CN116375677A - Synthesis and application of heterocyclic heterogeneous catalyst - Google Patents
Synthesis and application of heterocyclic heterogeneous catalyst Download PDFInfo
- Publication number
- CN116375677A CN116375677A CN202310295425.9A CN202310295425A CN116375677A CN 116375677 A CN116375677 A CN 116375677A CN 202310295425 A CN202310295425 A CN 202310295425A CN 116375677 A CN116375677 A CN 116375677A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- ionic liquid
- substituted
- hours
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 125000000623 heterocyclic group Chemical group 0.000 title claims abstract description 12
- 239000002638 heterogeneous catalyst Substances 0.000 title abstract description 5
- 238000003786 synthesis reaction Methods 0.000 title description 4
- 230000015572 biosynthetic process Effects 0.000 title description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- 239000002608 ionic liquid Substances 0.000 claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 239000004593 Epoxy Substances 0.000 claims abstract description 22
- 150000005676 cyclic carbonates Chemical class 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 125000005496 phosphonium group Chemical group 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 6
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 3
- 229910003471 inorganic composite material Inorganic materials 0.000 claims abstract 3
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 5
- 239000001913 cellulose Substances 0.000 claims description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
- 125000006549 C4-C10 aryl group Chemical group 0.000 claims description 2
- 229920001661 Chitosan Polymers 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 150000002484 inorganic compounds Chemical class 0.000 claims 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
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims 1
- 239000002202 Polyethylene glycol Substances 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 229910010272 inorganic material Inorganic materials 0.000 claims 1
- 229920005610 lignin Polymers 0.000 claims 1
- 150000002894 organic compounds Chemical class 0.000 claims 1
- 229920001223 polyethylene glycol Polymers 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 46
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 22
- 239000000047 product Substances 0.000 description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 description 11
- 239000001569 carbon dioxide Substances 0.000 description 9
- 238000011068 loading method Methods 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- -1 phosphine compound Chemical group 0.000 description 6
- 238000001816 cooling Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000006352 cycloaddition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- ULXXSFVSTXMUSV-UHFFFAOYSA-N 2-phenoxyoxirane Chemical compound C1OC1OC1=CC=CC=C1 ULXXSFVSTXMUSV-UHFFFAOYSA-N 0.000 description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005810 carbonylation reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- 150000004714 phosphonium salts Chemical group 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- AVCVDUDESCZFHJ-UHFFFAOYSA-N triphenylphosphane;hydrochloride Chemical compound [Cl-].C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 AVCVDUDESCZFHJ-UHFFFAOYSA-N 0.000 description 2
- VXLQXFQDOGUAPA-UHFFFAOYSA-N (4-methoxyphenyl)phosphane Chemical compound COC1=CC=C(P)C=C1 VXLQXFQDOGUAPA-UHFFFAOYSA-N 0.000 description 1
- MGAXYKDBRBNWKT-UHFFFAOYSA-N (5-oxooxolan-2-yl)methyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OCC1OC(=O)CC1 MGAXYKDBRBNWKT-UHFFFAOYSA-N 0.000 description 1
- HXHGULXINZUGJX-UHFFFAOYSA-N 4-chlorobutanol Chemical compound OCCCCCl HXHGULXINZUGJX-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical group C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- CMSYDJVRTHCWFP-UHFFFAOYSA-N triphenylphosphane;hydrobromide Chemical compound Br.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 CMSYDJVRTHCWFP-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0287—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre
- B01J31/0288—Phosphorus
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
- B01J31/0294—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate by polar or ionic interaction with the substrate, e.g. glass
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
- B01J31/0295—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate by covalent attachment to the substrate, e.g. silica
-
- 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
-
- 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
- C07D317/44—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 ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D317/46—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 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for preparing cyclic carbonate by catalyzing a heterocyclic quaternary phosphonium ionic liquid loaded by a composite material, which is characterized in that an organic or inorganic composite material is used as a carrier to load a hetero-atom or heterocyclic substituted quaternary phosphonium ionic liquid for catalyzing CO 2 And synthesizing the cyclic carbonate by an epoxy compound. The catalyst can efficiently catalyze CO under optimal reaction conditions 2 The product is converted into cyclic carbonate, and the yield can reach 99 percent. Compared with the traditional heterogeneous catalyst, the catalyst has better catalytic effect, simple preparation method, good cycle performance, long service life, simple and easily-separated advantages and industrial application prospect.
