluorine-containing gases in plasma etching is generally performed with low conversion efficiency, which results in the exhaust gas containing a concentration of fluorine-containing gas. NF produced in 2018 was reported 3 There is 10% emissions to the atmosphere, and as the semiconductor industry expands, emissions are expected to increase further in recent years. Thermal plasma combustion decomposition is now used to destroy these fluorine-containing gases, which is a high energy consumption and environmental cost due to their excellent chemical stability. In addition, new fluorine-containing pollutants are generated after combustion, so that the treatment cost is further increased, and the green development of the semiconductor industry is not facilitated.
Recovery and recycle techniques provide near zero F-gas emissions during separation and purification. Adsorption separation based on nanoporous adsorbents is a promising candidate for recovery and purification of fluorine gas in waste streams due to its high energy utilization efficiency and operational feasibility. Suitable adsorbents play a critical role in the overall performance of the adsorptive separation process. Organic porous materials have received increasing attention in recent years in the field of gas separation as a novel class of porous materials.
Disclosure of Invention
The invention aims to provide an organic porous material for separating and purifying electron special gas and a preparation method thereof, so as to overcome the defects of the existing adsorbent technology.
In order to achieve the above purpose, the invention adopts the following technical scheme:
an organic porous material for separating and purifying electron special gas has a structural formula shown in formula (I):
according to the principle of dehalogenation reaction of aromatic hydrocarbon, bromoaromatic hydrocarbon and fluorine substituted aromatic hydrocarbon with active hydrogen atoms are subjected to condensation reaction under the weak alkaline condition to finally obtain a three-dimensional fluorine-containing organic porous framework material product with carbon-carbon bonds connected between reaction monomers;
the method specifically comprises the following steps:
step one: weighing tetrabromo-tetraphenyl methane and 1,2,4, 5-tetrafluorobenzene, mixing, adding a catalyst, a cocatalyst and a solvent, oscillating and uniformly mixing the materials to form a mixture, and then sealing under the condition of vacuumizing for heating reaction;
step two: cooling to room temperature after the reaction is finished, carrying out suction filtration on a product after the reaction, adopting DMF and methanol to wash in the suction filtration process to obtain a filter cake, putting the filter cake into DMF, stirring uniformly, carrying out suction filtration again, then carrying out Soxhlet extraction on the obtained product by using ethanol to further remove impurities, and carrying out vacuum drying on a solid obtained by Soxhlet extraction to obtain the organic porous material for electronic special gas separation and purification.
Further, the ratio of tetrabromotetraphenyl methane, 1,2,4, 5-tetrafluorobenzene, catalyst, cocatalyst and solvent in step one was 1mol:2mol:0.1mol:0.2mol:6L.
Further, the temperature of the heating reaction in the first step is 120-150 ℃ and the time is 48 hours.
Further, the solvent is a mixture of one or more of N, N-dimethylacetamide, N-dimethylformamide and azomethylpyrrolidone.
Further, the catalyst is palladium acetate, and the concentration of the catalyst in the mixture is 0.15mol/L.
Further, the cocatalyst was tri-tert-butylphosphine tetrafluoroborate, and the concentration of the cocatalyst in the mixture was 0.3mol/L.
Further, in the second step, the soxhlet extraction time of the obtained product is 24 hours by using ethanol.
Further, the temperature of vacuum drying in the second step is 100-150 ℃ and the time is 12 hours.
Compared with the prior art, the invention has the following beneficial technical effects:
the fluorine-containing organic porous framework material has a high specific surface area and a hydrophobic framework structure, and can regulate pores and has good chemical stability. Firstly, the high pore volume and the internally communicated pore structure thereof minimize the diffusion resistance of adsorbate; secondly, the high bond energy covalent bond enables the tolerance of F-POFs to high temperature, acid and alkali chemical environments and the like to be far higher than MOFs, which lays a good foundation for the repeated recycling of the F-POFs adsorbent in the severe environment; in addition, the fluorine-containing groups in the conjugated organic porous material skeleton endow the conjugated organic porous material skeleton with strong hydrophobicity, so that the adsorption and diffusion of water molecules can be inhibited, adsorption sites in the adsorbent are protected from being occupied by water, and the high-efficiency adsorption separation of electron special gases can be realized.
