CN117510970B - Spongy porous organic polymer material and preparation method and application thereof - Google Patents
Spongy porous organic polymer material and preparation method and application thereof Download PDFInfo
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- CN117510970B CN117510970B CN202410009907.8A CN202410009907A CN117510970B CN 117510970 B CN117510970 B CN 117510970B CN 202410009907 A CN202410009907 A CN 202410009907A CN 117510970 B CN117510970 B CN 117510970B
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- organic polymer
- porous organic
- polymer material
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- spongy porous
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- 229920000620 organic polymer Polymers 0.000 title claims abstract description 119
- 239000002861 polymer material Substances 0.000 title claims abstract description 116
- 238000002360 preparation method Methods 0.000 title abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 91
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 68
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000005977 Ethylene Substances 0.000 claims abstract description 52
- 238000006384 oligomerization reaction Methods 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 239000011259 mixed solution Substances 0.000 claims abstract description 39
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 35
- IZALUMVGBVKPJD-UHFFFAOYSA-N benzene-1,3-dicarbaldehyde Chemical compound O=CC1=CC=CC(C=O)=C1 IZALUMVGBVKPJD-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000001179 sorption measurement Methods 0.000 claims abstract description 30
- ZPDWRQORROQQLX-UHFFFAOYSA-N 4-[[2,4,4,6,6-pentakis(4-aminophenoxy)-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-trien-2-yl]oxy]aniline Chemical compound C1=CC(N)=CC=C1OP1(OC=2C=CC(N)=CC=2)=NP(OC=2C=CC(N)=CC=2)(OC=2C=CC(N)=CC=2)=NP(OC=2C=CC(N)=CC=2)(OC=2C=CC(N)=CC=2)=N1 ZPDWRQORROQQLX-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000047 product Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 12
- 150000003624 transition metals Chemical class 0.000 claims abstract description 11
- 239000003377 acid catalyst Substances 0.000 claims abstract description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 26
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 15
- JYLPOJPHFDVWCY-UHFFFAOYSA-K oxolane;trichlorochromium Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3].C1CCOC1 JYLPOJPHFDVWCY-UHFFFAOYSA-K 0.000 claims description 15
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 14
- 239000002262 Schiff base Substances 0.000 claims description 12
- 150000001336 alkenes Chemical class 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- 239000011651 chromium Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 24
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 16
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 27
- 239000007787 solid Substances 0.000 description 26
- 238000010276 construction Methods 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 24
- 239000000203 mixture Substances 0.000 description 18
- 238000005406 washing Methods 0.000 description 16
- 238000001914 filtration Methods 0.000 description 15
- 238000009210 therapy by ultrasound Methods 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 239000011521 glass Substances 0.000 description 12
- 150000004982 aromatic amines Chemical group 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 11
- 238000001291 vacuum drying Methods 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 150000004753 Schiff bases Chemical class 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000001788 irregular Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000000877 morphologic effect Effects 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000005935 nucleophilic addition reaction Methods 0.000 description 2
- 239000012434 nucleophilic reagent Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- -1 Schiff base imine Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
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- 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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- B01D53/34—Chemical or biological purification of waste gases
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- 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
- B01J20/28014—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 form
- B01J20/28042—Shaped bodies; Monolithic structures
- B01J20/28045—Honeycomb or cellular structures; Solid foams or sponges
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- 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
- B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
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- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
- C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2361/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08J2361/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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Abstract
The invention relates to a spongy porous organic polymer material, a preparation method and application thereof, and belongs to the technical field of porous organic polymer materials. The method comprises the following steps: dissolving isophthalaldehyde and hexa (4-aminophenoxy) cyclotriphosphazene in an organic solvent to obtain a mixed solution; the organic solvent is a mixed organic solvent containing dimethyl sulfoxide and ethanol; adding an acid catalyst into the mixed solution for reaction to obtain a reaction product; post-treating the reaction product to obtain spongy porous organic polymerA composite material. The porous organic polymer material prepared by the invention has the advantages of special appearance of sponge, strong adsorption capacity, large specific surface area, multiple alkaline sites, mild preparation condition, simple and easy operation, high product yield and the like, and can be used as high-quality CO 2 Adsorption material enrichment and separation of low concentration CO 2 But also can be used as a carrier of transition metal for catalyzing ethylene oligomerization to selectively prepare high-carbon olefin.
Description
Technical Field
The invention relates to the technical field of porous organic polymer materials, and relates to a spongy porous organic polymer material, a preparation method and application thereof.
Background
The porous organic polymer is a light porous network material constructed by covalent connection among organic ligands, and has larger specific surface area, changeable pore size and designable space structure. Porous organic polymers include super cross-linked polymers, inherently porous polymers, conjugated organic frameworks, and the like. The conjugated porous organic polymer material has excellent performance and application prospect in the fields of gas adsorption and heterogeneous catalysis by virtue of a high specific surface area, a highly conjugated framework structure, multiple active reaction sites and excellent stability.
Based on the ordered arrangement of the building units of the conjugated porous organic polymer material, the controllable active sites and pore diameters and other characteristics, a series of derivative materials with excellent physical properties and chemical properties can be prepared through the construction of the morphology of the conjugated porous organic polymer material, and the conjugated porous organic polymer material has also received a great deal of attention. At present, it has been reported that porous organic polymer materials having spherical, lamellar, brush-like morphology can be obtained by changing the types of the building units and the preparation methods. However, research on spongy porous organic polymer materials has not been reported, and under special environments, specific morphology construction plays a key role in application performance.
Porous organic polymer materials with spherical and flaky shapes are reported to be used for CO 2 But these porous organic polymer materials have poor adsorptivity and/or ethylene oligomerization, and have certain limitations; and the porous organic polymer materials are only used for preparing low-carbon olefin by ethylene oligomerization, and have great defects in preparing high-carbon olefin by ethylene oligomerization.