Description
Technical Field
The invention relates to the technical field of catalytic cyclic compounds, in particular to a method for synthesizing cyclic carbonate based on composite material supported heterocyclic ionic liquid catalysis.
Background
Carbon dioxide (CO) 2 ) Is a greenhouse gas and is an inexhaustible C1 resource, and the effective fixed conversion of the greenhouse gas is one of the most challenging subjects in the century, and CO is utilized 2 The synthesis of cyclic carbonates is one of the very good routes for the immobilization of the conversion. The cyclic carbonate is an important chemical product with low toxicity, biodegradability, high boiling point and the like, and is widely applied to power battery electrolyte, can be used as an organic synthesis intermediate, and is used for producing products such as dimethyl carbonate, ethylene glycol and the like in the fields of polycarbonate, medicine, paint and the like.
Currently, CO 2 The catalyst used for cycloaddition reaction with epoxide mainly comprises Metal Organic Framework (MOF) (CN 111454434A, CN 105481821A), transition metal complex (CN 107827857A, CN107827858A, CN 111215148A), compound catalyst (CN 111393402A, CN 107715918B) and other catalysts, and although part of the catalyst has higher catalytic activity, organic solvent with strong toxicity is needed to be used, thus causing difficulties for separation and purification of products and product quality. Meanwhile, the homogeneous catalyst has high use cost due to the problems of difficult separation of the catalyst and the product, short service life of the catalyst and the like, and further industrial application of the homogeneous catalyst is restricted.
Ionic liquids (CN 111362901 a) are receiving a great deal of attention as an emerging medium. The supported ionic liquid is used as a heterogeneous catalyst, so that the problem of separation of the catalyst and a product can be effectively solved. The supported ionic liquid catalyst is divided into physical supports according to the supporting modeAnd chemical loading, the physical loading adopts a physical adsorption mode, the stability of the catalyst is relatively poor and easy to run off, and the chemical loading is connected through chemical bonds formed between the ionic liquid and the carrier, so that the catalyst has higher stability while ensuring certain catalytic activity. CN107537564B discloses a catalyst for catalyzing CO 2 A heterogeneous catalyst for preparing cyclic carbonate with an epoxy compound, which is formed by copolymerizing an olefin-group-containing organophosphine ligand and an olefin-group-containing quaternary phosphonium salt to obtain a copolymer, and coordinating the copolymer with a Lewis acidic metal salt, the catalyst obtained by the method being capable of forming a dual-activation mode of multi-functional properties, but the active component of the copolymer being difficult to determine and the addition of the metal salt being such that the cost of the catalyst increases. CN104974128A discloses a method for preparing cyclic carbonate by using a supported catalyst, which carries p-methoxyphenylphosphine, but the loading and loading rate of active components are not further measured, so that the overall catalytic activity is required to be improved.
The invention designs and develops a composite material loaded heterocycle or heteroatom substituted quaternary phosphonium ionic liquid to catalyze CO 2 The cyclic carbonate is synthesized, the nucleophilic-electrophilic effect of the quaternary phosphonium ionic liquid is enhanced by utilizing heterocycle or heteroatom, and meanwhile, the thermal and mechanical properties of the resin are enhanced by designing the synthesized composite resin material, so that the catalyst has high loading rate and good activity and is used for catalyzing CO 2 And epoxy compounds to synthesize cyclic carbonate, so as to realize efficient and stable conversion of carbonylation reaction.
Disclosure of Invention
The invention aims to provide a method for preparing cyclic carbonate by catalyzing cycloaddition of an epoxy compound and carbon dioxide by using a composite material loaded heterocycle or heteroatom substituted quaternary phosphonium ionic liquid catalyst.
The reaction general formula of the invention is:
when R is 2 When H is represented, the epoxy compound used in the formula has the structure:
where m=l, 2, 3 or 4, n=0, l, 2, 3 or 4.
When R is 2 When the epoxy compound is not H, the structure of the epoxy compound is as follows:
a method for preparing cyclic carbonate by using supported ionic liquid is characterized in that a composite material supported heterocyclic or heteroatom substituted quaternary phosphonium ionic liquid is used as a catalyst, the catalyst dosage is 0.1-2.0mol% (calculated by ionic liquid content) of an epoxy compound, and the corresponding cyclic carbonate is synthesized by catalyzing cycloaddition of the epoxy compound and carbon dioxide under the conditions of reaction pressure of 0.1-10.0MPa, reaction temperature of 50-150 ℃ and reaction time of 0.5-10 hours. The synthesis method has the characteristics of high catalyst activity, low cost, long service life, easy product separation and catalyst recovery, and the like.
