CN116284822B - Preparation method and application of ultrahigh crosslinked ionic polymer metal-free heterogeneous catalyst - Google Patents
Preparation method and application of ultrahigh crosslinked ionic polymer metal-free heterogeneous catalyst Download PDFInfo
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- 239000002638 heterogeneous catalyst Substances 0.000 title claims abstract description 37
- 229920000831 ionic polymer Polymers 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 66
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 60
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 50
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000004132 cross linking Methods 0.000 claims abstract description 27
- 239000004593 Epoxy Substances 0.000 claims abstract description 25
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 25
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- 239000002608 ionic liquid Substances 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 16
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 15
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 13
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 9
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000001291 vacuum drying Methods 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 14
- -1 4-benzyl-3-ethyl pyridinium bromide Chemical compound 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 claims description 10
- RBZMSGOBSOCYHR-UHFFFAOYSA-N 1,4-bis(bromomethyl)benzene Chemical group BrCC1=CC=C(CBr)C=C1 RBZMSGOBSOCYHR-UHFFFAOYSA-N 0.000 claims description 7
- 238000007259 addition reaction Methods 0.000 claims description 5
- HUSSVLWECZGPPZ-UHFFFAOYSA-M 1-benzyl-3-ethylimidazol-1-ium bromide Chemical compound [Br-].C(C)[N+]1=CN(C=C1)CC1=CC=CC=C1 HUSSVLWECZGPPZ-UHFFFAOYSA-M 0.000 claims description 4
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 35
- 239000003054 catalyst Substances 0.000 abstract description 18
- 238000001035 drying Methods 0.000 abstract description 15
- 238000006352 cycloaddition reaction Methods 0.000 abstract description 9
- 150000005676 cyclic carbonates Chemical class 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 31
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 12
- 238000010992 reflux Methods 0.000 description 12
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- JVZRCNQLWOELDU-UHFFFAOYSA-N 4-Phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=NC=C1 JVZRCNQLWOELDU-UHFFFAOYSA-N 0.000 description 2
- SHQUDBFKCYPHRS-UHFFFAOYSA-N 4-chloro-5-methyl-1,3-dioxol-2-one Chemical compound CC=1OC(=O)OC=1Cl SHQUDBFKCYPHRS-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- KKKDZZRICRFGSD-UHFFFAOYSA-N 1-benzylimidazole Chemical compound C1=CN=CN1CC1=CC=CC=C1 KKKDZZRICRFGSD-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- DBOLXXRVIFGDTI-UHFFFAOYSA-N 4-benzylpyridine Chemical compound C=1C=NC=CC=1CC1=CC=CC=C1 DBOLXXRVIFGDTI-UHFFFAOYSA-N 0.000 description 1
- XHLKOHSAWQPOFO-UHFFFAOYSA-N 5-phenyl-1h-imidazole Chemical compound N1C=NC=C1C1=CC=CC=C1 XHLKOHSAWQPOFO-UHFFFAOYSA-N 0.000 description 1
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000019606 astringent taste Nutrition 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
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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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
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- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
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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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8609—Sulfur oxides
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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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2258/00—Sources of waste gases
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2387/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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Abstract
The invention discloses a preparation method of a metal-free heterogeneous catalyst of an ultra-high crosslinking ionic polymer, which comprises the steps of sequentially adding ionic liquid, alpha' -dibromo-p-xylene and anhydrous ferric trichloride into a reactor, adding 1, 2-dichloroethane for reaction, filtering and washing a reaction product in a vacuum manner by using methanol, and drying to obtain a porous polymer; sequentially adding a porous polymer, acetonitrile and 1, 3-tetramethylguanidine into a reactor for reaction, vacuum filtering and washing a reaction product by using acetonitrile, and drying to prepare the ultra-high crosslinking ionic polymer metal-free heterogeneous catalyst; the ultra-high crosslinking ionic polymer metal-free heterogeneous catalyst prepared by the invention can be used for catalyzing the cycloaddition reaction of an epoxy compound and carbon dioxide to prepare cyclic carbonate, and can also be used for catalyzing the copolymerization reaction of the epoxy compound and sulfur dioxide to prepare polysulfite; and the preparation method is simple. The catalyst has the advantages of small dosage in catalytic reaction, high activity, good reusability and wide substrate universality.
