CN116273185A - Immobilized bifunctional catalyst and method for preparing cyclic carbonate in outer loop reaction process - Google Patents
Immobilized bifunctional catalyst and method for preparing cyclic carbonate in outer loop reaction process Download PDFInfo
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- CN116273185A CN116273185A CN202310183650.3A CN202310183650A CN116273185A CN 116273185 A CN116273185 A CN 116273185A CN 202310183650 A CN202310183650 A CN 202310183650A CN 116273185 A CN116273185 A CN 116273185A
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- molar ratio
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- carbon dioxide
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 85
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 37
- 150000005676 cyclic carbonates Chemical class 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 27
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 112
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 56
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 56
- 238000004821 distillation Methods 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 43
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 39
- 230000032683 aging Effects 0.000 claims description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 21
- 125000002947 alkylene group Chemical group 0.000 claims description 20
- 238000004440 column chromatography Methods 0.000 claims description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000011261 inert gas Substances 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- PQMCFTMVQORYJC-UHFFFAOYSA-N 2-aminocyclohexan-1-ol Chemical compound NC1CCCCC1O PQMCFTMVQORYJC-UHFFFAOYSA-N 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 238000011049 filling Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000005859 coupling reaction Methods 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- NJWIMFZLESWFIM-UHFFFAOYSA-N 2-(chloromethyl)pyridine Chemical compound ClCC1=CC=CC=N1 NJWIMFZLESWFIM-UHFFFAOYSA-N 0.000 claims description 3
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- 238000010923 batch production Methods 0.000 claims description 3
- 238000010924 continuous production Methods 0.000 claims description 3
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 claims description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 3
- 229920002866 paraformaldehyde Polymers 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 239000012312 sodium hydride Substances 0.000 claims description 3
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- NMLXKNNXODLJIN-UHFFFAOYSA-M zinc;carbanide;chloride Chemical compound [CH3-].[Zn+]Cl NMLXKNNXODLJIN-UHFFFAOYSA-M 0.000 claims description 3
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-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
- 238000001704 evaporation Methods 0.000 claims description 2
- 239000003622 immobilized catalyst Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000011344 liquid material Substances 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 229920002521 macromolecule Polymers 0.000 claims description 2
- 230000001105 regulatory effect Effects 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
- 239000006185 dispersion Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 8
- 239000007858 starting material Substances 0.000 description 8
- 239000003480 eluent Substances 0.000 description 6
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000013589 supplement Substances 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-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
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002262 Schiff base Substances 0.000 description 2
- 150000004753 Schiff bases Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000004714 phosphonium salts Chemical group 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005865 alkene metathesis reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000002608 ionic liquid Chemical group 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- 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
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
- C07D317/38—Ethylene carbonate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/069—Aluminium compounds without C-aluminium linkages
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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- B01J2531/31—Aluminium
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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
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Abstract
The invention provides an immobilized bifunctional catalyst and a method for preparing cyclic carbonate in an outer loop reaction process, belonging to the technical field of carbonate preparation. The double-function catalyst is a polymer-supported heteronuclear bimetallic complex, and can be applied to an outer loop reaction process to effectively strengthen gas-liquid-solid multiphase mixed mass transfer and improve reaction efficiency. Avoiding separation of catalyst and reaction products under the condition of ensuring high activity catalysis, and reducing distillation energy consumption. The reaction may be carried out at a lower carbon dioxide pressure and a milder reaction temperature. The invention provides a sustainable stable continuous operation mode. Solves the problem of low reaction degree in the prior art, and has good industrial application value.
Description
Technical Field
The invention belongs to the technical field of carbonate preparation, relates to a method for preparing cyclic carbonate by combining an immobilized difunctional heteronuclear bimetallic complex catalyst with an outer loop process, and relates to a method for preparing cyclic carbonate by coupling reaction of alkylene oxide and carbon dioxide.
Background
Carbon dioxide (CO) 2 ) As an important carbon source on earth, it can be converted into carbohydrates by photosynthesis while releasing oxygen, which is one of the most important reactions to maintain ecological cycle. Today CO in human daily life and industrial production 2 The excessive emission of (2) breaks the balance of natural balance, so that CO 2 Become the main gas causing the greenhouse effect. Thus, CO 2 Has become one of the most interesting strategic research subjects worldwide, both in terms of emissions reduction and in terms of chemical or physical fixation. Under the action of a catalyst, carbon dioxide can be subjected to coupling reaction with alkylene oxide to prepare cyclic carbonate. The cyclic carbonates are widely used as high-boiling point and high-polarity organic solvents with excellent performance in the fields of organic synthesis, cosmetic industry, gas separation, battery electrolyte, metal extraction and the like.