Thus, there remains a need to continue to study and explore new porous organic polymeric materials for increasing CO 2 The adsorption and ethylene oligomerization high selectivity preparation of the high-carbon olefin are of great significance.
Disclosure of Invention
In order to solve one or more technical problems in the prior art, the invention provides a spongy porous organic polymer material, and a preparation method and application thereof.
The present invention provides in a first aspect a method of preparing a spongy porous organic polymer material, the method comprising the steps of:
(1) Dissolving isophthalaldehyde and hexa (4-aminophenoxy) cyclotriphosphazene in an organic solvent to obtain a mixed solution; the organic solvent is a mixed organic solvent containing dimethyl sulfoxide and ethanol;
(2) Adding an acid catalyst into the mixed solution for reaction to obtain a reaction product;
(3) And (3) carrying out post-treatment on the reaction product to obtain the spongy porous organic polymer material.
Preferably, the molar ratio of the isophthalaldehyde to the hexa (4-aminophenoxy) cyclotriphosphazene is (3-4): 1, a step of; and/or the concentration sum of the isophthalaldehyde and the hexa (4-aminophenoxy) cyclotriphosphazene in the mixed solution is 0.01-0.15 mmol/mL.
Preferably, the volume ratio of the dimethyl sulfoxide to the ethanol is (5-10): 1.
preferably, the acid catalyst is one or more of acetic acid solution, formic acid solution and hydrochloric acid solution; the concentration of the acid catalyst is 1-3 mol/L; and/or the molar ratio of solute in the acidic catalyst to isophthalaldehyde is 1: (5-30).
Preferably, the reaction temperature is 50-80 ℃, and the reaction time is 24-72 h.
Preferably, the post-treatment is: the reaction product was filtered, washed and dried sequentially.
The present invention provides in a second aspect a spongy porous organic polymer material produced by the method of the invention described in the first aspect.
The present invention provides in a third aspect a spongy porous organic polymer material as CO produced by the process of the first aspect of the invention 2 Application of the adsorption material.
In a fourth aspect, the present invention provides the use of a spongy porous organic polymer material according to the invention as a carrier for transition metals in ethylene oligomerization.
Preferably, the ethylene oligomerization is carried out in a system comprising a spongy porous organic polymer material, chromium tetrahydrofuran chloride, triethylaluminum, diethylaluminum chloride and cyclohexane and being fed with ethylene gas; the mass ratio of the triethylaluminum to the diethylaluminum chloride is (1.5-2.5): 1, a step of; the molar ratio of the total amount of aluminum contained in the triethylaluminum and aluminum contained in the diethylaluminum chloride to chromium contained in the chromium chloride tetrahydrofuran is (100 to 500): 1, a step of; the spongy porous organic polymer materialThe molar ratio of the Schiff base imino contained in the catalyst to the tetrahydrofuran chromium chloride is (2-6): 1, a step of; the ethylene oligomerization pressure is 1.5-4.0 MPa; the ethylene oligomerization temperature is 60-80 ℃; the ethylene oligomerization time is 20-40 min; c in the product obtained by oligomerization of ethylene 8 The sum of the mass percentages of the olefins is not less than 60 percent.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) The porous organic polymer material prepared by the invention has the advantages of special appearance of sponge, strong adsorption capacity, large specific surface area, multiple alkaline sites, mild preparation condition, simple and easy operation method, high product yield and the like; the spongy porous organic polymer material with multiple alkaline sites prepared by the invention not only can be used as high-quality CO 2 Adsorption material enrichment and separation of low concentration CO 2 But also can be used as a carrier of transition metal for catalyzing ethylene oligomerization to selectively prepare high-carbon olefin; in addition, the spongy porous organic polymer material prepared by the invention has excellent cycling stability and wide application prospect.
(2) The spongy porous organic polymer material prepared by the invention is prepared in pure CO 2 In the environment, for CO 2 The adsorption capacity is more than 2.06mmol/g and is N 2 And CO 2 In a mixed environment, for low concentration CO 2 The adsorption quantity is more than 1.12mmol/g; in addition, the spongy porous organic polymer material prepared by the invention is used as a transition metal center carrier, and the catalytic activity of catalyzing ethylene oligomerization is more than 1 multiplied by 10 6 g·(mol Cr·h) -1 C in oligomerization product 8 The mass percentage of the olefin is not less than 60 percent.
Drawings
FIG. 1 is an infrared spectrum of a spongy porous organic polymer material prepared in example 1 of the present invention;
FIG. 2 is a SEM image at a lower magnification of a spongy porous organic polymer material prepared according to example 1 of the invention;
FIG. 3 is an SEM image at a higher magnification of a spongy porous organic polymer material prepared according to example 1 of the invention;
FIG. 4 is an SEM image of a lamellar porous organic polymeric material prepared according to comparative example 1 of the present invention;
FIG. 5 is an SEM image of a spherical porous organic polymer material prepared according to comparative example 3 of the present invention;
fig. 6 is an SEM image of the irregularly particulate porous organic polymeric material obtained in comparative example 4 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below in connection with the embodiments of the present invention. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The present invention provides in a first aspect a method of preparing a spongy porous organic polymer material, the method comprising the steps of:
(1) Dissolving isophthalaldehyde and hexa (4-aminophenoxy) cyclotriphosphazene (alias: hexa (p-aminophenoxy) cyclotriphosphazene) in an organic solvent to obtain a mixed solution; the organic solvent is a mixed organic solvent containing dimethyl sulfoxide and ethanol; in the invention, the ethanol refers to absolute ethanol; in some specific embodiments, the organic solvent consists of dimethyl sulfoxide and ethanol; in the invention, the hexa (4-aminophenoxy) cyclotriphosphazene is used as a central building unit, and the isophthalaldehyde is used as a linear building unit;
(2) Adding an acid catalyst into the mixed solution for reaction to obtain a reaction product; in the present invention, the reaction is a schiff base condensation reaction; in the present invention, the reaction is performed under a nitrogen atmosphere;
(3) Post-processing the reaction product to obtain a spongy porous organic polymer material; in the present invention, the post-treatment is, for example, filtration, washing and then drying of the reaction product at room temperature; the conditions of filtration, washing and drying are not particularly limited in the present invention, and may be routinely selected by those skilled in the art; in the present invention, the room temperature is, for example, 20 to 30 ℃.