Description
Technical Field
The invention relates to a preparation method of a multi-active-center ultrahigh cross-linked ionic polymer metal-free heterogeneous catalyst and application of the catalyst in catalyzing copolymerization of sulfur dioxide and an epoxy compound and cycloaddition of carbon dioxide and the epoxy compound.
Background
Sulfur dioxide is a colorless gas with a irritating choking smell and a strong astringency, which is considered as one of the main pollutants in the atmosphere, and the excessive emission of sulfur dioxide has been seriously harmful to human health and environment at present. In terms of the problem, the sulfur fixation desulfurization technology accelerates the construction of sulfur dioxide emission reduction projects, but the technology has limitation to preservative, bleaching agent and other aspects, and has little application to the synthesis of functional materials by utilizing sulfur dioxide. Therefore, the effective recycling of sulfur dioxide is a key for solving the problem of excessive emission of sulfur dioxide. The sulfur-containing polymer has excellent electrochemical performance, mechanical performance and optical performance, and simultaneously has better metal adhesion, heat resistance, chemical corrosion resistance, biocompatibility, antibacterial property and the like, and has wide development and application prospects. In recent years, researchers have proposed to use epoxy compounds and other monomers to copolymerize sulfur dioxide with sulfur dioxide to form sulfur-containing polymer materials, and the method gives higher value to the utilization of sulfur dioxide, so that not only can sulfur-containing polymer materials with excellent performance be obtained, but also sulfur dioxide can be effectively utilized. However, there are some disadvantages that in the copolymerization system, the monomer is difficult to form a product with sulfur dioxide or the relative molecular mass of the product is low, and thus the copolymerization is difficult to realize industrialization. It is therefore important to explore the development of novel high-efficiency catalysts to improve the efficiency of the copolymerization reaction and to regulate the structure of the copolymer. Researchers have also developed various catalysts to catalyze the copolymerization of sulfur dioxide, such as: various catalysts such as organometallic, peroxide, lewis acid, lewis base, and the like. However, these catalysts still have problems such as metal ion content, difficulty in separation, poor catalytic effect, etc. Therefore, it is urgent to find an environment-friendly and efficient metal-free catalyst.
In recent years, with the rapid development of industry, a great deal of fossil fuels such as natural gas, petroleum, coal and the like are combusted, more and more carbon dioxide is discharged into the atmosphere, carbon dioxide is a typical greenhouse gas which causes global warming, and is also a rich, environment-friendly and renewable C 1 resource, and the conversion of the carbon dioxide into chemicals and fuels has great significance for the sustainable development of the environment, so that the carbon dioxide has become the leading field of chemical research. Because of the thermodynamic stability and kinetic inertness of carbon dioxide, researchers have focused on developing efficient catalysts that are converted by thermocatalytic, electrocatalytic, photocatalytic, and the like. However, this faces a problem that activating carbon dioxide and effecting conversion under metal-free conditions is a great challenge, whereas catalysts such as metal oxides, organic bases, etc. present problems of environmental pollution, difficulty in separation, etc. Thus, there is a need to develop green, efficient, low cost catalysts.
In recent years, researchers have developed an efficient green ionic liquid catalyst capable of chemically capturing carbon dioxide, which not only serves as a catalyst, but also can serve as a solvent, has a series of advantages of low vapor pressure, low melting point, low volatility, good thermal stability and the like, and is a novel green safe pollution-free catalyst. The ionic liquid mainly comprises conventional ionic liquids such as imidazole salts, pyridines, quaternary ammonium salts, quaternary phosphonium salts and the like and various group functionalized ionic liquids, and belongs to a homogeneous catalyst which is difficult to recycle because of high viscosity of the ionic liquid.
Disclosure of Invention
Aiming at the problems of harsh conditions of copolymerization of sulfur dioxide and an epoxy compound and cycloaddition reaction of the carbon dioxide and the epoxy compound, low activity of the traditional catalyst, environmental pollution and the like, the invention provides a preparation method of an ultra-high crosslinking ionic polymer metal-free heterogeneous catalyst.