At present, a plurality of patent reports on the preparation of cyclic carbonate by coupling carbon dioxide and alkylene oxide exist at home and abroad. For example, tetrahydrocarbon quaternary ammonium salt, quaternary phosphonium salt, ionic liquid, tetradentate Schiff base containing quaternary ammonium salt in molecule and the like are adopted as catalysts to realize the preparation of the cyclic carbonate, but the problem of dependence on high temperature and high pressure is generally existed. In recent years, the tetradentate Schiff base aluminum complex is used as a catalyst, under the synergistic effect of quaternary ammonium salt or quaternary phosphonium salt, the coupling reaction of carbon dioxide and alkylene oxide is realized, and the corresponding cyclic carbonates (CN 1416953, CN 1415416 and CN 1544431) are synthesized, so that the reaction activity is greatly improved. In addition, we report that the enhanced cyclic carbonate preparation method (CN 110003163, CN 110028483) and the heteronuclear bimetallic complex bimetallic system have remarkable effects of alkylene oxide activation and carbon dioxide insertion (CN 113321688) by adopting a loop spray and jet reactor to carry out gas-liquid mixing process, the gas-liquid mass transfer is further improved on the basis of the original high-activity bifunctional catalyst, the reaction pressure is reduced, the reaction can be carried out at a low pressure of 0.8MPa, but the high-activity catalyst still faces the problems that a homogeneous catalyst needs to be separated, and the like, and the olefin metathesis polymerization is carried out on the original heteronuclear bimetallic catalyst, so that the immobilized bifunctional catalyst is obtained.
Disclosure of Invention
The invention mainly aims to provide an immobilized difunctional heteronuclear bimetallic complex catalyst and a method for synthesizing cyclic carbonate by combining the catalyst with an outer loop reaction process to strengthen gas-liquid mass transfer and efficiently realizing coupling reaction of carbon dioxide and alkylene oxide.
The technical scheme of the invention is as follows:
an immobilized bifunctional catalyst, which is a heteronuclear bimetallic complex loaded by a macromolecule and has the structure as follows:
wherein: x is X - Is Cl -1 、Br -1 、I -1 Negative ions; n and m are positive integers.
The synthesis reaction formula of the immobilized bifunctional catalyst is as follows:
the preparation method of the immobilized bifunctional catalyst comprises the following steps:
dissolving a raw material 1 in toluene under the protection of inert gas, adding triethylamine with the molar ratio of 1-1.5:1 to the raw material, stirring for 5-10 min, slowly dropwise adding tin tetrachloride with the molar ratio of 0.3-0.5:1 to the raw material 1, keeping the temperature at 30 ℃ or below, keeping the temperature for 5-10 min after dropwise adding paraformaldehyde with the molar ratio of 5-7:1 to the raw material 1, heating to 80-100 ℃, and reacting for 10-15 h; after the reaction is finished, cooling to room temperature, filtering to remove filter cakes, collecting filtrate, evaporating toluene to obtain a viscous crude intermediate 1, adding methanol with the mass ratio of 3-5:1 to the crude intermediate 1, cooling to-5-0 ℃, stirring for 2-4 h to separate out a product, filtering and drying to obtain the intermediate 1.
Dissolving the intermediate 1 and the raw material 2 with the molar ratio of 1:1 by using dichloromethane under the protection of inert gas, dripping 1, 2-cyclohexanediamine with the molar ratio of 1:1 with the intermediate 1 at a constant speed within 1-2 h at room temperature, reacting for 3-5 h at room temperature after dripping, distilling under reduced pressure to remove dichloromethane, and purifying by column chromatography to obtain the intermediate 2.
Adding the intermediate 2 and potassium carbonate with the molar ratio of 1:2-3 into acetone under the protection of inert gas, stirring uniformly, adding triethylamine with the molar ratio of 2-3:1 into the mixture, heating the mixture to reflux, reacting the mixture for 20-24 hours, distilling the mixture under reduced pressure to remove the acetone, and purifying the mixture by column chromatography to obtain the intermediate 3.
Dissolving 2-aminocyclohexanol in tetrahydrofuran under the protection of inert gas, adding sodium hydride with the molar ratio of 1-1.2:1 with 2-aminocyclohexanol, stirring for 20-30 min, adding 2-chloromethylpyridine with the molar ratio of 1:1 with 2-aminocyclohexanol, heating to reflux reaction for 20-25 h, and performing column chromatography purification after removing tetrahydrofuran by reduced pressure distillation to obtain an intermediate 4.