The porous organic polymer material prepared by the invention has the advantages of special appearance of sponge, strong adsorption capacity, large specific surface area, multiple alkaline sites, mild preparation condition, simple and easy operation method, high product yield and the like; the spongy porous organic polymer material with multiple alkaline sites prepared by the invention not only can be used as high-quality CO 2 Adsorption material enrichment and separation of low concentration CO 2 But also can be used as a carrier of transition metal for catalyzing ethylene oligomerization to selectively prepare high-carbon olefin; in addition, the spongy porous organic polymer material prepared by the invention has excellent cycling stability and wide application prospect; the invention discovers that compared with porous organic polymer materials such as spherical, lamellar, hairbrush and the like reported in the prior art, the spongy porous organic polymer material prepared by the invention has the advantages of high CO resistance 2 The spongy porous organic polymer material prepared by the invention can be used as a carrier of transition metal to catalyze ethylene oligomerization to selectively prepare high-carbon olefin, and C in an ethylene oligomerization product 8 The mass percentage of the olefin is not less than 60 percent.
Compared with the prior art, the invention adopts the mixed organic solvent containing dimethyl sulfoxide and ethanol to obviously influence the morphology of the prepared porous organic polymer material, and the invention discovers that if the adopted organic solvent is unsuitable, lamellar or spherical or irregular granular porous organic polymer material is formed instead of the sponge porous organic polymer material, and the porous organic polymer material can cause the porous organic polymer material to influence CO 2 Is obviously lower in adsorption performanceThe activity of catalyzing ethylene oligomerization is obviously reduced, and the low-carbon olefin is taken as a main component in an ethylene oligomerization product, so that the catalyst cannot be used as a carrier of transition metal for catalyzing ethylene oligomerization to efficiently prepare high-carbon olefin; the invention discovers that the dimethyl sulfoxide has higher polarity and strong dissolving capacity, and can well dissolve isophthalaldehyde and hexa (4-aminophenoxy) cyclotriphosphazene, so that the reaction is carried out in a homogeneous system, and the reaction rate is improved; ethanol is taken as a weak nucleophilic reagent to attack carbonyl of aldehyde, so that the nucleophilic addition reaction speed is accelerated; the reaction involved in the invention is Schiff base reaction, belongs to nucleophilic addition reaction, and is reversible reaction. According to the invention, a mixed system of dimethyl sulfoxide and ethanol is used as a reaction solvent, so that on one hand, the dimethyl sulfoxide in the system can well dissolve two monomers to form a homogeneous reaction system, and meanwhile, porous organic materials generated by the reaction can be well dispersed, thereby being beneficial to the formation of a porous structure; on the other hand, ethanol in the system is used as a nucleophilic reagent, and under the acidic condition, carbonyl in aldehyde molecules is attacked and activated, so that the reaction of aldehyde and amine is accelerated, the reaction rate of Schiff base is improved, and the interaction of two solvents promotes the formation of spongy porous organic polymer materials.
According to some preferred embodiments, the molar ratio of isophthalaldehyde to hexa (4-aminophenoxy) cyclotriphosphazene is (3-4): 1 (e.g., 3:1, 3.5:1, or 4:1), preferably (3-3.5): 1, a step of; in the present invention, it is preferable that the molar ratio of the isophthalaldehyde to the hexa (4-aminophenoxy) cyclotriphosphazene is (3 to 4): 1, the spongy porous organic polymer material prepared by the method has a plurality of C=N alkaline site porous structures with high carbon dioxide adsorption performance, so that the material has stronger carbon dioxide adsorption capacity in application, and has higher catalytic activity when being used as a carrier of transition metal for catalyzing ethylene oligomerization to selectively prepare high-carbon olefin, so that C in oligomerization products 8 The sum of the mass percentages of the olefins is more than or equal to 60 percent; and/or the sum of the concentrations of isophthalaldehyde and hexa (4-aminophenoxy) cyclotriphosphazene in the mixed solution is 0.01 to 0.15mmol/mL (for example, 0.01, 0.02, 0.03),0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14 or 0.15 mmol/mL), preferably 0.01 to 0.13mmol/mL, more preferably 0.01 to 0.1mmol/mL.
According to some preferred embodiments, the volume ratio of the dimethyl sulfoxide to the ethanol is (5-10): 1 (e.g., 5:1, 6:1, 7:1, 8:1, 9:1, or 10:1), preferably (7-10): 1.
in the present invention, preferably, the volume ratio of the dimethyl sulfoxide to the ethanol is (5 to 10): 1, the catalyst is favorable for ensuring that the prepared catalyst has better carbon dioxide adsorption performance, and has higher catalytic activity when being used as a carrier of transition metal for catalyzing ethylene oligomerization to selectively prepare high-carbon olefin, so that C in oligomerization products 8 The spongy porous organic polymer material with higher mass percent of olefin; according to the invention, if the volume ratio of dimethyl sulfoxide to ethanol is larger than 10:1, ethanol molecules in the system are fewer, the ethanol molecules which attack carbonyl groups in aldehyde molecules are reduced, the Schiff base reaction is slowed down, the yield is lower, the application performance of the formed spongy porous organic polymer material is affected, and if the volume ratio of dimethyl sulfoxide to ethanol is smaller than 5:1, the ethanol molecules which attack carbonyl groups in the aldehyde molecules are increased, the Schiff base reaction is quicker, and although the spongy porous organic polymer material can be formed, the generated spongy porous organic polymer material is poorer in dispersion in the system due to the smaller dimethyl sulfoxide amount in the system, so that agglomeration is caused, and the application performance is also poorer.