In the method, the ionic liquid is prepared by a conventional solvothermal method or is obtained commercially.
Sequentially adding ionic liquid, alpha' -dibromo-paraxylene and anhydrous ferric trichloride into a reactor, adding 1, 2-dichloroethane, reacting at 65-80 ℃ for 24 hours, cooling to room temperature, vacuum filtering and washing a reaction product with methanol for 3-4, and vacuum drying to obtain a porous polymer; sequentially adding the porous polymer, acetonitrile and 1, 3-tetramethylguanidine into a reactor, reacting for 24 hours at 65-80 ℃ in a nitrogen atmosphere, cooling to room temperature, vacuum filtering and washing the reaction product with acetonitrile for 3-4, and vacuum drying to obtain the ultra-high crosslinking ionic polymer metal-free heterogeneous catalyst.
Wherein the ionic liquid is one of 1-benzyl-3-ethyl imidazolium bromide, 4-benzyl-3-ethyl pyridinium bromide, 4-phenyl-3-ethyl pyridinium bromide and 4-phenyl-3-ethyl imidazolium bromide; the molar ratio of the ionic liquid to the alpha, alpha' -dibromo-p-xylene is 1:1-5, and the molar ratio of the ionic liquid to the ferric trichloride is 1:4-7.
The mass ratio of the porous polymer to the 1, 3-tetramethylguanidine is 5-7:1.
The invention also aims to apply the ultra-high crosslinking ionic polymer metal-free heterogeneous catalyst prepared by the method to catalyzing the copolymerization reaction of sulfur dioxide and epoxy compounds; the preparation method comprises the steps of sequentially adding an ultra-high crosslinking ionic polymer metal-free heterogeneous catalyst and an epoxy compound into a high-pressure reaction kettle, then introducing nitrogen with the volume concentration of 99.99% into the high-pressure reaction kettle, replacing the nitrogen with air in the kettle for 2-3 times, introducing sulfur dioxide with the volume concentration of 99%, reacting for 4-12 hours at the temperature of 60-120 ℃ under the pressure of 0.2MPa, cooling to room temperature, dissolving a reactant by adopting dichloromethane, adding methanol for precipitation, filtering, collecting the precipitate, washing the precipitate with methanol for 3-4 times, and then drying to obtain the sulfur dioxide and epoxide copolymer namely the polysulfite.
The invention further aims to apply the ultra-high crosslinking ionic polymer metal-free heterogeneous catalyst prepared by the method to the addition reaction of catalytic carbon dioxide and an epoxy compound, specifically, the ultra-high crosslinking ionic polymer metal-free heterogeneous catalyst and the epoxy compound are sequentially added into a high-pressure reaction kettle, then nitrogen with the volume concentration of 99.99% is introduced into the high-pressure reaction kettle to replace the nitrogen with air in the kettle for 2-3 times, carbon dioxide with the volume concentration of 99.99% is introduced, the pressure of the carbon dioxide is 0.5-3 MPa, the reaction is carried out for 4-12 hours at the temperature of 60-120 ℃, the temperature is reduced to the room temperature, and the product is the cyclic carbonate after the reaction is finished.
The epoxy cyclohexane, propylene oxide, 1, 2-butylene oxide, styrene oxide and epichlorohydrin.
Compared with the prior art, the invention has the following advantages:
(1) The invention maintains the advantages of the ionic liquid, and changes the ionic liquid homogeneous catalyst into a porous heterogeneous catalyst through Friedel-crafts alkylation reaction on the basis of the prior ionic liquid homogeneous catalyst;
(2) The method synthesizes the ultra-high crosslinking ionic polymer metal-free heterogeneous catalyst for the first time, and the catalyst not only can be used for preparing the polysulfite by the copolymerization of sulfur dioxide and an epoxy compound, but also can be used for preparing the cyclic carbonate by the cycloaddition of the epoxy compound and carbon dioxide, and has high product yield and good selectivity;
(3) The preparation method is simple, easy to operate, low in cost, high in catalytic efficiency, free of metal pollution, easy to recycle the catalyst and easy to realize green industrial production.
