CN115960326A - For CO 2 Ionic covalent organic framework catalyst for preparing cyclic carbonate through cycloaddition, preparation method and application - Google Patents
For CO 2 Ionic covalent organic framework catalyst for preparing cyclic carbonate through cycloaddition, preparation method and application Download PDFInfo
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- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 47
- 239000003054 catalyst Substances 0.000 title claims abstract description 33
- 238000006352 cycloaddition reaction Methods 0.000 title claims abstract description 31
- 150000005676 cyclic carbonates Chemical class 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 28
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 16
- 150000002924 oxiranes Chemical class 0.000 claims description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- -1 halogen anions Chemical class 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 238000007126 N-alkylation reaction Methods 0.000 claims description 4
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 claims description 3
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 3
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- HLVFKOKELQSXIQ-UHFFFAOYSA-N 1-bromo-2-methylpropane Chemical compound CC(C)CBr HLVFKOKELQSXIQ-UHFFFAOYSA-N 0.000 claims description 2
- VVHFXJOCUKBZFS-UHFFFAOYSA-N 2-(chloromethyl)-2-methyloxirane Chemical compound ClCC1(C)CO1 VVHFXJOCUKBZFS-UHFFFAOYSA-N 0.000 claims description 2
- UPSXAPQYNGXVBF-UHFFFAOYSA-N 2-bromobutane Chemical compound CCC(C)Br UPSXAPQYNGXVBF-UHFFFAOYSA-N 0.000 claims description 2
- SSZWWUDQMAHNAQ-UHFFFAOYSA-N 3-chloropropane-1,2-diol Chemical compound OCC(O)CCl SSZWWUDQMAHNAQ-UHFFFAOYSA-N 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- RKSOPLXZQNSWAS-UHFFFAOYSA-N tert-butyl bromide Chemical compound CC(C)(C)Br RKSOPLXZQNSWAS-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- ZWAJLVLEBYIOTI-OLQVQODUSA-N (1s,6r)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CCC[C@@H]2O[C@@H]21 ZWAJLVLEBYIOTI-OLQVQODUSA-N 0.000 claims 1
- PQXKWPLDPFFDJP-UHFFFAOYSA-N 2,3-dimethyloxirane Chemical compound CC1OC1C PQXKWPLDPFFDJP-UHFFFAOYSA-N 0.000 claims 1
- MRXPNWXSFCODDY-UHFFFAOYSA-N 2-methyl-2-phenyloxirane Chemical compound C=1C=CC=CC=1C1(C)CO1 MRXPNWXSFCODDY-UHFFFAOYSA-N 0.000 claims 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 claims 1
- 238000005804 alkylation reaction Methods 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 125000004433 nitrogen atom Chemical class N* 0.000 abstract description 3
- 238000007210 heterogeneous catalysis Methods 0.000 abstract description 2
- 238000007306 functionalization reaction Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 239000002608 ionic liquid Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- MHXLAKJJNRIVDR-UHFFFAOYSA-N 2,4,6-trihydroxybenzene-1,3,5-tricarboxylic acid Chemical compound OC1=C(C(=C(C(=C1C(=O)O)O)C(=O)O)O)C(=O)O MHXLAKJJNRIVDR-UHFFFAOYSA-N 0.000 description 2
- QEIRCDAYPQFYBI-UHFFFAOYSA-N 6-(5-aminopyridin-2-yl)pyridin-3-amine Chemical compound N1=CC(N)=CC=C1C1=CC=C(N)C=N1 QEIRCDAYPQFYBI-UHFFFAOYSA-N 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 229920000831 ionic polymer Polymers 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- WDFZWSZNOFELJY-OLQVQODUSA-N (1R,6S)-7-oxabicyclo[4.1.0]hepta-2,4-diene Chemical compound C1=CC=C[C@H]2O[C@H]21 WDFZWSZNOFELJY-OLQVQODUSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- IKOZPOIFMWUXMP-UHFFFAOYSA-N 1-bromophenanthridine Chemical compound C1=CC=CC2=C3C(Br)=CC=CC3=NC=C21 IKOZPOIFMWUXMP-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000002181 crystalline organic material Substances 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- ZMMJGEGLRURXTF-UHFFFAOYSA-N ethidium bromide Chemical compound [Br-].C12=CC(N)=CC=C2C2=CC=C(N)C=C2[N+](CC)=C1C1=CC=CC=C1 ZMMJGEGLRURXTF-UHFFFAOYSA-N 0.000 description 1
- 229960005542 ethidium bromide Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- QQOWHRYOXYEMTL-UHFFFAOYSA-N triazin-4-amine Chemical compound N=C1C=CN=NN1 QQOWHRYOXYEMTL-UHFFFAOYSA-N 0.000 description 1
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention belongs to CO 2 The technical field of heterogeneous catalysis of resource utilization and discloses a catalyst for CO 2 An ionic covalent organic framework catalyst for preparing cyclic carbonate by cycloaddition, a preparation method and application thereof. The invention takes TpBpy as an original COF framework, and builds reaction sites on elements to carry out functionalization by carrying out alkylation reaction on different halogenated alkanes and N atoms in the framework, thereby obtaining the ionic covalent organic framework material in one step. The material can be used as a catalyst to catalyze CO under the conditions of no metal, no solvent and no promoter 2 Cycloaddition reaction to obtain high yield of cyclic carbonate. The material has excellent propertiesThe method has the advantages of high cycle stability and wide application prospect.