According to some preferred embodiments, the acidic catalyst is one or more of acetic acid solution (acetic acid aqueous solution), formic acid solution (formic acid aqueous solution), hydrochloric acid solution (hydrochloric acid aqueous solution); the concentration of the acid catalyst is 1-3 mol/L (for example, 1, 1.5, 2, 2.5 or 3 mol/L); and/or the molar ratio of solute in the acidic catalyst to isophthalaldehyde is 1: (5-30) (e.g., 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, 1:20, 1:21, 1:22, 1:23, 1:24, 1:25, 1:26, 1:27, 1:28, 1:29, or 1:30), preferably 1: (5-20), more preferably 1: (5-12).
According to some preferred embodiments, the temperature of the reaction is 50-80 ℃ (e.g., 50 ℃, 60 ℃, 70 ℃, or 80 ℃), and the time of the reaction is 24-72 hours (e.g., 24, 36, 48, 60, or 72 hours); in the invention, preferably, the reaction temperature is 50-80 ℃ and the reaction time is 24-72 h, so that the preparation of the catalyst with better carbon dioxide adsorption performance is facilitated, and the catalyst has higher catalytic activity when the catalyst is used as a carrier of transition metal for catalyzing ethylene oligomerization to selectively prepare high-carbon olefin, so that C in oligomerization products 8 The spongy porous organic polymer material with higher mass percent of olefin; according to the invention, if the reaction temperature is too low, the reaction activity is low, which is not beneficial to the formation of a porous structure, while if the reaction temperature is too high, ethanol serving as a nucleophilic activating reagent is easy to exist in a gaseous form in a reaction system, the concentration of effective ethanol molecules in a liquid reaction system is reduced, so that the product yield is low, and the formation of a spongy porous morphology is not beneficial; in addition, the schiff base reaction in the present invention is a reversible reaction, and if the reaction time is too short, the reaction is insufficient, resulting in lower yield, while if the reaction time is too long, the energy consumption is increased.
According to some preferred embodiments, the post-treatment is: the reaction product was filtered, washed and dried sequentially.
The present invention provides in a second aspect a spongy porous organic polymeric material produced by the method of the invention described in the first aspect; in the invention, the spongy porous organic polymer material is obtained by reacting linear building unit isophthalaldehyde with central building unit hexa (4-aminophenoxy) cyclotriphosphazene.
The present invention provides in a third aspect a spongy porous organic polymer material as CO produced by the process of the first aspect of the invention 2 Application of the adsorption material.
In some embodiments, the pure CO is at a test temperature of 298.15K 2 In the environment, the spongy porous organic polymer material is used for preparing the CO 2 The adsorption quantity of the catalyst is more than 2.06mmol/g.
In other embodiments, the test temperature is 298.15. 298.15K, N 2 And CO 2 Under the mixed environment, N 2 With CO 2 At a volume ratio of 5:1, the spongy porous organic polymer material is specific to CO 2 The adsorption quantity of the catalyst is more than 1.12mmol/g.
In a fourth aspect, the present invention provides the use of a spongy porous organic polymer material according to the invention as a carrier for transition metals in ethylene oligomerization.
According to some preferred embodiments, the ethylene oligomerization is carried out in a system comprising a spongy porous organic polymer material, chromium tetrahydrofuran chloride, triethylaluminum, diethylaluminum chloride and cyclohexane and being fed with ethylene gas; the mass ratio of the triethylaluminum to the diethylaluminum chloride is (1.5-2.5): 1 (e.g., 1.5:1, 2:1, or 2.5:1), preferably 2:1; the molar ratio of the total amount of aluminum contained in the triethylaluminum and aluminum contained in the diethylaluminum chloride to chromium contained in the chromium chloride tetrahydrofuran is (100 to 500): 1 (e.g., 100:1, 150:1, 200:1, 250:1, 300:1, 350:1, 400:1, 450:1, or 500:1); the molar ratio of the Schiff base imino contained in the spongy porous organic polymer material to the tetrahydrofuran chromium chloride is (2-6): 1 (e.g., 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, or 6:1); the ethylene oligomerization pressure is 1.5-4.0MPa (e.g. 1.5, 2, 2.5, 3, 3.5 or 4.0 MPa); the ethylene oligomerization temperature is 60-80 ℃ (for example 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃); the ethylene oligomerization time is 20-40 min (for example, 20, 25, 30, 35 or 40 min), preferably 30min; c in the product obtained by oligomerization of ethylene 8 The sum of the mass percentages of the olefins is not less than 60 percent.
According to some specific embodiments, a spongy porous organic polymer material, chromium chloride tetrahydrofuran, triethylaluminum, diethyl aluminum chloride and cyclohexane are added into a 250mL stainless steel reaction kettle and uniformly mixed, then ethylene gas is introduced, and ethylene oligomerization is carried out under the condition that the ethylene pressure is 1.5-4.0 MPa; wherein the mass ratio of triethylaluminum to diethyl aluminum monochloride is 2:1, and the molar ratio of the total calculated amount of Al in triethylaluminum to Al in diethyl aluminum monochloride to chromium in chromium tetrahydrofuran chloride is (100-500): 1, wherein the molar ratio of Schiff base imino contained in the spongy porous organic polymer material to the tetrahydrofuran chromium chloride is (2-6): 1, a step of; the ethylene oligomerization temperature is 60-80 ℃ (for example 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃); the ethylene oligomerization time is 20-40 min.