Dissolving the intermediate 4 and the raw material 2 with ethanol in a molar ratio of 1:1 under the protection of inert gas, heating to reflux, reacting for 8-10 h, distilling under reduced pressure to remove ethanol, and purifying by column chromatography to obtain an intermediate 5.
Dissolving an intermediate 5, an intermediate 3 and a raw material 3 in a molar ratio of 1:1:1 with dichloromethane under the protection of inert gas, adding N, N' -dicyclohexylcarbodiimide in a molar ratio of 1-1.2:1 with the intermediate 5, reacting for 68-72 h at room temperature, filtering, collecting a filter cake, and purifying by column chromatography to obtain the intermediate 6.
Dissolving the intermediate 6 in chloroform under the protection of inert gas, adding diethyl aluminum chloride with the molar ratio of 1:1 with the intermediate 6 at constant speed within 2-3 h at room temperature, continuing to react for 2-3 h after the addition, distilling under reduced pressure to remove chloroform, and purifying by column chromatography to obtain the intermediate 7.
Dissolving the intermediate 7 in chloroform under the protection of inert gas, adding methyl zinc chloride with the molar ratio of 1:1 with the intermediate 7 at constant speed within 2-3 h at room temperature, continuing to react for 2-3 h after the addition, distilling under reduced pressure to remove chloroform, and purifying by column chromatography to obtain an intermediate 8.
Dissolving intermediate 8 with the molar ratio of n to m and norbornene in toluene under the protection of inert gas, adding azodiisobutyronitrile with the molar ratio of 1 to 200-500 to the intermediate 8, heating to 60-80 ℃, reacting for 6-8 h, and distilling under reduced pressure to remove the solvent to obtain the immobilized bifunctional catalyst.
The method for preparing the cyclic carbonate by the immobilized bifunctional catalyst in the outer loop reaction process adopts an outer loop reactor, and uses the immobilized bifunctional catalyst to carry out coupling reaction on carbon dioxide and alkylene oxide as raw materials under the reaction pressure of 0.4-3.0 MPa and the reaction temperature of 50-150 ℃.
The reaction process can be classified into a batch process and a continuous process.
The batch reaction process comprises the following steps: filling an immobilized bifunctional catalyst in an outer loop reactor, and adding a certain amount of cyclic carbonate as an initial circulating material; heating the initial materials to the reaction temperature through a heat exchanger, and introducing carbon dioxide to the reaction system pressure which is the reaction pressure; after the preparation is finished, introducing alkylene oxide and carbon dioxide into the outer loop reactor for reaction, and maintaining the reaction pressure; after the addition of the alkylene oxide is finished, continuing to react until the alkylene oxide is completely consumed, then cooling and discharging pressure to transfer the material into a flash tank, and removing carbon dioxide to obtain cyclic carbonate; and the next kettle reaction can be carried out after the outer loop reactor is emptied.
The continuous reaction process comprises the following steps:
filling the outer loop reactor and an aging tank with a supported bifunctional catalyst, and adding cyclic carbonate into the outer loop reactor as an initial circulating material; heating the initial materials to the reaction temperature through a heat exchanger, and introducing carbon dioxide to the reaction system pressure which is the reaction pressure; continuously introducing alkylene oxide and carbon dioxide into the outer loop reactor, transferring a reaction material part of the outer loop reactor into an aging tank while feeding, and discharging liquid materials in the aging tank through a discharge pipe and a back pressure valve to form a liquid seal; regulating the pressure between the outer loop reactor and the aging tank to be unchanged through carbon dioxide, and continuously outputting the aged materials to a flash tank to discharge carbon dioxide to obtain cyclic carbonate; in the whole process, the balance of the materials in the outer loop reactor, the ageing tank and the flash tank is controlled, and the steady state of continuous feeding reaction and discharge collection is maintained.
The reaction pressure of the cyclic carbonate reaction process is preferably 0.6-1.2 MPa, and the reaction temperature is preferably 80-120 ℃.
The mass ratio of the alkylene oxide to the catalyst is 10-0.1 g/g.h -1 。
The alkylene oxide is propylene oxide, ethylene oxide, epichlorohydrin, styrene oxide, phenyl glycidyl ether or epoxycyclohexane.
The outer loop reactor comprises a spray or jet reactor.
The loading mode of the immobilized catalyst is material package, loop filling, reactor space filling or dispersing and the like.
The invention has the beneficial effects that:
(1) The outer loop reaction process can effectively strengthen gas-liquid-solid multiphase mixed mass transfer and improve the reaction efficiency.