The F-POF material prepared by the invention has the pore size distribution of about 0.5nm, belongs to a super-microporous structure, has basically consistent pore size and BET specific surface area of 1074m 2 And the F-POF material obtained by the invention has good adsorption capacity on fluorine-containing electron special gas.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is a powder diffraction (PXRD) pattern of the F-POF-1 material prepared in example 1;
FIG. 2 shows the F-POF-1 material obtained in example 1N of (2) 2 Adsorption-desorption drawing;
FIG. 3 is a scanning electron microscope image of the F-POF-1 material prepared in example 1;
FIG. 4 is a graph showing pore size distribution of the F-POF-1 material prepared in example 1;
FIG. 5 is a powder diffraction (PXRD) pattern of the F-POF-2 material prepared in example 2;
FIG. 6 is a diagram showing N of the F-POF-2 material prepared in example 2 2 Adsorption-desorption drawing;
FIG. 7 is a scanning electron microscope image of the F-POF-2 material prepared in example 2;
FIG. 8 is a graph showing the pore size distribution of the F-POF-2 material prepared in example 2.
Detailed Description
The present invention will be described in further detail below:
the invention provides an organic porous material for separating and purifying electron special gas, which has a structural formula shown in formula (I):
the invention also provides a preparation method of the organic porous material for separating and purifying the electron special gas, wherein the reaction formula is as follows:
the method comprises the following steps:
step one: in a 10L reaction kettle, 1mol of tetrabromo-tetraphenyl methane and 2mol of 1,2,4,5 tetrafluorobenzene are weighed and added, then 0.1mol of catalyst, 0.2mol of cocatalyst and 6L of solvent are added, the materials are uniformly mixed in an oscillating way, after nitrogen protection is finished, the temperature is set to 120-150 ℃, and the heating is carried out for 48 hours.
Step two: after the reaction is completed, the reaction product is cooled to room temperature, and the reaction product is poured into a material barrel, and residues in the kettle can be washed by methanol. The resulting mixture was suction-filtered, and washed three times with DMF and methanol as washing solvents, respectively, to obtain a cake. The filter cake was placed in a beaker containing a DMF solution, stirred for 1h with a magnetic stirrer, and then suction filtered. And carrying out Soxhlet extraction on the obtained product for 24 hours by using an ethanol reagent to further remove impurities, and vacuum drying the solid subjected to Soxhlet extraction at 100-150 ℃ for 12 hours to obtain black powder, namely the organic porous material F-POF with the electron specific gas adsorption performance.
According to the invention, tetrabromo-tetraphenyl methane and 1,2,4,5 tetrafluorobenzene are firstly added into a reaction vessel, then a solvent, a catalyst and a cocatalyst are added into the reaction vessel, and the mixture is reacted for 48 hours at 100-150 ℃ to obtain a mixed solution; the molar ratio of tetrabromo-tetraphenyl methane to 1,2,4,5 tetrafluorobenzene is preferably 1:2.
The volume mole ratio of the reaction solvent to the tetrabromo-tetraphenyl methane serving as the reaction raw material is as follows: v (V) Reaction solvent ：n Tetrabromotetraphenyl methane =6l:1 mol, the reaction solvent is preferably a mixture of one or more of N, N-dimethylacetamide, N-dimethylformamide, and azamethylpyrrolidone.
The catalyst is palladium acetate (the concentration is 0.15 mol/L), and the promoter is tri-tert-butylphosphine tetrafluoroborate (the concentration is 0.3 mol/L).
The present invention will be described in detail with reference to examples. It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other.
The following detailed description is of embodiments, and is intended to provide further details of the invention. Unless defined otherwise, all technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments in accordance with the invention.
Example 1
Step one: weighing 1mol of tetrabromotetraphenyl methane and 2mol of 1,2,4,5 tetrafluorobenzene in a 10L reaction kettle, adding 0.1mol of palladium acetate, 0.2mol of tri-tert-butylphosphine tetrafluoroborate and 6LDMF, oscillating and uniformly mixing materials, introducing nitrogen for protection, setting the temperature to 120 ℃ and heating for 48 hours to obtain a mixed solution;
step two: and (3) cooling the mixed solution obtained in the step (A) to room temperature, pouring the mixed solution into a material barrel, carrying out suction filtration on the obtained mixture, and washing three times by using DMF and methanol as washing solvents to obtain a filter cake. The filter cake was placed in a beaker containing a DMF solution, stirred for 1h with a magnetic stirrer, and then suction filtered. And carrying out Soxhlet extraction on the obtained product for 24 hours by using an ethanol reagent to further remove impurities, and carrying out vacuum drying on the solid subjected to Soxhlet extraction at 150 ℃ for 12 hours to obtain black powder F-POF-1.