According to some preferred embodiments, the spongy porous organic polymer material is a chromium metal center support, and the catalytic activity of the catalytic ethylene oligomerization is greater than 1×10 6 g·(mol Cr·h) -1 C in oligomerization product 8 The total mass percent of the olefins is more than or equal to 60 percent.
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. Unless otherwise specified, each of the reaction raw materials used in the examples and comparative examples of the present invention can be obtained commercially or synthesized by an existing method.
Example 1
The embodiment provides a preparation method of a spongy porous organic polymer material, which comprises the following specific steps:
weighing 1.00mmol of central building unit hexa (4-aminophenoxy) cyclotriphosphazene containing six aromatic amine groups and 3.00mmol of linear building unit isophthalaldehyde, adding into a 100mL three-necked glass bottle, adding 30mL of dimethyl sulfoxide and 3mL of ethanol, and heating at 25 ℃ and N 2 Performing ultrasonic treatment for 10 minutes under the condition to completely dissolve the central construction unit and the linear construction unit to obtain a mixed solution; then, 0.2mL of an aqueous acetic acid solution having a concentration of 3mol/L was added to the mixed solution, and the mixture was replaced with nitrogen three times and reacted at 80℃for 48 hours to obtain a reaction product. After the reaction is finished, the obtained reaction product is filtered under negative pressure,and washing the obtained solid with dimethyl sulfoxide for 3-5 times, and vacuum drying the washed solid at 65 ℃ for 12 hours to obtain the spongy porous organic polymer material.
The invention carries out structural and morphological analysis on the spongy porous organic polymer material obtained in the example 1, and the results are shown in fig. 1, 2 and 3; fig. 1 is an infrared spectrum of the spongy porous organic polymer material obtained in this example, and fig. 2 and 3 are scanning electron microscope images of the spongy porous organic polymer material obtained in this example at different magnifications. As can be seen from FIG. 1, at 3435cm -1 Near amino (-NH) 2 ) Is 2850cm -1 And 2915cm -1 The vicinity is the characteristic absorption peak of-CH-on benzene ring, 1690cm -1 Characteristic absorption peak with c=n nearby, 1190cm -1 And 950cm -1 Characteristic adsorption peaks near P=N-and P-N, 1630cm -1 And 1505cm -1 The vicinity is characteristic absorption peak of benzene ring skeleton, 1270cm -1 And 1180cm -1 Characteristic adsorption peak of C-N nearby 860cm -1 、830cm -1 And 785cm -1 The characteristic peak of benzene ring disubstituted shows that the central building unit hexa (4-aminophenoxy) cyclotriphosphazene reacts with linear building unit isophthalaldehyde to obtain a Schiff base imine bridged organic polymer material; as can be seen from fig. 2 and 3, the organic polymer material has a special morphology of spongy porous.
Example 2
The embodiment provides a preparation method of a spongy porous organic polymer material, which comprises the following specific steps:
weighing 1.00mmol of central building unit hexa (4-aminophenoxy) cyclotriphosphazene containing six aromatic amine groups and 3.00mmol of linear building unit isophthalaldehyde, adding into a 100mL three-necked glass bottle, then adding 35mL of dimethyl sulfoxide and 5mL of ethanol, and heating at 25 ℃ and N 2 Ultrasonic treatment is carried out for 10 minutes under the condition, so that the central construction unit and the linear construction unit are completely dissolved, and a mixed solution is obtained; then adding 0.2mL of 3mol/L acetic acid aqueous solution into the mixed solution, replacing the solution with nitrogen for three times, and reacting at 60 ℃ for 48 hours to obtain the reactionThe product is obtained. And after the reaction is finished, filtering the obtained reaction product under negative pressure, washing the obtained solid with dimethyl sulfoxide for 3-5 times, and vacuum drying the washed solid for 12 hours at 65 ℃ to obtain the spongy porous organic polymer material.
Example 3
The embodiment provides a preparation method of a spongy porous organic polymer material, which comprises the following specific steps:
weighing 1.00mmol of central building unit hexa (4-aminophenoxy) cyclotriphosphazene containing six aromatic amine groups and 3.50mmol of linear building unit isophthalaldehyde, adding into a 100mL three-necked glass bottle, then adding 40mL of dimethyl sulfoxide and 5mL of ethanol, and heating at 25 ℃ and N 2 Ultrasonic treatment is carried out for 10 minutes under the condition, so that the central construction unit and the linear construction unit are completely dissolved, and a mixed solution is obtained; then, 0.3mL of 1mol/L acetic acid aqueous solution was added to the mixed solution, and the mixture was replaced with nitrogen three times and reacted at 70℃for 36 hours to obtain a reaction product. And after the reaction is finished, filtering the obtained reaction product under negative pressure, washing the obtained solid with dimethyl sulfoxide for 3-5 times, and vacuum drying the washed solid for 12 hours at 65 ℃ to obtain the spongy porous organic polymer material.
Example 4
Example 4 was substantially the same as example 1 except that 0.2mL of an aqueous formic acid solution having a concentration of 3mol/L was added to the mixed solution, and the other conditions were not changed.
Example 5
Example 5 was substantially the same as example 1 except that 0.1mL of 1mol/L aqueous hydrochloric acid was added to the mixed solution, and the other conditions were not changed.
Example 6
The embodiment provides a preparation method of a spongy porous organic polymer material, which comprises the following specific steps:
1.00mmol of the central building unit hexa (4-aminophenoxy) cyclotriphosphazene containing six aromatic amine groups and 2.00mmol of the linear building unit isophthalaldehyde are weighed and added into a 100mL three-necked glass bottle, 22.5mL of dimethyl sulfoxide and 2.25mL of ethanol are then added, and the mixture is heated at 25 ℃ and N 2 Performing ultrasonic treatment for 10 minutes under the condition to completely dissolve the central construction unit and the linear construction unit to obtain a mixed solution; then, 0.2mL of an aqueous acetic acid solution having a concentration of 2mol/L was added to the mixed solution, and the mixture was replaced with nitrogen three times and reacted at 80℃for 48 hours to obtain a reaction product. And after the reaction is finished, filtering the obtained reaction product under negative pressure, washing the obtained solid with dimethyl sulfoxide for 3-5 times, and vacuum drying the washed solid for 12 hours at 65 ℃ to obtain the spongy porous organic polymer material.