(2) The immobilized bifunctional heteronuclear bimetallic catalyst avoids separation of the catalyst and reaction products under the condition of ensuring high activity catalysis, and reduces distillation energy consumption.
(3) The reaction may be carried out at a lower carbon dioxide pressure and a milder reaction temperature.
(4) A manner of sustainable stable continuous operation is provided.
(5) Solves the problem of low reaction degree in the prior art, and has good industrial application value.
Drawings
FIG. 1 is a schematic diagram of an external loop reaction batch process system according to the present invention.
FIG. 2 is a schematic diagram of an external loop reaction continuous process system according to the present invention.
Detailed Description
The technical solutions of the present invention are further stated below by examples.
Example 1-1
Dissolving a raw material 1 (0.99 g,3.85 mmol) in toluene (5.00 g) under the protection of nitrogen, adding triethylamine (0.58 g,5.78 mmol) with a 1:1 molar ratio to the raw material 1, stirring for 10min, slowly dropwise adding tin tetrachloride (0.54 g,1.54 mmol) with a 0.4:1 molar ratio to the raw material 1, keeping the temperature at not more than 30 ℃, keeping the temperature for 10min after dropwise adding paraformaldehyde (0.69 g,23.10 mmol) with a 6:1 molar ratio to the raw material 1, and heating to 95 ℃ for reaction for 15h; after the reaction was completed, the reaction mixture was cooled to room temperature, the filter cake was removed by filtration, the filtrate was collected, toluene was distilled off to obtain a crude intermediate 1 (2.05 g) in a viscous form, methanol (10.25 g) was added in a mass ratio of 5:1 with respect to the crude intermediate 1, the temperature was lowered to-5 ℃, the solid was precipitated by stirring for 2 hours, and intermediate 1 (0.74 g,2.60mmol, yield 68%) was obtained by filtration and drying.
Intermediate 1 (2.03 g,7.11 mmol) and starting material 2 (1.38 g,7.11 mmol) in a molar ratio of 1:1 were dissolved in methylene chloride (25.00 g) under nitrogen protection, 1, 2-cyclohexanediamine (0.82 g,7.11 mmol) in a molar ratio of 1:1 to intermediate 1 was added dropwise at a constant rate over 2h at room temperature, the mixture was reacted at room temperature for 3h, and after removal of methylene chloride by distillation under reduced pressure, column chromatography (eluent: methanol=10:1) was carried out to purify intermediate 2 (2.61 g,4.69mmol, yield 66%).
Intermediate 2 (3.47 g,6.23 mmol) and potassium carbonate (1.72 g,12.46 mmol) in a molar ratio of 1:2 were added to acetone (20.00 g) under nitrogen protection, stirred well, triethylamine (1.58 g,15.58 mmol) in a molar ratio of 2.5:1 to intermediate 2 was added, heated to reflux, reacted for 24h, distilled under reduced pressure to remove acetone, and purified by column chromatography (eluent volume ratio: dichloromethane: methanol=1:1) to give intermediate 3 (3.70 g,5.61mmol, yield 90%).
2-aminocyclohexanol was dissolved in tetrahydrofuran under nitrogen protection, sodium hydride (0.19 g,7.72 mmol) was added in a molar ratio to 2-aminocyclohexanol (0.89 g,7.72 mmol) of 1:1, stirred for 30min, 2-chloromethylpyridine (0.98 g,7.72 mmol) in a molar ratio to 2-aminocyclohexanol of 1:1 was added, heated to reflux for 24h, and after removal of tetrahydrofuran by distillation under reduced pressure, column chromatography (eluent volume ratio: dichloromethane: methanol=5:1) was performed to give intermediate 4 (1.27 g,6.18mmol, yield 80%).
Intermediate 4 (1.35 g,6.56 mmol) and starting material 2 (1.27 g,6.56 mmol) were dissolved in ethanol (30.00 g) under nitrogen protection, heated to reflux, reacted for 10h, distilled under reduced pressure to remove ethanol, and purified by column chromatography (eluent volume ratio dichloromethane: methanol=5:1) to give intermediate 5 (2.36 g,6.17mmol, yield 94%).
Intermediate 5 (2.36 g,6.17 mmol), intermediate 3 (4.07 g,6.17 mmol) and starting material 3 (1.12 g,6.17 mmol) were dissolved in methylene chloride at a molar ratio of 1:1:1 under nitrogen, N' -dicyclohexylcarbodiimide (1.53 g,7.40 mmol) was added to the molar ratio of 1.2:1 to intermediate 5, reacted at room temperature for 72h, filtered, and the filter cake was collected and purified by column chromatography (eluent volume ratio methylene chloride: methanol=2:1) to give intermediate 6 (3.47 g,2.96mmol, yield 48%).