Description
Technical Field
The invention belongs to CO 2 The technical field of heterogeneous catalysis for resource utilization, and relates to a catalyst for CO 2 An ionic covalent organic framework catalyst for preparing cyclic carbonate by cycloaddition, a preparation method and application thereof.
Background
With the progress of the industrialized age, CO in the atmosphere 2 The concentration is rising day by day, and the greenhouse effect caused by the rising concentration becomes a big problem for human beings. However, CO 2 As a reproducible nontoxic C1 resource, the product can be converted into a chemical with a high added value under certain conditions, thereby realizing the efficient utilization of the resource and reducing the environmental hazard. With CO 2 Cycloaddition reaction with epoxide to generate cyclic carbonate with atom utilization rate up to 100%, which meets the requirement of green chemical production and becomes CO 2 Research in the field of resource utilization is hot.
Is currently applied to CO 2 The catalyst for cycloaddition of an epoxide to form a cyclic carbonate includes homogeneous catalysts and heterogeneous catalysts. Homogeneous catalysts such as ionic liquids, alkali metal salts and organic bases have the disadvantage of being difficult to recover after the reaction. Heterogeneous catalysts such as metal oxides, metal organic framework materials, zeolite molecular sieves, polyionic liquids, etc. are easy to recover, but still have many problems, such as metal release from metal oxides during the reaction process, poor cycle stability of metal organic framework materials (ACS appl. Mater. Interfaces 2020,12, 24868-24876), difficulty in modifying zeolite molecular sieves, dependence on promoters, and generally low catalytic activity of polyionic liquids, and need of high catalyst usage (CN 112159386A), (CN 113637163A), (CN 115340629A), etc.
Covalent Organic Frameworks (COFs) are a porous crystalline organic material formed by strong covalent bonds. COF materials have attracted much attention because of their properties such as large specific surface area, high thermal stability, and easy modification. However, the absence of halide nucleophilic groups in COF generally requires the addition of a CO-catalyst such as tetrabutylammonium bromide to effect the reaction of the epoxide with CO 2 High efficiency cycloaddition reaction. Chinese patent CN 11535353599A discloses an ionic liquid/ionic covalent organic framework compositeThe material is prepared by taking 1,3, 5-trialdehyde phloroglucinol and ethidium bromide or bromophenanthridine as structural monomers and performing one-step synthesis reaction with ionic liquid by a one-pot method, and is applied to CO 2 Cycloaddition reaction with an epoxide. The method can conveniently prepare the catalyst for the cycloaddition reaction, and has high catalytic efficiency, but the method uses tetrabutylammonium bromide as a homogeneous cocatalyst, which increases the recovery difficulty of the catalyst. Chinese patent CN114832858A discloses a preparation process of a functional modified CTF-based composite material, namely different Ionic Liquids (ILs) are grafted on a two-dimensional iminotriazine COF (CTF) material and applied to CO 2 In a cycloaddition reaction with an epoxide. The method can catalyze the cycloaddition of carbon dioxide and epoxide under the condition of no solvent and no promoter, and the yield of cyclic carbonate is high. However, the preparation process of the ILs @ CTF composite material needs three steps, namely synthesis of COF, modification of COF by alkyl halide and final obtaining of the ILs @ CTF composite material, and the complicated material preparation process also limits industrialization to a certain extent.