The invention relates to a composite material loaded ionic liquid which has the following structure:
wherein n=0 to 6, R1, R2 and R3 are one, two or three groups simultaneously substituted with the following functional groups, H, F, cl, br, I,
P (CH 3) 2 or N (CH 3) 2;
the preferred cationic structure is as follows,
x is any one of the following anions:
wherein R is any one of C1-C6 alkyl, C4-C10 cycloalkyl and C4-C10 aryl.
The carrier according to claim 1, wherein the carrier is an organic polymer, such as any one of carbon material composite polystyrene, chitosan and cellulose.
The supported quaternary phosphonium salt catalyst is prepared according to the following steps:
1) Pretreatment of the carrier: to a flask containing 250mL of dimethylacetamide was added 40g of anhydrous lithium chloride, which was then stirred at 70-100deg.C for 2h to dissolve as a homogeneous solution, cooled to room temperature, 10g of cellulose was added, then warmed to 70-100deg.C and stirred overnight, cooled to room temperature and stirred until dissolved. And adding a mixed solution of the triethylamine and the dimethylacetamide in the same volume ratio of two times of molar equivalent into the solution, cooling to 8 ℃, dropwise adding a mixed solution of the p-toluenesulfonyl chloride and 30-60mL of dimethylacetamide in one time of molar equivalent, and stirring the reaction solution for 20-40h. The reaction mixture was slowly poured into a large amount of ice water and the product precipitated. Stirring, filtering, washing with a large amount of ethanol, and vacuum drying at 30-60 ℃ to obtain the product cellulose p-toluenesulfonate;
2) Preparation of ionic liquid: 5-10g of 4-chloro-1-butanol and 50-100mL of acetonitrile are added into a 250mL four-neck flask, nitrogen protection is adopted, a tertiary phosphine compound with double molar equivalent is slowly added when the temperature is raised to 40-50 ℃, and then the temperature is raised to 60-90 ℃ continuously, and stirring reaction is carried out for 24-48h. After stopping the reaction, rotary steaming to obtain homogeneous ionic liquid, washing with ethyl acetate until no tertiary phosphine compound exists, and vacuum drying at 50-75 ℃ for 12-24 hours to obtain quaternary phosphonium ionic liquid;
3) Preparing a loaded chloridion liquid: 10-20g of the modified cellulose carrier obtained in the step 3), 50-100mL of acetonitrile and twice molar equivalent of the ionic liquid obtained in the step 2) are added into a 250mL four-neck flask, and the temperature is raised to 60-90 ℃ under the protection of nitrogen, and the mixture is stirred and reacted for 24-48h. After stopping the reaction, rotary steaming to obtain homogeneous ionic liquid, washing with ethyl acetate, and vacuum drying at 50-75 ℃ for 12-24 hours to obtain quaternary phosphonium ionic liquid;
4) Anion exchange of quaternary phosphonium-based supported ionic liquids: 10g of the supported catalyst obtained in the step 3) and twice molar equivalent of KX are added into a three-necked flask, 150ml of methanol and nitrogen are then added, a constant temperature heating stirrer is opened to heat the mixture in the flask to 75 ℃, and reflux reaction is carried out for 24 hours. And after the reaction is finished, standing and cooling the mixture to room temperature, removing supernatant, taking out the supported catalyst, washing the catalyst with deionized water until the supernatant does not contain inorganic salt KX, and vacuum drying the catalyst at 50-75 ℃ for 12-24 hours to obtain the corresponding anion quaternary phosphonium supported catalyst.
5) Measuring the loading amount of the quaternary phosphonium loaded ionic liquid: taking the ionic liquid obtained in the step 3) or the step 4), carrying out XRF (X-ray diffraction) measurement on the content of the P element, and calculating to know that the loading range is 88% -100%
Preferably, the cyclic carbonate is selected from at least one or two of ethylene carbonate, propylene carbonate, epoxy chloropropene ester, cyclohexene oxide ester and phenyl carbonate.