Intermediate 6 (1.17 g,1.00 mmol) was dissolved in chloroform (5.00 g) under nitrogen protection, diethyl aluminum chloride (1.00 ml,1.00mmol, toluene solution with a concentration of 1 mol/L) was added at a constant rate over 3h at room temperature to intermediate 6, the reaction was continued for 2h after the addition, and column chromatography (eluent volume ratio chloroform: methanol=1:2) purification was performed after distillation under reduced pressure to give intermediate 7 (0.73 g,0.59mmol, yield 59%).
Intermediate 7 (0.73 g,0.59 mmol) was dissolved in chloroform (4.00 g) under nitrogen protection, methyl zinc chloride (0.295 mL,0.59mmol, 2mol/L diethyl ether solution) was added at a 1:1 molar ratio to intermediate 7 at a constant rate over 3h at room temperature, and the reaction was continued for 3h after the addition, and the solvent was distilled off under reduced pressure to give intermediate 8 (0.77 g,0.59mmol, yield 100%).
Intermediate 8 (0.66 g,0.50 mmol) and norbornene (0.05 g,0.50 mmol) in a molar ratio of 1:1 were dissolved in toluene (3.0 g) under nitrogen protection, azobisisobutyronitrile (0.41 mg,0.0025 mmol) in a molar ratio of 1:200 to intermediate 8 was added, the temperature was raised to 80℃for 8 hours, and the solvent was distilled off under reduced pressure to give an immobilized bifunctional catalyst (0.69 g, yield 100%). 1 HNMR(DMSO-d 6 ,400MHz):δ1.18-1.45(m,38H),1.48-1.89(m,18H),1.95-2.13(m,8H),2.91-3.05(m,5H),3.18-3.22(m,8H),3.56(m,2H),3.69(m,2H),4.93(s,2H),5.11-5.21(m,2H),6.23-6.35(m,4H),7.10-7.54(m,6H),7.56(m,1H),7.91(m,1H),8.43(m,1H)。
Examples 1 to 2
The Br of the raw material 1 in example 1-1 was changed to I to obtain I - Is a catalyst for immobilization.
Example 2: 200g of an immobilized bifunctional catalyst (X) was charged in an outer-loop injection reactor having an effective volume of 10L - Is Br -1 N=m=10), 1kg of ethylene carbonate was added as a starting recycle; the starting material was heated to 120℃by means of a heat exchanger and carbon dioxide was introduced to 0.8MPa. In the feeding process, the feeding amount of ethylene oxide and the feeding amount of carbon dioxide are kept almost consistent, the system pressure is kept at 0.8MPa, 4kg of ethylene oxide is consumed for 4 hours, and the pressure is not changed after the continuous reaction for 45 minutes after the feeding is finished. The reaction mass was transferred to a flash tank and after removal of carbon dioxide, about 9kg of ethylene carbonate was obtained (selectivity 99% by gas chromatography).
Example 3: 200g of immobilized bifunctional catalyst (X) was charged into each of an outer loop injection reactor having an effective volume of 10L and an aging tank - Is Br -1 N=m=10), and 4kg of ethylene carbonate was added as a starting bedding material to each of the reactor and the aging tank. Starting the reactor for circulation, heating the initial materials in the reactor and the ageing tank to 120 ℃ through a heat exchanger, and introducing carbon dioxide until the pressure of the system is 0.8MPa. Ethylene oxide was added to the reactor at a rate of 2.0kg/h, carbon dioxide was continuously fed (rate was maintained at 1.8-2.0 kg/h), and the system pressure was controlled at 0.8MPa. In the feeding process, the materials in the reactor are controlled to be maintained at 4kg through the interlocking of a liquid level meter and an electromagnetic valve, and the materials growing in the reactor are pressed into an aging tank. Along with the material adding, the ageing tank is interlocked with the electromagnetic valve through the liquid level meter to control the material in the ageing tank to be maintained at 4kg, and carbon dioxide is used as pressure supplement to maintain the pressure of the ageing tank to be 0.8MPa. And transferring the aged material into a flash tank, and discharging carbon dioxide to obtain the carbonate product. The ageing time of the material in the ageing tank under the balance is about 60min, and the conversion rate of the ethylene oxide is more than 99%. The operation was continued for 12 hours, giving about 48kg of ethylene carbonate (selectivity 99% by gas chromatography).