Drawings
FIG. 1 is a Fourier transform infrared spectroscopy (FTIR) plot of a multi-active-site ultra-high crosslinked ionomer metal-free heterogeneous catalyst of example 1; wherein DBX is alpha, alpha' -dibromo-p-xylene, HBIM is a porous polymer, and HBIM@TMG is an ultra-high crosslinking ionic polymer metal-free heterogeneous catalyst;
FIG. 2 is a Fourier infrared transform infrared spectroscopy (FTIR) plot of the polysulfides prepared in example 1;
FIG. 3 is a chart showing H NMR of cyclic carbonate 1 prepared in example 1;
FIG. 4 is a H NMR chart of the polysulfite 1 prepared in example 1.
Detailed Description
The present invention will be described in further detail by way of examples and drawings, but the protection of the present invention is not limited to the description.
Example 1
(1) Sequentially adding 0.1977g of 1-benzyl imidazole, 0.1737g of bromoacetic acid and 20mL of acetonitrile into a 250mL three-neck flask, heating the three-neck flask in an oil bath kettle at 70 ℃, introducing nitrogen to reflux and react for 24h, transferring the reaction liquid into the single-neck flask after the reaction is finished, evaporating acetonitrile in a vacuum way at 80 ℃, and drying the mixture in a vacuum drying box at 60 ℃ for 24h to obtain 1-benzyl-3-ethylimidazolium bromide;
(2) Placing 0.3715g of 1-benzyl-3-ethylimidazolium bromide in a 250mL single-neck flask, sequentially adding 0.875g of alpha, alpha' -Dibromoparaxylene (DBX) and 0.9732g of anhydrous ferric trichloride, placing the single-neck flask in an oil bath kettle, heating and refluxing for 24h at 70 ℃, cooling to room temperature after the reaction is finished, vacuum filtering and washing a reaction product with methanol for 3 times, and drying in a vacuum drying oven at 60 ℃ for 24h to obtain a porous polymer (HBIM);
(3) Placing 1.1009g of porous polymer into a 250mL single-neck flask, sequentially adding 0.2mL of 1, 3-tetramethylguanidine and 20mL of acetonitrile, placing into an oil bath kettle at 70 ℃, introducing nitrogen, heating and refluxing for 24 hours, cooling to room temperature after the reaction is finished, vacuum filtering and washing a reaction product with acetonitrile for 4 times, and then placing into a vacuum drying oven at 60 ℃ for drying for 24 hours to prepare the ultra-high crosslinking ionic polymer metal-free heterogeneous catalyst HBIM@TMG;
The resulting catalyst was characterized using fourier-infrared-transformed infrared spectroscopy (FTIR), as shown in fig. 1; the bands at 3000-3100 cm -1, about 2900 cm -1 are due to the C-H stretching vibration of-CH 2 -in the polymer backbone, and the absorption bands in the range of 3000-3100 cm -1 and 1608cm -1 are from sp 2 C-H and C=C stretching vibrations, respectively, and observations of these bands indicate an aromatic polymer backbone. The presence of the imidazolinium ion moiety is reflected by bands at 1672cm -1 and 1568cm -1 (typical c=n stretching vibration of imidazole), the absorption peak at 1750cm -1 in the infrared spectrum of HBIM is attributed to c=o stretching vibration of the carboxyl group, and the disappearance of the peak at 1750cm-1 in hbim@tmg initially indicates successful catalyst synthesis.