TpBpy has a two-dimensional planar hexagonal structure, has better structural regularity than triazine COFs materials as one of imino COF materials, and is equivalent to the crystallinity of boron-containing COFs. The current synthetic method for tpbppy is mainly solvothermal (j. Mater. Chem. A,2016,4 (7), 2682-2690). It is reported that,
as a catalyst for the carbon dioxide cycloaddition reaction, the catalyst can be used for obtaining the yield of 95 percent of cyclic carbonate under the mild condition without solvent or cocatalyst. However, the inevitable detachment of copper ions from the catalyst during the reaction and the complicated modification method of the catalyst have limited their application (j.am. Chem. Soc.2016,138, 15790-15796). Since the hexagonal side of TpBpy contains rich bipyridyl sites, nitrogen atoms on the bipyridyl sites can perform N-alkylation reaction with halogenated alkane, and the ionic covalent bond can be generated in only one stepMachine frame (cof). The material has abundant halogen ions, and can catalyze the cycloaddition reaction of carbon dioxide and epoxide under the conditions of no metal, no solvent and no promoter.
Disclosure of Invention
The invention aims to provide a preparation method of a novel ionic covalent organic framework and catalytic application thereof, aiming at the defects in the prior art. Taking TpBpy as an original COF framework, functionalizing by constructing reaction sites on motifs to obtain the ionic covalent organic framework material in one step, and investigating the CO pair 2 Catalytic properties of cycloaddition reactions. The catalyst can catalyze CO under the condition of no metal, no solvent and no promoter 2 Cycloaddition reaction and high yield of cyclic carbonate at relatively low temperature and pressure. Besides, the catalyst can keep good stability in the reaction system.
The technical scheme of the invention is as follows:
for CO 2 The ionic covalent organic framework catalyst for preparing cyclic carbonate by cycloaddition takes a covalent organic framework TpBpy as a framework, halogenated alkane is grafted to a COF material by N alkylation reaction, and the ionic covalent organic framework catalyst with different halogen anions and different alkyl groups is obtained, and the structural formula is as follows:
wherein X = Cl, br, I.
For CO 2 The preparation method of the ionic covalent organic framework catalyst for preparing the cyclic carbonate through cycloaddition comprises the following preparation steps:
mixing an organic solvent with a covalent organic frame material TpBpy according to the mass ratio of 50-100, or no organic solvent; then adding halogenated alkane, and controlling the mass ratio of the halogenated alkane to the covalent organic framework material TpBpy to be 1-50; and carrying out reflux reaction for 6-72 h under the protection of nitrogen, cooling, filtering the product, washing with acetonitrile for multiple times, and drying overnight to obtain the ionic covalent organic framework catalyst.
The organic solvent is any one of acetonitrile, N-dimethylformamide and toluene.
The halogenated alkane is any one of n-butyl chloride, n-butyl bromide, n-butyl iodide, sec-butyl bromide, tert-butyl bromide, iso-butyl bromide, epichlorohydrin, epibromohydrin and 3-chloro-1, 2-propanediol.
The ionic covalent organic framework catalyst is applied to catalyzing cycloaddition reaction of epoxide and carbon dioxide under the condition of no solvent and no promoter, the epoxide and the ionic covalent organic framework catalyst are added into a high-pressure kettle, the usage amount of the catalyst is 0.1-1 mmol percent based on the content of halogen ions, the reaction pressure is 0.1-2 MPa, the reaction temperature is 25-150 ℃, and the reaction time is 6-48 h.
The epoxide is one of epoxypropane, epoxybutane, epichlorohydrin, epoxybromopropane, styrene oxide, 2-phenyl epoxypropane, methyl epoxypropane, 2- (chloromethyl) -1, 2-epoxypropane and epoxycyclohexane.
The invention has the beneficial effects that:
1. the catalyst takes COF as a framework material, and is carried on CO in comparison with other carriers such as MOF and the like 2 The stability in the cycloaddition reaction is greatly improved.
TpBpy has rich N sites, and the ionic covalent organic framework material can be prepared by only one-step N alkylation reaction.