FIG. 1 is a scanning electron microscope image of the F-POF-1 material prepared in example 1; from the figure it can be seen that the material is composed of amorphous particles.
FIG. 2 is an elemental analysis energy spectrum diagram of the F-POF-1 material prepared in example 1; as can be seen from fig. 2, the material is mainly composed of C, F, br element.
FIG. 3 is a drawing showing nitrogen adsorption stripping of the F-POF-1 material prepared in example 1; from fig. 3, it can be calculated that the specific surface area (BET) of the material is 1071.9 square meters per gram.
FIG. 4 is a graph showing pore size distribution of the F-POF-1 material prepared in example 1; the average pore diameter was found to be 0.5nm.
Example 2
Step one: weighing 1mol of tetrabromotetraphenyl methane and 2mol of 1,2,4,5 tetrafluorobenzene in a 10L reaction kettle, adding 0.1mol of palladium acetate, 0.2mol of tri-tert-butylphosphine tetrafluoroborate and 6L of nitrogen methyl pyrrolidone, oscillating and uniformly mixing the materials, introducing nitrogen to protect, setting the temperature to 150 ℃ after the completion of nitrogen protection, and heating for 48 hours to obtain a mixed solution;
step two: and (3) cooling the mixed solution obtained in the step (A) to room temperature, pouring the mixed solution into a material barrel, carrying out suction filtration on the obtained mixture, and flushing the mixture for three times by using ethanol and methanol as flushing solvents to obtain a filter cake. The filter cake was placed in a beaker containing a DMF solution, stirred for 1h with a magnetic stirrer, and then suction filtered. And carrying out Soxhlet extraction on the obtained product for 24 hours by using an ethanol reagent to further remove impurities, and carrying out vacuum drying on the solid subjected to Soxhlet extraction at 100 ℃ for 12 hours to obtain brown powder F-POF-2.
FIG. 5 is a scanning electron microscope image of the F-POF-2 material prepared in example 2; from the figure it can be seen that the material is composed of amorphous particles.
FIG. 6 is an elemental analysis energy spectrum diagram of the F-POF-2 material prepared in example 2; as can be seen from fig. 6, the material is mainly composed of C, F, br element.
FIG. 7 is a drawing showing nitrogen adsorption stripping of the F-POF-2 material prepared in example 2; from FIG. 7, it can be calculated that the specific surface area (BET) of the material is 818.3 square meters per gram
FIG. 8 is a graph showing pore size distribution of F-POF-2 material prepared in example 2; the average pore diameter was found to be 0.51nm.
Table 1 shows the adsorption amounts of sulfur hexafluoride, carbon tetrafluoride and nitrogen trifluoride in mmol/g by the organic porous materials F-POF-1 and F-POF-2 prepared in examples 1 and 2.
TABLE 1 adsorption amount of F-POF-1 and F-POF-2 to Sulfur hexafluoride, carbon tetrafluoride and Nitrogen trifluoride
As can be seen from Table 1, the F-POF-1 and F-POF-2 materials have good adsorption to sulfur hexafluoride, carbon tetrafluoride and nitrogen trifluoride at room temperature.
Example 3
Step one: weighing 1mol of tetrabromotetraphenyl methane and 2mol of 1,2,4,5 tetrafluorobenzene in a 10L reaction kettle, adding 0.1mol of palladium acetate, 0.2mol of tri-tert-butylphosphine tetrafluoroborate and 6L of nitrogen methyl pyrrolidone, oscillating and uniformly mixing the materials, introducing nitrogen to protect, setting the temperature to 130 ℃ after the completion of nitrogen protection, and heating for 48 hours to obtain a mixed solution;
step two: and (3) cooling the mixed solution obtained in the step (A) to room temperature, pouring the mixed solution into a material barrel, carrying out suction filtration on the obtained mixture, and flushing the mixture for three times by using methanol as a flushing solvent to obtain a filter cake. The filter cake was placed in a beaker containing a DMF solution, stirred for 1h with a magnetic stirrer, and then suction filtered. And carrying out Soxhlet extraction on the obtained product for 24 hours by using an ethanol reagent to further remove impurities, and carrying out vacuum drying on the solid subjected to Soxhlet extraction at 120 ℃ for 12 hours to obtain brown powder F-POF-3.