(4) Sequentially adding 2mL of cyclohexene oxide and 0.0848g of ultra-high crosslinking ionic polymer metal-free heterogeneous catalyst into a 50mL high-pressure reaction kettle; then introducing nitrogen with the volume concentration of 99.99% into the high-pressure reaction kettle, repeatedly introducing nitrogen for 3 times, and then introducing sulfur dioxide with the volume concentration of 99% into the high-pressure reaction kettle, wherein the sulfur dioxide pressure is 0.2MPa; after the air is introduced, the inlet valve and the outlet valve are closed, the rotating speed is set to be 280r/min, the temperature is 110 ℃, and the reaction time is 8 hours; after the reaction is finished, dissolving a reaction product by using methylene dichloride, adding methanol for precipitation, filtering to obtain a precipitate, washing the precipitate with methanol for 3 times, placing the washed precipitate in a vacuum drying oven, and vacuum drying at 40 ℃ for 24 hours to obtain a copolymer of sulfur dioxide and an epoxy compound, wherein the conversion rate of the epoxy cyclohexane is 98% (see figure 4), and the selectivity of the polysulfite is 95%; characterization of the resulting product by fourier transform infrared spectroscopy (FTIR) resulted in fig. 2, which shows the appearance of vibrational peaks associated with s=o and S-O at 1208cm-1 and 728cm-1, respectively, confirming the presence of sulfur dioxide on the backbone;
(5) Sequentially adding 2mL of epichlorohydrin and 0.0848g of ultra-high crosslinking ionic polymer metal-free heterogeneous catalyst into a 50mL high-pressure reaction kettle, then introducing nitrogen with the volume concentration of 99.99% into the high-pressure reaction kettle, repeatedly introducing nitrogen for 3 times, and then introducing carbon dioxide with the volume concentration of 99% into the high-pressure reaction kettle; after the introduction, the inlet valve and the outlet valve are closed, the rotating speed is 280r/min, the temperature is 110 ℃, the carbon dioxide pressure is 1MPa, the reaction time is 8H, the cycloaddition product cyclic carbonate of carbon dioxide and epoxy compound is obtained after cooling, the product yield is 99%, the selectivity is 99%, the obtained product is characterized by adopting a 1H NMR spectrogram, the result is shown in figure 3, the chemical displacement of the product chloropropene carbonate in the figure is respectively d=5.06 ppm,4.63ppm,4.43ppm,3.87ppm and 3.75ppm, and the chloropropene carbonate is determined to be generated by the cycloaddition reaction of carbon dioxide and epoxy compound.
Example 2
(1) Adding 0.2115g of 4-benzyl-pyridine, 0.1954g of bromoacetic acid and 20mL of acetonitrile into a 250mL three-neck flask in sequence, placing the three-neck flask into an oil bath pan, heating at 70 ℃, introducing nitrogen, refluxing for reaction for 24 hours, transferring the reaction liquid into a single-neck flask after the reaction is finished, evaporating acetonitrile in a vacuum way at 80 ℃, and drying at 60 ℃ for 24 hours in a vacuum drying box to prepare 4-benzyl-3-ethylpyridinium bromide;
(2) Placing 0.1623g of 4-benzyl-3-ethyl pyridinium bromide in a 250mL single-neck flask, sequentially adding 0.6492g of alpha, alpha' -dibromo-p-xylene and 0.9735g of anhydrous ferric trichloride, placing the single-neck flask in an oil bath kettle, heating and refluxing for 24h at 70 ℃, cooling to room temperature after the reaction is finished, vacuum filtering and washing a reaction product with methanol for 4 times, and drying in a vacuum drying oven at 60 ℃ for 24h to obtain a porous polymer;
(3) Placing 1.1004g of porous polymer into a 250mL single-neck flask, sequentially adding 0.2mL of 1, 3-tetramethylguanidine and 20mL of acetonitrile, placing into an oil bath kettle at 70 ℃, introducing nitrogen, heating and refluxing for 24 hours, cooling to room temperature after the reaction is finished, vacuum filtering and washing a reaction product with acetonitrile for 3 times, and then placing into a vacuum drying oven at 60 ℃ for drying for 24 hours to obtain the ultra-high crosslinking ionic polymer metal-free heterogeneous catalyst;
(4) The ultra-high crosslinking ionic polymer metal-free heterogeneous catalyst prepared in the step (3) is applied to copolymerization of epoxycyclohexane and sulfur dioxide, and the embodiment is the same as that of example 1, so that a copolymer of sulfur dioxide and an epoxy compound is obtained, wherein the conversion rate of epoxycyclohexane is 97.5%, and the selectivity of polysulfite is 94%;
(5) The ultra-high crosslinking ionic polymer metal-free heterogeneous catalyst prepared in the step (3) is applied to the addition reaction of epichlorohydrin and carbon dioxide, the implementation mode is the same as in the example 1, and the cycloaddition product cyclic carbonate of carbon dioxide and an epoxy compound is obtained, and the product yield is 99.5% and the selectivity is 99%.