3. The prepared ionic covalent organic framework material contains abundant halogen ions and can efficiently catalyze CO under the conditions of no metal, no solvent and no cocatalyst 2 And (3) performing cycloaddition reaction.
Drawings
FIG. 1 is an XRD pattern of TpBpy and TpBpy-nBuBr prepared in example 1 of the present invention.
FIG. 2 is an SEM picture of TpBpy-nBuBr prepared in example 1 of the present invention.
FIG. 3 shows TpBpy prepared in examples 1,2, 3 and 4 and different ionic covalent organic frameworksN of the shelf 2 Adsorption and desorption isotherm diagrams.
Detailed Description
The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.
Example 1
Preparation of Ionic covalent organic framework Material TpBpy-nBuBr
2,4, 6-trihydroxy-1, 3, 5-benzenetricarboxylic acid and 2,2 '-bipyridine-5, 5' -diamine were added to a Schlenk tube in a molar ratio of 2:3, a mixed solvent of 6mLN, N-dimethylacetamide (4.5 mL) and o-dichlorobenzene (1.5 mL) was added, ultrasonic treatment was performed, 0.6mL of 6M aqueous acetic acid was added, degassing was performed three times, and heating was performed at 120 ℃ for 72 hours. After cooling, the product is filtered off and washed with N, N-dimethylacetamide and methanol and dried overnight at 100 ℃ to give TpBpy. 100mg of TpBpy material was weighed, added with 10g of N, N-dimethylformamide, followed by 2g of n-butyl bromide, and reacted under reflux under nitrogen for 48 hours. After cooling the product was filtered off and washed several times with acetonitrile and dried overnight to give the ionic covalent organic framework tpbppy-nbubbr.
Example 2
Preparation of Ionic covalent organic framework Material TpBpy-nBuCl
Analogously to example 1, the other conditions were unchanged, except that n-butyl bromide was replaced by n-butyl chloride.
Example 3
Preparation of Ionic covalent organic framework Material TpBpy-nBuI
Similar to example 1, the other conditions were unchanged, except that n-butyl bromide was replaced with n-butyl iodide and the alkylation reaction time was 24h.
Example 4
Preparation of Ionic covalent organic framework Material TpBpy-ECH
2,4, 6-trihydroxy-1, 3, 5-benzenetricarboxylic acid and 2,2 '-bipyridine-5, 5' -diamine were added to a Schlenk tube in a molar ratio of 2. After cooling the product was filtered off and washed with N, N-dimethylacetamide and methanol and dried overnight at 100 ℃ to give TpBpy. 100mg of TpBpy material is weighed, 5g of epichlorohydrin is added, and the reflux reaction is carried out for 48 hours under the protection of nitrogen. After cooling the product was filtered off and washed several times with acetonitrile and dried overnight to yield the ionic covalent organic framework TpBpy-ECH.
Example 5
TpBpy-nBuBr catalyzed CO 2 Study on cycloaddition performance of epichlorohydrin
20mmol of epichlorohydrin and 50mg of TpBpy-nBuBr were placed in a 100mL autoclave using CO 2 The gas is replaced three times and 0.7MPa of CO is introduced 2 And heating the reaction kettle to 100 ℃ and then reacting for 24 hours. After the completion of the reaction, the reaction vessel was cooled to room temperature, and the reaction solution was filtered, and the yield of the reaction was 83.9% by gas chromatography analysis.
Example 6
TpBpy-nBuCl catalyzed CO 2 Study on cycloaddition performance of epichlorohydrin
Similar to example 5, except that TpBpy-nBuBr was replaced with TpBpy-nBuCl, the reaction yield was 41.3% by gas chromatography analysis.
Example 7
TpBpy-nBuI catalyzed CO 2 Study on cycloaddition performance of epichlorohydrin
Similar to example 5, other conditions were changed except that TpBpy-nBuBr was replaced with TpBpy-nBuI, and the yield of the reaction was 99.9% by gas chromatography.
Example 8
TpBpy-ECH catalyzed CO 2 Study on cycloaddition performance of epichlorohydrin
Similar to example 5, the other conditions were changed except that TpBpy-nBuBr was replaced with TpBpy-ECH, and the yield of the reaction was 49% by gas chromatography.