Example 4: an outer loop injection reactor having an effective volume of 10L was charged with 1000g of an immobilized bifunctional catalyst (X - Is Br -1 N=m=10), 1kg of ethylene carbonate was added as a starting recycle; the starting material was heated to 50℃by means of a heat exchanger and carbon dioxide was introduced to 0.4MPa. The feeding amount of ethylene oxide and carbon dioxide is kept almost consistent in the feeding process, the system pressure is kept at 0.4MPa, 1kg of ethylene oxide is consumed in 10 hours, and the pressure is not changed after the continuous reaction for 1.5 hours after the feeding is finished. The reaction mass was transferred to a flash tank and after carbon dioxide was vented, about 3kg of ethylene carbonate was obtained (gas chromatography detection selectivity 99%).
Example 5: an outer loop injection reactor having an effective volume of 10L was charged with 100g of an immobilized bifunctional catalyst (X - Is Br -1 N=m=10), 1kg of ethylene carbonate was added as a starting recycle; the starting material was heated to 150℃by means of a heat exchanger and carbon dioxide was introduced to 3.0MPa. In the feeding process, the feeding amount of ethylene oxide and the feeding amount of carbon dioxide are kept almost consistent, the system pressure is kept at 3.0MPa, 4kg of ethylene oxide is consumed for 4 hours, and the pressure is not changed after the continuous reaction for 30 minutes after the feeding is finished. The reaction mass was transferred to a flash tank and after carbon dioxide was vented, about 8kg of ethylene carbonate was obtained (98% selectivity by gas chromatography).
Example 6: 200g of immobilized bifunctional catalyst (X) was charged into each of an outer loop injection reactor having an effective volume of 10L and an aging tank - Is Br -1 N=m=10), and 4kg of ethylene carbonate was added as a starting bedding material to each of the reactor and the aging tank. Starting the reactor for circulation, heating the initial materials in the reactor and the ageing tank to 80 ℃ through a heat exchanger, and introducing carbon dioxide until the pressure of the system is 1.2MPa. Ethylene oxide was added to the reactor at a rate of 1.6kg/h, carbon dioxide was continuously fed (rate was maintained at 1.5-1.6 kg/h), and the system pressure was controlled at 1.2MPa. In the feeding process, the materials in the reactor are controlled to be maintained at 4kg through the interlocking of a liquid level meter and an electromagnetic valve, and the materials growing in the reactor are pressed into an aging tank. Along with the material adding, the aging tank is interlocked with the electromagnetic valve through the liquid level meter to control agingThe material in the ageing tank is maintained at 8kg, and the pressure of the ageing tank is maintained at 1.2MPa by taking carbon dioxide as pressure supplement. And transferring the aged material into a flash tank, and discharging carbon dioxide to obtain the carbonate product. The ageing time of the material in the ageing tank under the balance is about 75min, and the conversion rate of the ethylene oxide is more than 99%. The operation was continued for 12 hours, giving about 38.4kg of ethylene carbonate (selectivity greater than 99.5% by gas chromatography).
Example 7: an outer loop spray reactor having an effective volume of 10L was charged with 200g of an immobilized bifunctional catalyst (X - Is I -1 N=6, m=5), 1kg of propylene carbonate was added as starting recycle; the starting material was heated to 120℃by means of a heat exchanger and carbon dioxide was introduced to 0.8MPa. Propylene oxide is added at the speed of 0.75kg/h for reaction, the system pressure is maintained at 0.8MPa by supplementing carbon dioxide in the feeding process, 4.5kg of propylene oxide is consumed for about 6 hours, and the pressure is not changed after the continuous reaction for 50 minutes after the feeding is finished. The reaction mass was transferred to a flash tank and after carbon dioxide was vented, about 7.9kg of propylene carbonate was obtained (gas chromatography detection selectivity 99%).
Example 8: 200g of immobilized bifunctional catalyst (X) was charged into each of an outer-loop spray reactor and an aging tank having an effective volume of 10L - Is I -1 N=6, m=5), 4kg of propylene carbonate was added to the reactor and 6kg of propylene carbonate was added to the aging tank as a starting bedding material. Starting the reactor for circulation, heating the initial materials in the reactor and the ageing tank to 120 ℃ through a heat exchanger, and introducing carbon dioxide until the pressure of the system is 0.8MPa. Propylene oxide was added to the reactor at a rate of 2.0kg/h, carbon dioxide was continuously replenished, and the system pressure was maintained at 0.8MPa. In the feeding process, the materials in the reactor are controlled to be maintained at 4kg through the interlocking of a liquid level meter and an electromagnetic valve, and the materials growing in the reactor are pressed into an aging tank. Along with the material adding, the ageing tank is interlocked with the electromagnetic valve through the liquid level meter to control the material in the ageing tank to be maintained at 6kg, and carbon dioxide is used as pressure supplement to maintain the pressure of the ageing tank to be 0.8MPa. And transferring the aged material into a flash tank, and discharging carbon dioxide to obtain the carbonate product. The ageing time of the material in the ageing tank is about 1.7h, and the epoxy is carried out under the balanceThe propane conversion was greater than 99%. The operation was continued for 12 hours, to obtain about 42.2kg of propylene carbonate (selectivity 97% by gas chromatography).