Example 3
(1) Adding 0.2551g of 4-phenyl-pyridine, 0.1742g of bromoacetic acid and 20mL of acetonitrile into 250mL of three-neck flask in sequence, heating the three-neck flask in an oil bath kettle at 70 ℃, introducing nitrogen for reflux reaction for 24h, transferring the reaction liquid into a single-neck flask after the reaction is finished, evaporating acetonitrile in a vacuum way at 80 ℃, and drying the mixture in a vacuum drying box at 60 ℃ for 24h to obtain 4-phenyl-3-ethylpyridinium bromide;
(2) Placing 0.1676g of 4-phenyl-3-ethyl pyridinium bromide in a 250mL single-neck flask, sequentially adding 0.6754g of alpha, alpha' -dibromo-p-xylene and 1.0056g of anhydrous ferric trichloride, placing the single-neck flask in an oil bath kettle, heating and refluxing for 24 hours at 70 ℃, cooling to room temperature after the reaction is finished, vacuum filtering and washing a reaction product with methanol for 4 times, and drying in a vacuum drying oven at 60 ℃ for 24 hours to obtain a porous polymer;
(3) Placing 1.1004g of porous polymer into a 250mL single-neck flask, sequentially adding 0.2mL of 1, 3-tetramethylguanidine and 20mL of acetonitrile, placing into an oil bath kettle at 70 ℃, introducing nitrogen, heating and refluxing for 24 hours, cooling to room temperature after the reaction is finished, vacuum filtering and washing a reaction product with acetonitrile for 3 times, and then placing into a vacuum drying oven at 60 ℃ for drying for 24 hours to obtain the ultra-high crosslinking ionic polymer metal-free heterogeneous catalyst;
(4) The non-metal heterogeneous catalyst prepared in the step (3) is applied to copolymerization of epoxycyclohexane and sulfur dioxide, the implementation mode is the same as that of the example 1, a copolymer of sulfur dioxide and an epoxy compound is obtained, the conversion rate of epoxycyclohexane is 97.57%, and the selectivity of polysulfite is 95%;
(5) The metal-free heterogeneous catalyst prepared in the step (3) is applied to the addition reaction of epichlorohydrin and carbon dioxide, the implementation mode is the same as in example 1, and the cycloaddition product cyclic carbonate of carbon dioxide and an epoxy compound is obtained, and the product yield is 99.04% and the selectivity is 96%.
Example 4
(1) Adding 0.1737g of 4-phenyl-imidazole, 0.1944g of bromoacetic acid and 20mL of acetonitrile into a 250mL three-neck flask in sequence, heating the three-neck flask in an oil bath kettle at 75 ℃, introducing nitrogen to reflux and react for 24h, transferring the reaction liquid into a single-neck flask after the reaction is finished, evaporating acetonitrile in a vacuum way at 80 ℃, and drying the mixture in a vacuum drying box at 60 ℃ for 24h to obtain 4-phenyl-3-ethylimidazolium bromide;
(2) Placing 0.6628g of 4-phenyl-3-ethyl imidazolium bromide in a 250mL single-neck flask, sequentially adding 0.9200g of alpha, alpha' -dibromo-p-xylene and 2.5612g of anhydrous ferric trichloride, placing the single-neck flask in an oil bath kettle, heating and refluxing for 24h at 75 ℃, cooling to room temperature after the reaction is finished, vacuum filtering and washing a reaction product with methanol for 4 times, and drying in a vacuum drying oven at 60 ℃ for 24h to obtain a porous polymer;
(3) Placing 1.1371g of porous polymer into a 250mL single-neck flask, sequentially adding 0.2mL of 1, 3-tetramethylguanidine and 20mL of acetonitrile, placing into an oil bath pot at 75 ℃, introducing nitrogen, heating and refluxing for 24 hours, cooling to room temperature after the reaction is finished, vacuum filtering and washing a reaction product with acetonitrile for 3 times, and then placing into a vacuum drying oven at 60 ℃ for drying for 24 hours to obtain the multi-active-center ultrahigh crosslinked ionic polymer metal-free heterogeneous catalyst;
(4) The non-metal heterogeneous catalyst prepared in the step (3) is applied to the copolymerization of the epoxycyclohexane and the sulfur dioxide, the implementation mode is the same as that of the example 1, the copolymer of the sulfur dioxide and the epoxy compound is obtained, the conversion rate of the epoxycyclohexane is 98%, and the selectivity of the polysulfite is 95%;
(5) The metal-free heterogeneous catalyst prepared in the step (3) is applied to the addition reaction of epichlorohydrin and carbon dioxide, the implementation mode is the same as in the example 1, and the cycloaddition product cyclic carbonate of carbon dioxide and an epoxy compound is obtained, and the product yield is 99.6% and the selectivity is 99%.