Example 9
TpBpy-nBuBr catalyzed CO 2 Study on cycloaddition Properties to styrene oxide
20mmol of benzene oxide was added to a 100mL autoclaveEthylene with 75mg of TpBpy-nBuBr using CO 2 The gas is replaced three times, and 0.7MPa of CO is introduced 2 And heating the reaction kettle to 100 ℃ and then reacting for 24 hours. After the reaction was completed, the reaction vessel was cooled to room temperature, and the reaction solution was filtered, and the reaction yield was 85.3% by gas chromatography
Example 10
TpBpy-ECH catalyzed CO 2 Study on cycloaddition stability of epichlorohydrin
20mmol of epichlorohydrin and 50mg of TpBpy-ECH were placed in a 100mL autoclave using CO 2 The gas is replaced three times and 0.7MPa of CO is introduced 2 And heating the reaction kettle to 100 ℃ and then reacting for 24 hours. After completion of the reaction, the reaction vessel was cooled to room temperature, and the reaction solution was filtered, and the yield of the reaction was analyzed using gas chromatography. The filtered catalyst was washed with ethyl acetate, dried and applied to the next reaction, and the reuse data are shown in the following table. Since epichlorohydrin is a good N alkylation reagent and can generate alkylation reaction with N in TpBpy to generate iCOF, during the process of catalyzing epichlorohydrin by using TpBpy-ECH, epichlorohydrin can continuously generate alkylation reaction with vacant N atoms in TpBpy-ECH, so that the concentration of chloride ions at active sites of the reaction is increased, and the product yield in a circulation experiment is increased.
TABLE 1 TpBpy-ECH catalyzes CO 2 Cycloaddition and reuse result with epichlorohydrin
The above description is only a preferred embodiment of the present invention, but the present invention is not limited to the above embodiment, and all modifications, substitutions, etc. based on the innovative principles of the present invention are within the protection of the present invention.
Claims (6)
1. For CO 2 The ionic covalent organic framework catalyst for preparing the cyclic carbonate by cycloaddition is characterized in that the ionic covalent organic framework catalyst with different halogen anions and different alkyl groups is obtained by taking a covalent organic framework TpBpy as a framework and grafting halogenated alkane to a COF material through N alkylation reaction, and the structural formula is as follows:
wherein X = Cl, br, I.
2. The method of claim 1, comprising the steps of:
mixing an organic solvent with a common organic frame material TpBpy according to a mass ratio of 50-100, or no organic solvent; then adding halogenated alkane, and controlling the mass ratio of the halogenated alkane to the covalent organic framework material TpBpy to be 1-50; and carrying out reflux reaction for 6-72 h under the protection of nitrogen, cooling, filtering out the product, washing with acetonitrile for multiple times, and drying overnight to obtain the ionic covalent organic framework catalyst.
3. The method according to claim 2, wherein the organic solvent is any one of acetonitrile, N-dimethylformamide and toluene.
4. The method according to claim 2 or 3, wherein the halogenated alkane is any one of n-butyl chloride, n-butyl bromide, n-butyl iodide, sec-butyl bromide, tert-butyl bromide, iso-butyl bromide, epichlorohydrin, epibromohydrin, and 3-chloro-1, 2-propanediol.
5. The ionic covalent organic framework catalyst of claim 1 is applied to catalyzing cycloaddition reaction of epoxide and carbon dioxide under the condition of no solvent and no promoter, and is characterized in that the epoxide and the ionic covalent organic framework catalyst are added into an autoclave, the usage amount of the catalyst is 0.1-1 mmol percent based on the content of halogen ions, the reaction pressure is 0.1-2 MPa, the reaction temperature is 25-150 ℃, and the reaction time is 6-48 h.
6. The ionic covalent organic framework catalyst of claim 5, applied to a solvent-free and cocatalyst-free condition for catalyzing cycloaddition reaction of epoxide and carbon dioxide, wherein the epoxide is one of propylene oxide, butylene oxide, epichlorohydrin, bromohydrin, styrene oxide, 2-phenylpropylene oxide, methylpropylene oxide, 2- (chloromethyl) -1, 2-propylene oxide, and cyclohexene oxide.
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| CN113912805A (en) * | 2021-11-14 | 2022-01-11 | 福州大学 | Organic porous polymer for catalyzing cycloaddition of epoxide and carbon dioxide |
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