Preferably, the molar ratio of the ionic liquid added to the epoxy compound is 0.5 to 1.5%, for example, 0.1%, 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0%, 5.5%, 6.0%, 6.5%, 7.0%, 7.5%, 8.0%, 8.5%, 9.0%, 9.5%, 10.0%, etc., preferably 0.5 to 1.5%.
Preferably, the catalytic reaction is operated at a pressure of 1 to 5MPa, for example, 0.1MPa, 0.5MPa, 1.0MPa, 1.5MPa, 2.0MPa, 2.5MPa, 3.0MPa, 3.5MPa, 4.0MPa, 4.5MPa, 5.0MPa, 5.5MPa, 6.0MPa, 6.5MPa, 7.0MPa, 7.5MPa, 8.0MPa, 8.5MPa, 9.0MPa, 9.5MPa or 10.0MPa, etc., preferably 1 to 5MPa.
Preferably, the catalytic reaction is operated at a temperature of from 80 to 160 c, for example, 60 ℃, 70 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃,120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 215 ℃, 220 ℃, or the like can be used, and 80-160 ℃ is preferred. Preferably, the reaction time of the catalytic reaction is 2 to 5 hours, and may be, for example, 0.25 hours, 0.5 hours, 1.0 hours, 1.5 hours, 2.0 hours, 2.5 hours, 3.0 hours, 3.5 hours, 4.0 hours, 4.5 hours, 5.0 hours, 5.5 hours, 6.0 hours, 8.0 hours, 10.0 hours, 12.0 hours, 14.0 hours, 16.0 hours, 18.0 hours, 20.0 hours, 22.0 hours, 24.0 hours, or the like, preferably 2 to 5 hours.
Stopping stirring after the reaction is finished, cooling the temperature in the reaction kettle to room temperature, and then disassembling the kettle, and sucking the upper liquid to obtain the required cyclic carbonate product.
Detailed Description
The present invention is described in the following examples, but the present invention is not limited to the following examples, and various modifications are included in the technical scope of the present invention without departing from the spirit and scope of the present invention.
Example 1
The implementation method comprises the following steps: in a 15ml stainless steel autoclave, a cellulose-supported triphenylphosphine bromide (in the formula
X=br) 0.3g (0.5 mmol, in terms of ionic liquid content, 0.5mol% to epoxide, hereinafter the same applies) 7ml propylene oxide (la) (0.1 mol), at room temperature, with an appropriate amount of CO2 charge, closing the reactor vent valve; placing the reaction kettle into an automatic temperature-controlled heating furnace, regulating the pressure of the reaction kettle to 1MPa, keeping the reaction kettle for 15 minutes to 2.5MPa after the temperature reaches the target temperature of 120 ℃ in order to prevent the carbonylation reaction at the initial stage from being too severe, reacting for 2 hours at 120 ℃, cooling the reaction kettle to room temperature after the reaction is finished, slowly discharging unreacted CO2, filtering and separating out the catalyst, and taking out a trace of reaction liquid Agilent 889 for use0, the conversion and selectivity analysis was carried out, the propylene carbonate product selectivity was 99.7% and the conversion was 99.8%.
Example 2
As in example 1, the catalyst used was cellulose-supported tris (2-furyl) phosphorus chloride (in the structural formula,
x=cl) 0.12g (about 0.5 mmol), the other conditions being unchanged, yields a product (2 a) with a selectivity of 99.3% and a conversion of 99.5%.
Example 3
As in example 1, 0.1g (about 0.5 mmol) of cellulose-supported triphenylphosphine chloride (X=Cl, R=Ph in the formula) was used as the catalyst, and the other conditions were unchanged, to give (2 a) having a selectivity of 99.7% and a conversion of 99.3%.
Example 4
The catalyst used was resin-supported triphenylphosphine chloride, the additive was sodium phenoxide, the temperature was 80℃and the others were unchanged, as in example 1, to give (2 a) a selectivity of 99.7% and a conversion of 99.4%.
Example 5
As in example 1, the temperature was 80℃and the others were unchanged, giving (2 a) a selectivity of 99.7% and a conversion of 89.4%.
Example 6
As in example 1, the temperature was 160℃and the others were unchanged, giving (2 a) a selectivity of 99.7% and a conversion of 99.8%.
Example 7
The reaction time was 3.5 hours as in example 1, and the selectivity (2 a) was 99.7% with the other conditions unchanged, and the conversion was 95.5%.
Example 8
The reaction time was 5 hours as in example 1, and the selectivity (2 a) was 99.7% with the other conditions unchanged, and the conversion was 99.6%.