Claims (7)
1. A preparation method of an ultra-high crosslinking ionic polymer metal-free heterogeneous catalyst is characterized by comprising the following steps of: sequentially adding an ionic liquid, alpha' -dibromo-p-xylene and anhydrous ferric trichloride into a reactor, adding 1, 2-dichloroethane, reacting at 65-80 ℃ for 24 hours, cooling to room temperature, vacuum filtering and washing the reaction product with methanol for 3-4 times, and vacuum drying to obtain a porous polymer; sequentially adding the porous polymer, acetonitrile and 1, 3-tetramethylguanidine into a reactor, reacting for 24 hours at 65-80 ℃ in a nitrogen atmosphere, cooling to room temperature, vacuum filtering and washing the reaction product with acetonitrile for 3-4 times, and vacuum drying to obtain the ultra-high crosslinking ionic polymer metal-free heterogeneous catalyst.
2. The method for preparing the ultra-high crosslinking ionic polymer metal-free heterogeneous catalyst according to claim 1, wherein the method comprises the following steps: the ionic liquid is one of 1-benzyl-3-ethyl imidazolium bromide, 4-benzyl-3-ethyl pyridinium bromide, 4-phenyl-3-ethyl pyridinium bromide and 4-phenyl-3-ethyl imidazolium bromide.
3. The method for preparing the ultra-high crosslinking ionic polymer metal-free heterogeneous catalyst according to claim 1, wherein the method comprises the following steps: the molar ratio of the ionic liquid to the alpha, alpha' -dibromo-p-xylene is 1:1-5, and the molar ratio of the ionic liquid to the ferric trichloride is 1: 4-7.
4. The method for preparing the ultra-high crosslinking ionic polymer metal-free heterogeneous catalyst according to claim 1, wherein the method comprises the following steps: the mass ratio of the porous polymer to the 1, 3-tetramethylguanidine is 5-7:1.
5. The use of the ultra-high crosslinking ionic polymer metal-free heterogeneous catalyst prepared by the preparation method of the ultra-high crosslinking ionic polymer metal-free heterogeneous catalyst in catalyzing copolymerization of sulfur dioxide and an epoxy compound.
6. The use of the ultra-high crosslinking ionic polymer metal-free heterogeneous catalyst prepared by the preparation method of the ultra-high crosslinking ionic polymer metal-free heterogeneous catalyst in catalyzing an addition reaction of carbon dioxide and an epoxy compound.