Example 7
The embodiment provides a preparation method of a spongy porous organic polymer material, which comprises the following specific steps:
weighing 1.00mmol of central building unit hexa (4-aminophenoxy) cyclotriphosphazene containing six aromatic amine groups and 5.00mmol of linear building unit isophthalaldehyde, adding into a 100mL three-necked glass bottle, then adding 45mL of dimethyl sulfoxide and 4.5mL of ethanol, and heating at 25 ℃ and N 2 Performing ultrasonic treatment for 10 minutes under the condition to completely dissolve the central construction unit and the linear construction unit to obtain a mixed solution; then, 0.5mL of an aqueous acetic acid solution having a concentration of 2mol/L was added to the mixed solution, and the mixture was replaced with nitrogen three times and reacted at 80℃for 48 hours to obtain a reaction product. And after the reaction is finished, filtering the obtained reaction product under negative pressure, washing the obtained solid with dimethyl sulfoxide for 3-5 times, and vacuum drying the washed solid for 12 hours at 65 ℃ to obtain the spongy porous organic polymer material.
Example 8
The embodiment provides a preparation method of a spongy porous organic polymer material, which comprises the following specific steps:
1.00mmol of the central building unit hexa (4-aminophenoxy) cyclotriphosphazene containing six aromatic amine groups and 3.00mmol of the linear building unit isophthalaldehyde are weighed and added into a 100mL three-necked glass bottle, 26.4mL of dimethyl sulfoxide and 6.6mL of ethanol are then added, and the mixture is heated at 25 ℃ and N 2 Performing ultrasonic treatment for 10 minutes under the condition to completely dissolve the central construction unit and the linear construction unit to obtain a mixed solution; then, 0.2mL of an aqueous acetic acid solution having a concentration of 3mol/L was added to the mixed solution, usingAfter three times of nitrogen substitution, the reaction is carried out for 48 hours at 80 ℃ to obtain a reaction product. And after the reaction is finished, filtering the obtained reaction product under negative pressure, washing the obtained solid with dimethyl sulfoxide for 3-5 times, and vacuum drying the washed solid for 12 hours at 65 ℃ to obtain the spongy porous organic polymer material.
Example 9
The embodiment provides a preparation method of a spongy porous organic polymer material, which comprises the following specific steps:
weighing 1.00mmol of central building unit hexa (4-aminophenoxy) cyclotriphosphazene containing six aromatic amine groups and 3.00mmol of linear building unit isophthalaldehyde, adding into a 100mL three-port glass bottle, then adding 31.35mL of dimethyl sulfoxide and 1.65mL of ethanol, and heating at 25 ℃ and N 2 Performing ultrasonic treatment for 10 minutes under the condition to completely dissolve the central construction unit and the linear construction unit to obtain a mixed solution; then, 0.2mL of an aqueous acetic acid solution having a concentration of 3mol/L was added to the mixed solution, and the mixture was replaced with nitrogen three times and reacted at 80℃for 48 hours to obtain a reaction product. And after the reaction is finished, filtering the obtained reaction product under negative pressure, washing the obtained solid with dimethyl sulfoxide for 3-5 times, and vacuum drying the washed solid for 12 hours at 65 ℃ to obtain the spongy porous organic polymer material.
Comparative example 1
The comparative example provides a preparation method of lamellar porous organic polymer material, which comprises the following specific steps:
weighing 1.00mmol of central building unit hexa (4-aminophenoxy) cyclotriphosphazene containing six aromatic amine groups and 3.00mmol of linear building unit isophthalaldehyde, adding into a 100mL three-necked glass bottle, then adding 30mL of 1, 4-dioxane and 3mL of toluene, and heating at 25 ℃ and N 2 Ultrasonic treatment is carried out for 10 minutes under the condition, so that the central construction unit and the linear construction unit are completely dissolved, and a mixed solution is obtained; then, 0.2mL of an aqueous acetic acid solution having a concentration of 3mol/L was added to the mixed solution, and the mixture was replaced with nitrogen three times and reacted at 80℃for 48 hours to obtain a reaction product. After the reaction is finished, filtering the obtained reaction product under negative pressure, washing the obtained solid with 1, 4-dioxane for 3-5 times, and carrying out true filtration on the washed solid at 65 DEG CAnd (5) air-drying for 12 hours to obtain the lamellar porous organic polymer material.
The porous organic polymer material obtained in comparative example 1 of the present invention was subjected to morphology analysis, and as shown in fig. 4, it can be seen from fig. 4 that the porous organic polymer material synthesized in comparative example 1 has a lamellar morphology.
Comparative example 2
The comparative example provides a preparation method of lamellar porous organic polymer material, which comprises the following specific steps:
weighing 1.00mmol of central building unit hexa (4-aminophenoxy) cyclotriphosphazene containing six aromatic amine groups and 3.00mmol of linear building unit isophthalaldehyde, adding into a 100mL three-necked glass bottle, then adding 35mL of 1, 4-dioxane and 5mL of toluene, and heating at 25 ℃ and N 2 Ultrasonic treatment is carried out for 10 minutes under the condition, so that the central construction unit and the linear construction unit are completely dissolved, and a mixed solution is obtained; then, 0.2mL of an aqueous acetic acid solution having a concentration of 3mol/L was added to the mixed solution, and the mixture was replaced with nitrogen three times and reacted at 60℃for 48 hours to obtain a reaction product. And after the reaction is finished, filtering the obtained reaction product under negative pressure, washing the obtained solid with 1, 4-dioxane for 3-5 times, and vacuum drying the washed solid for 12 hours at 65 ℃ to obtain the lamellar porous organic polymer material.