Example 9: an outer loop spray reactor having an effective volume of 10L was charged with 200g of an immobilized bifunctional catalyst (X - Is I -1 N=8, m=7), 1kg of chloropropene carbonate is added as a starting recycle material; the starting material was heated to 120℃by means of a heat exchanger and carbon dioxide was introduced to 0.8MPa. Adding epichlorohydrin at the speed of 0.8kg/h for reaction, wherein the pressure of the system is maintained to be 0.8MPa by supplementing carbon dioxide in the feeding process, 4.8kg of epichlorohydrin is consumed for about 6 hours, and the pressure is not changed after the feeding is finished and the reaction is continued for 1 hour. The reaction mass was transferred to a flash tank and after carbon dioxide was vented, about 7kg of chloropropene carbonate was obtained (gas chromatography detection selectivity 99%).
Claims (8)
1. The immobilized bifunctional catalyst is characterized by being a macromolecule supported heteronuclear bimetallic complex, and has the structure as follows:
wherein: x is X - Is Cl -1 、Br -1 、I -1 Negative ions; n and m are positive integers.
2. The method for preparing the immobilized bifunctional catalyst of claim 1, wherein the synthesis reaction formula of the immobilized bifunctional catalyst is:
the preparation method of the immobilized bifunctional catalyst comprises the following steps:
dissolving a raw material 1 in toluene under the protection of inert gas, adding triethylamine with the molar ratio of 1-1.5:1 to the raw material, stirring for 5-10 min, slowly dropwise adding tin tetrachloride with the molar ratio of 0.3-0.5:1 to the raw material 1, keeping the temperature at 30 ℃ or below, keeping the temperature for 5-10 min after dropwise adding paraformaldehyde with the molar ratio of 5-7:1 to the raw material 1, heating to 80-100 ℃, and reacting for 10-15 h; after the reaction is finished, cooling to room temperature, filtering to remove filter cakes, collecting filtrate, evaporating toluene to obtain a viscous crude intermediate 1, adding methanol with the mass ratio of 3-5:1 to the crude intermediate 1, cooling to-5-0 ℃, stirring for 2-4 h to separate out a product, filtering and drying to obtain the intermediate 1;
dissolving the intermediate 1 and the raw material 2 with the molar ratio of 1:1 with dichloromethane under the protection of inert gas, dripping 1, 2-cyclohexanediamine with the molar ratio of 1:1 with the intermediate 1 at a constant speed within 1-2 h at room temperature, reacting for 3-5 h at room temperature after dripping, distilling under reduced pressure to remove dichloromethane, and purifying by column chromatography to obtain the intermediate 2;
adding the intermediate 2 and potassium carbonate with the molar ratio of 1:2-3 into acetone under the protection of inert gas, stirring uniformly, adding triethylamine with the molar ratio of 2-3:1 into the mixture, heating the mixture to reflux, reacting the mixture for 20-24 hours, distilling the mixture under reduced pressure to remove the acetone, and purifying the mixture by column chromatography to obtain an intermediate 3;
dissolving 2-aminocyclohexanol in tetrahydrofuran under the protection of inert gas, adding sodium hydride with the molar ratio of 1-1.2:1 with 2-aminocyclohexanol, stirring for 20-30 min, adding 2-chloromethylpyridine with the molar ratio of 1:1 with 2-aminocyclohexanol, heating to reflux reaction for 20-25 h, and performing column chromatography purification after removing tetrahydrofuran by reduced pressure distillation to obtain an intermediate 4;
dissolving the intermediate 4 and the raw material 2 in a molar ratio of 1:1 with ethanol under the protection of inert gas, heating to reflux, reacting for 8-10 h, distilling under reduced pressure to remove ethanol, and purifying by column chromatography to obtain an intermediate 5;
dissolving an intermediate 5, an intermediate 3 and a raw material 3 in a molar ratio of 1:1:1 with dichloromethane under the protection of inert gas, adding N, N' -dicyclohexylcarbodiimide in a molar ratio of 1-1.2:1 with the intermediate 5, reacting for 68-72 hours at room temperature, filtering, collecting a filter cake, and purifying by column chromatography to obtain an intermediate 6;
dissolving the intermediate 6 in chloroform under the protection of inert gas, adding diethyl aluminum chloride with the molar ratio of 1:1 with the intermediate 6 at constant speed within 2-3 h at room temperature, continuing to react for 2-3 h after the addition, and performing column chromatography purification after removing chloroform by reduced pressure distillation to obtain an intermediate 7;
dissolving the intermediate 7 in chloroform under the protection of inert gas, adding methyl zinc chloride with the molar ratio of 1:1 with the intermediate 7 at constant speed within 2-3 h at room temperature, continuing to react for 2-3 h after the addition, and performing column chromatography purification after removing the chloroform by reduced pressure distillation to obtain an intermediate 8;
dissolving intermediate 8 with the molar ratio of n to m and norbornene in toluene under the protection of inert gas, adding azodiisobutyronitrile with the molar ratio of 1 to 200-500 to the intermediate 8, heating to 60-80 ℃, reacting for 6-8 h, and distilling under reduced pressure to remove the solvent to obtain the immobilized bifunctional catalyst.