7. Use according to claim 5 or 6, characterized in that: the epoxy compound is one of epoxycyclohexane, epoxypropane, 1, 2-epoxybutane, styrene oxide and epoxychloropropane.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1208423A (en) * | 1966-10-27 | 1970-10-14 | Hoechst Ag | Process for the manufacture of polycondensates containing halogenomethyl groups |
| US3819583A (en) * | 1971-09-10 | 1974-06-25 | Dainichi Nippon Cables Ltd | Method of preparing ferrocene polymers |
| CN102875601A (en) * | 2012-10-10 | 2013-01-16 | 中山大学 | Preparation method and application for phosphine-oxazoline ligand, and ionic metal complex, enantiomer or racemate thereof |
| CN105218820A (en) * | 2015-10-19 | 2016-01-06 | 昆明理工大学 | The preparation method of a kind of sulfurous gas, carbonic acid gas and epoxy compound composition copolymer |
| CN108948350A (en) * | 2018-06-07 | 2018-12-07 | 华东师范大学 | A kind of preparation and its application of high crosslinking imidazole ion liquid porous organic polymer |
| CN109675634A (en) * | 2019-01-02 | 2019-04-26 | 昆明理工大学 | The preparation method and application of heterogeneous Schiff base catalyst |
| CN110003510A (en) * | 2019-04-16 | 2019-07-12 | 东北大学 | The preparation method of the anion-exchange membrane of main chain group containing imidazole salts |
| CN110484530A (en) * | 2019-07-25 | 2019-11-22 | 山东师范大学 | A kind of Pickering lotion and its preparation method and application based on the load covalent organic frame base hybrid microspheres of enzyme |
| CN110606952A (en) * | 2019-08-27 | 2019-12-24 | 昆明理工大学 | Method for catalyzing copolymerization of sulfur dioxide and epoxy compound by organic porous material |
| KR20200134572A (en) * | 2019-05-22 | 2020-12-02 | 한국과학기술원 | Heterogeneous Organic Catalyst Based on Imidazoline and Method of Preparing Cyclic Carbonate Using the Same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8697884B2 (en) * | 2012-04-13 | 2014-04-15 | I-Shou University | Method of manufacturing cyclic carbonate by using ionic liquid polymer |
-
2023
- 2023-03-17 CN CN202310261681.6A patent/CN116284822B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1208423A (en) * | 1966-10-27 | 1970-10-14 | Hoechst Ag | Process for the manufacture of polycondensates containing halogenomethyl groups |
| US3819583A (en) * | 1971-09-10 | 1974-06-25 | Dainichi Nippon Cables Ltd | Method of preparing ferrocene polymers |
| CN102875601A (en) * | 2012-10-10 | 2013-01-16 | 中山大学 | Preparation method and application for phosphine-oxazoline ligand, and ionic metal complex, enantiomer or racemate thereof |
| CN105218820A (en) * | 2015-10-19 | 2016-01-06 | 昆明理工大学 | The preparation method of a kind of sulfurous gas, carbonic acid gas and epoxy compound composition copolymer |
| CN108948350A (en) * | 2018-06-07 | 2018-12-07 | 华东师范大学 | A kind of preparation and its application of high crosslinking imidazole ion liquid porous organic polymer |
| CN109675634A (en) * | 2019-01-02 | 2019-04-26 | 昆明理工大学 | The preparation method and application of heterogeneous Schiff base catalyst |
| CN110003510A (en) * | 2019-04-16 | 2019-07-12 | 东北大学 | The preparation method of the anion-exchange membrane of main chain group containing imidazole salts |
| KR20200134572A (en) * | 2019-05-22 | 2020-12-02 | 한국과학기술원 | Heterogeneous Organic Catalyst Based on Imidazoline and Method of Preparing Cyclic Carbonate Using the Same |
| CN110484530A (en) * | 2019-07-25 | 2019-11-22 | 山东师范大学 | A kind of Pickering lotion and its preparation method and application based on the load covalent organic frame base hybrid microspheres of enzyme |
| CN110606952A (en) * | 2019-08-27 | 2019-12-24 | 昆明理工大学 | Method for catalyzing copolymerization of sulfur dioxide and epoxy compound by organic porous material |
Non-Patent Citations (3)
| Title |
|---|
| "One-Pot Synthesis of Polyhydroquinoline Derivatives through Organic-Solid-Acid-Catalyzed Hantzsch Condensation Reaction";Mondal, Sujan 等;《CHEMCATCHEM》;20170421;第9卷(第8期);1469-1475 * |
| "三氯化铁离子液体催化异丁烯的齐聚反应";杨淑清，等;《化工学报》;20160831;第67卷(第S1期);276-282 * |
| "二氧化硫在化学资源化利用中的研究进展";陈颖，等;《应用化学》;20220210;第39卷(第2期);223-234 * |
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