Example 4
Step one: weighing 1mol of tetrabromotetraphenyl methane and 2mol of 1,2,4,5 tetrafluorobenzene in a 10L reaction kettle, adding 0.1mol of palladium acetate, 0.2mol of tri-tert-butylphosphine tetrafluoroborate and 6LDMF, oscillating and uniformly mixing materials, introducing nitrogen for protection, setting the temperature to 140 ℃ and heating for 48 hours to obtain a mixed solution;
step two: and (3) cooling the mixed solution obtained in the step (A) to room temperature, pouring the mixed solution into a material barrel, carrying out suction filtration on the obtained mixture, and flushing the mixture with methanol serving as a flushing solvent for three times to obtain a filter cake. The filter cake was placed in a beaker containing a DMF solution, stirred for 1h with a magnetic stirrer, and then suction filtered. And carrying out Soxhlet extraction on the obtained product for 24 hours by using an ethanol reagent to further remove impurities, and carrying out vacuum drying on the solid subjected to Soxhlet extraction at 130 ℃ for 12 hours to obtain black powder F-POF-4.
The above-described embodiments are only preferred embodiments of the present invention, and should not be construed as limiting the present invention, and the embodiments and features of the embodiments in the present application may be arbitrarily combined with each other without collision. The protection scope of the present invention is defined by the claims, and the protection scope includes equivalent alternatives to the technical features of the claims. I.e., equivalent replacement modifications within the scope of this invention are also within the scope of the invention.
Claims (6)
1. The preparation method of the organic porous material for separating and purifying the electron special gas is characterized in that the structural formula of the organic porous material is shown as the formula (I):
according to the dehalogenation reaction principle of aromatic hydrocarbon, the bromoaromatic hydrocarbon and fluorine substituted aromatic hydrocarbon with active hydrogen atoms are subjected to condensation reaction under the weak alkaline condition, and finally a three-dimensional fluorine-containing organic porous framework material product which is formed by connecting reaction monomers through carbon-carbon bonds is obtained;
the method specifically comprises the following steps:
step one: weighing tetrabromo-tetraphenyl methane and 1,2,4, 5-tetrafluorobenzene, mixing, adding a catalyst, a cocatalyst and a solvent, oscillating and uniformly mixing the materials to form a mixture, and then sealing under the condition of vacuumizing for heating reaction; the ratio of tetrabromo-tetraphenyl methane, 1,2,4, 5-tetrafluorobenzene, catalyst, cocatalyst and solvent is 1mol:2mol:0.1mol:0.2mol:6L; the temperature of the heating reaction is 120-150 ℃ and the time is 48 hours;
step two: cooling to room temperature after the reaction is finished, carrying out suction filtration on a product after the reaction, adopting DMF and methanol to wash in the suction filtration process to obtain a filter cake, putting the filter cake into DMF, stirring uniformly, carrying out suction filtration again, then carrying out Soxhlet extraction on the obtained product by using ethanol to further remove impurities, and carrying out vacuum drying on a solid obtained by Soxhlet extraction to obtain the organic porous material for electronic special gas separation and purification.
2. The method for preparing an organic porous material for separation and purification of electron gas according to claim 1, wherein the solvent is a mixture of one or more of N, N-dimethylacetamide, N-dimethylformamide and azamethylpyrrolidone.
3. The method for preparing the organic porous material for separating and purifying electron gas according to claim 1, wherein the catalyst is palladium acetate, and the concentration of the catalyst in the mixture is 0.15mol/L.
4. The method for preparing an organic porous material for separation and purification of electron gas according to claim 1, wherein the cocatalyst is tri-tert-butylphosphine tetrafluoroborate, and the concentration of the cocatalyst in the mixture is 0.3mol/L.
5. The method for preparing an organic porous material for separation and purification of electron-specific gas according to claim 1, wherein the soxhlet extraction time of the obtained product with ethanol in the second step is 24 hours.
6. The method for preparing an organic porous material for separation and purification of electron gas according to claim 1, wherein the vacuum drying temperature in the second step is 100-150 ℃ and the time is 12h.
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