Comparative example 3
The comparative example provides a preparation method of a spherical porous organic polymer material, which comprises the following specific steps:
weighing 1.00mmol of central building unit hexa (4-aminophenoxy) cyclotriphosphazene containing six aromatic amine groups and 3.00mmol of linear building unit isophthalaldehyde, adding into a 100mL three-necked glass bottle, then adding 30mL of 1, 4-dioxane and 3mL of mesitylene, and heating at 25 ℃ and N 2 Ultrasonic treatment is carried out for 10 minutes under the condition, so that the central construction unit and the linear construction unit are completely dissolved, and a mixed solution is obtained; then, 0.2mL of an aqueous acetic acid solution having a concentration of 3mol/L was added, and the mixture was replaced with nitrogen three times and reacted at 80℃for 48 hours to obtain a reaction product. After the reaction is finished, filtering the obtained reaction product under negative pressure, washing the obtained solid with 1, 4-dioxane for 3-5 times, and vacuum drying the washed solid for 12h at 65 DEG CA spherical porous organic polymer material is obtained.
The porous organic polymer material obtained in the comparative example 3 is subjected to morphological analysis, and the result is shown in fig. 5; as can be seen from fig. 5, the porous organic polymer material synthesized in comparative example 3 has a spherical morphology.
Comparative example 4
The comparative example provides a method for preparing an irregular granular porous organic polymer material, which comprises the following specific steps:
weighing 1.00mmol of central building unit hexa (4-aminophenoxy) cyclotriphosphazene containing six aromatic amine groups and 3.00mmol of linear building unit isophthalaldehyde, adding into a 100mL three-necked glass bottle, adding 33mL of dimethyl sulfoxide, and heating at 25deg.C and N 2 Performing ultrasonic treatment for 10 minutes under the condition to completely dissolve the central construction unit and the linear construction unit to obtain a mixed solution; then, 0.2mL of an aqueous acetic acid solution having a concentration of 3mol/L was added to the mixed solution, and the mixture was replaced with nitrogen three times and reacted at 80℃for 48 hours to obtain a reaction product. And after the reaction is finished, filtering the obtained reaction product under negative pressure, washing the obtained solid with dimethyl sulfoxide for 3-5 times, and vacuum drying the washed solid for 12 hours at 65 ℃ to obtain the irregular granular porous organic polymer material.
The porous organic polymer material obtained in comparative example 4 is subjected to morphological analysis, and the result is shown in fig. 6; as can be seen from fig. 6, the porous organic polymer material synthesized in comparative example 4 has an irregular granular morphology.
Comparative example 5
Weighing melamine 2.00mmol and isophthalaldehyde 3.00mmol, adding into 100mL three-necked glass bottle, adding dimethyl sulfoxide 30mL and ethanol 3mL, and heating at 25deg.C under N 2 Ultrasonic treatment is carried out for 10 minutes under the condition, so that melamine and isophthalaldehyde are completely dissolved, and a mixed solution is obtained; then, 0.2mL of an aqueous acetic acid solution having a concentration of 3mol/L was added to the mixed solution, and the mixture was replaced with nitrogen three times and reacted at 80℃for 48 hours to obtain a reaction product. After the reaction is finished, filtering the obtained reaction product under negative pressure, washing the obtained solid with dimethyl sulfoxide for 3-5 times, and washing the washed solid at 65 DEG CAnd (5) drying in vacuum for 12h to obtain the porous organic polymer material.
Comparative example 6
32mg of carbohydrazide is added to the ampoule; 48mg of terephthalaldehyde was then added; then adding 3mL of 1, 4-dioxane and 0.3mL of acetic acid aqueous solution with the concentration of 6mol/L, and heating at 25 ℃ and N 2 And carrying out ultrasonic treatment for 15min under the condition to uniformly mix the components in the solution to obtain a mixed solution. Sealing the obtained mixed solution in a vacuum state, and then placing the sealed mixed solution at 120 ℃ for reaction for 72 hours; finally, cleaning the material with N, N-dimethylformamide and anhydrous tetrahydrofuran in sequence to remove the reaction solvent and the small molecular oligomer, thereby preparing the porous organic polymer material.
Comparative example 7
Respectively dissolving 108mg of m-phenylenediamine and 134mg of terephthalaldehyde in 10mL of ethanol, wherein the molar ratio of the m-phenylenediamine to the terephthalaldehyde is 1:1, stirring ultrasonically for 15min until the terephthalaldehyde is dissolved, adding the mixture into a reaction kettle, stirring until the mixture is homogeneous, dropwise adding 2mL of acetic acid, continuing stirring, stirring until the mixture is homogeneous, performing ultrasonic treatment, finally placing the reaction kettle at 120 ℃ for reacting for 72h to obtain a yellow solid-liquid mixture, filtering the yellow solid-liquid mixture to obtain a yellow solid crude product, washing the solid crude product with methanol, ethanol and N, N-dimethylformamide for 10 times to remove a solvent, a catalyst and unreacted monomers, and finally placing the dried product into a vacuum drying box for drying to obtain the porous organic polymer material.
The porous organic polymer materials prepared in each example and each comparative example are subjected to specific surface area and CO by adopting a full-automatic specific surface area and pore size distribution analyzer (TriStar II 3020) 2 Adsorption Performance test, wherein the specific surface area was measured at 77K, CO 2 The test temperature of adsorption performance is 298.15K, specific surface area and CO 2 The adsorption properties were all measured under normal pressure conditions, and the results are shown in table 1:
table 1: adsorption properties of the porous organic polymer materials in each example and each comparative example.