3. The method for preparing cyclic carbonate by using the immobilized bifunctional catalyst in an outer loop reaction process as claimed in claim 1, wherein the method is characterized in that the outer loop reactor is adopted, and the bifunctional catalyst is used for carrying out coupling reaction on carbon dioxide and alkylene oxide serving as raw materials at a reaction pressure of 0.4-3.0 MPa and a reaction temperature of 50-150 ℃.
4. A method for preparing cyclic carbonate by using an immobilized bifunctional catalyst in an outer loop reaction process as claimed in claim 3, wherein the outer loop reaction process is divided into a batch process and a continuous process;
the batch reaction process comprises the following steps:
filling an immobilization bifunctional catalyst in an outer loop reactor, and adding cyclic carbonate as an initial circulating material; heating the initial materials to the reaction temperature through a heat exchanger, and introducing carbon dioxide to the reaction system pressure which is the reaction pressure; after the preparation is finished, introducing alkylene oxide and carbon dioxide into the outer loop reactor for reaction, and maintaining the reaction pressure; after the addition of the alkylene oxide is finished, continuing to react until the alkylene oxide is completely consumed, then cooling and discharging pressure to transfer the material into a flash tank, and removing carbon dioxide to obtain cyclic carbonate; the next kettle reaction can be carried out after the outer loop reactor is emptied;
the continuous reaction process comprises the following steps:
filling the outer loop reactor and an aging tank with a supported bifunctional catalyst, and adding cyclic carbonate into the outer loop reactor as an initial circulating material; heating the initial materials to the reaction temperature through a heat exchanger, and introducing carbon dioxide to the reaction system pressure which is the reaction pressure; continuously introducing alkylene oxide and carbon dioxide into the outer loop reactor, transferring a reaction material part of the outer loop reactor into an aging tank while feeding, and discharging liquid materials in the aging tank through a discharge pipe and a back pressure valve to form a liquid seal; regulating the pressure between the outer loop reactor and the aging tank to be unchanged through carbon dioxide, and continuously outputting the aged materials to a flash tank to discharge carbon dioxide to obtain cyclic carbonate; in the whole process, the balance of the materials in the outer loop reactor, the ageing tank and the flash tank is controlled, and the steady state of continuous feeding reaction and discharge collection is maintained.
5. The method for preparing cyclic carbonate by using the immobilized bifunctional catalyst of claim 3 or 4, wherein the reaction pressure is 0.6-1.2 MPa, and the reaction temperature is 80-120 ℃.
6. The method for preparing cyclic carbonate by using immobilized bifunctional catalyst in outer loop reaction process as claimed in claim 3 or 4, wherein the mass ratio of alkylene oxide to catalyst is 0.1-10 g/g.h -1 。
7. The method for preparing cyclic carbonate by using the immobilized bifunctional catalyst in an outer loop reaction process as defined in claim 3 or 4, wherein the alkylene oxide is propylene oxide, ethylene oxide, epichlorohydrin, styrene oxide, phenyl glycidyl ether or cyclohexane oxide; the outer loop reactor is a spray or jet reactor.
8. The method for preparing cyclic carbonate by using the immobilized bifunctional catalyst of claim 3 or 4, wherein the loading manner of the immobilized catalyst is a material package, loop filling, reactor space filling or dispersion.
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