In table 1, the symbol "/" indicates that the performance index was not tested. As can be seen from the results of Table 1, the spongy porous organic polymer material prepared according to the present invention was resistant to CO 2 All have good adsorption performance, and the spongy porous organic polymer material prepared in the preferred embodiments 1-5 of the invention has larger specific surface area and is pure CO 2 In the environment, for CO 2 The adsorption quantity is above 2.06 mmol/g; at N 2 And CO 2 In a mixed environment with the volume ratio of 5:1, for CO 2 The adsorption quantity is 1.12mmol/g; the porous organic polymer materials prepared in comparative examples 1 to 7 were used for the treatment of CO in two environments 2 The adsorption quantity is smaller.
The invention tests the catalytic performance of the porous organic polymer materials in each example and each comparative example in ethylene oligomerization, and the test method is as follows: the invention adopts a 250mL stainless steel reaction kettle to add porous organic polymer material, chromium tetrahydrofuran chloride, triethylaluminum, diethyl aluminum monochloride and cyclohexane, and introduces ethylene, and carries out ethylene oligomerization for 30min under the conditions of ethylene pressure (ethylene oligomerization pressure) of 2.0MPa and ethylene oligomerization temperature of 70 ℃, and the ethylene oligomerization results are shown in Table 2; wherein the mass ratio of triethylaluminum to diethylaluminum monochloride is 2:1, the molar ratio of the total amount of aluminum (Al) in triethylaluminum to aluminum (Al) in diethylaluminum monochloride to chromium in chromium chloride tetrahydrofuran is 300:1, and the molar ratio of Schiff base imino (-C=N-) contained in the porous organic polymer material to chromium chloride tetrahydrofuran is 4:1.
Table 2: catalytic performance of the porous organic polymeric materials in each example and each comparative example.
As can be seen from the results in Table 2, the spongy porous organic polymer material prepared according to some preferred embodiments of the present invention has a catalytic activity of greater than 1X 10 when used as a chromium metal center support for catalyzing ethylene oligomerization 6 g·(mol Cr·h) -1 Alignment ofC in the polymerization product 8 The sum of the mass percentages of the olefins is not less than 60 percent. The porous organic polymer material prepared in comparative examples 1-7 has a catalytic activity of less than 1×10 when used as a chromium metal center carrier for catalyzing ethylene oligomerization 6 g·(mol Cr·h) -1 Less than C in oligomerization products 8 Higher olefins content.
The invention is not described in detail in a manner known to those skilled in the art.
Finally, it should be noted that: the high-efficiency spongy porous organic polymer material, the preparation method and the application thereof disclosed in the embodiment of the invention are described in detail, and specific examples are used for describing the implementation mode and the like of the invention, and the description of the above embodiment is only used for helping to understand the method and the core idea of the invention; meanwhile, as one skilled in the art will have variations in the specific embodiments and application scope in accordance with the ideas of the present invention, the present description should not be construed as limiting the present invention in summary; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (8)
1. A method for preparing a spongy porous organic polymer material, the method comprising the steps of:
(1) Dissolving isophthalaldehyde and hexa (4-aminophenoxy) cyclotriphosphazene in an organic solvent to obtain a mixed solution; the molar ratio of the isophthalaldehyde to the hexa (4-aminophenoxy) cyclotriphosphazene is (3-4): 1, a step of; the organic solvent is a mixed system of dimethyl sulfoxide and ethanol, and the volume ratio of the dimethyl sulfoxide to the ethanol is (5-10): 1, a step of;
(2) Adding an acid catalyst into the mixed solution for reaction to obtain a reaction product; the reaction temperature is 50-80 ℃, and the reaction time is 24-72 h;
(3) And (3) carrying out post-treatment on the reaction product to obtain the spongy porous organic polymer material.
2. The method of manufacturing according to claim 1, characterized in that:
the concentration sum of the isophthalaldehyde and the hexa (4-aminophenoxy) cyclotriphosphazene in the mixed solution is 0.01-0.15 mmol/mL.
3. The method of manufacturing according to claim 1, characterized in that:
the acid catalyst is one or more of acetic acid solution, formic acid solution and hydrochloric acid solution;
the concentration of the acid catalyst is 1-3 mol/L; and/or
The molar ratio of the solute in the acidic catalyst to the isophthalaldehyde is 1: (5-30).
4. The method of manufacturing according to claim 1, characterized in that:
the post-treatment is as follows: the reaction product was filtered, washed and dried sequentially.
5. A spongy porous organic polymer material produced by the production process of any one of claims 1 to 4.
6. A spongy porous organic polymer material as CO produced by the production process of any one of claims 1 to 4 2 Application of the adsorption material.
7. Use of a spongy porous organic polymer material produced by the production process of any one of claims 1 to 4 as a carrier for transition metals in ethylene oligomerization.
8. The use according to claim 7, characterized in that:
the ethylene oligomerization is carried out in a system which comprises spongy porous organic polymer material, chromium tetrahydrofuran chloride, triethylaluminum, diethyl aluminum chloride and cyclohexane and is filled with ethylene gas;
the mass ratio of the triethylaluminum to the diethylaluminum chloride is (1.5-2.5): 1, a step of;
the molar ratio of the total amount of aluminum contained in the triethylaluminum and aluminum contained in the diethylaluminum chloride to chromium contained in the chromium chloride tetrahydrofuran is (100 to 500): 1, a step of;
the molar ratio of the Schiff base imino contained in the spongy porous organic polymer material to the tetrahydrofuran chromium chloride is (2-6): 1, a step of;
the ethylene oligomerization pressure is 1.5-4.0 MPa;
the ethylene oligomerization temperature is 60-80 ℃;
the ethylene oligomerization time is 20-40 min;
c in the product obtained by oligomerization of ethylene 8 The sum of the mass percentages of the olefins is not less than 60 percent.
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