Example 9
The catalyst was used in an amount of 0.6g (molar ratio to the epoxy compound: 1.0 mol%) at a reaction temperature of 140℃for 4.0 hours, and the selectivity (2 a) was 99.7% and the conversion was 99.7% as in example 1.
Example 10
The catalyst was used in an amount of 1.2g (molar ratio to the epoxy compound: 1.5 mol%) at a reaction temperature of 120℃for 2.0 hours, and the selectivity (2 a) was 99.7% and the conversion was 99.9% as in example 1.
Example 11
The reaction pressure was 1.0MPa, and the other conditions were the same, to give (2 a) a selectivity of 99.7% and a conversion of 97.5%.
Example 12
The reaction pressure was 5.0MPa, and the other conditions were the same, to give (2 a) a selectivity of 99.6% and a conversion of 99.3%.
Example 13
After 8 uses of the catalyst as in example 1, (2 a) selectivity of 99.4% and conversion of 97.1% were obtained.
Example 14
As in example 1, the epoxide compound used was ethylene oxide (1 b), the other being unchanged, a selectivity of (2 b) of 99.2% was obtained, and the conversion was 98.9%.
Example 15
As in example 1, ethylene oxide (1 b) was used as the epoxy compound, and 0.6g (molar ratio to the epoxy compound: 1.0 mol%) of catalyst was used, except that the other conditions were not changed, to obtain (2 b) having a selectivity of 99.5% and a conversion of 99.4%.
Example 16
As in example 1, epichlorohydrin (1 c) was used as the epoxy compound, and the other conditions were unchanged, to give (2 c) having a selectivity of 93.7% and a conversion of 99.7%.
Example 17
As in example 1, the epoxy compound used was epoxystyrene (1 d), and the other conditions were unchanged, to give (2 d) selectivity of 98.0% and conversion of 99.3%.
Example 18
As in example 1, the epoxy compound used was phenoxyethylene oxide (1 e) under the same conditions, and the selectivity (2 e) was 97.8% and the conversion was 99.1%.
Example 19
As in example 1, the epoxy compound used was epoxycyclohexane (lf), the reaction temperature was 140 ℃, the pressure was 5MPa, the time was 8 hours, and other conditions were unchanged, to obtain (2 f) having a selectivity of 99.0% and a conversion of 99.6%.
Example 20
As in example 1, the epoxy compound used was allyl ethylene oxide (lg), the catalyst amount was 2.0mol% of the epoxy compound, and the other conditions were unchanged, resulting in (2 g) selectivity of 99.0% and conversion of 99.5%.
Claims (10)
1. Composite material-based heterocyclic ionic liquid supported CO catalysis 2 A process for synthesizing cyclic carbonate features that the organic or inorganic composite material is used to load the quaternary phosphonium ionic liquid substituted by heterocycle or heteroatom as catalyst or the trace additive is added to it 2 The cyclic carbonate is synthesized as a raw material.
2. The process according to claim 1, characterized in that the heterocyclic ring-carrying or heteroatom-substituted quaternary phosphonium ionic liquid used has the following structural formula:
wherein n=0 to 6, R1, R2 and R3 are one, two or three groups simultaneously substituted with the following functional groups, H, F, cl, br, I,
P(CH 3 ) 2 Or N (CH) 3 ) 2 ；
The preferred cationic structure is as follows,
x is any one of the following anions:
Cl - Br - I - BF 4 - OH - HCO 3 - 
wherein R is any one of C1-C6 alkyl, C4-C10 cycloalkyl and C4-C10 aryl.
3. The carrier according to claim 1 is an organic or inorganic composite material, wherein the organic composite material is preferably any one of cellulose, polyethylene glycol, lignin, chitosan and carbon material composite polystyrene; the inorganic compound is preferably any one of MCM-41, SAB-15 and ZSM-5.
4. The micro-additive according to claim 1, wherein the micro-additive is a metal inorganic or organic compound, the addition amount of the micro-additive is 10-10000ppm, and the anions are any one of the following:
Cl - Br - I - BF 4 - OH - HCO 3 - 
5. the method of claim 1, wherein the catalytic reaction has the formula:
wherein R is one of a substituted or unsubstituted C1-C20 linear or branched alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C3-C20 heterocycloalkyl group, and a substituted or unsubstituted C6-C20 aryl group.
6. The method according to claim 4, wherein the molar ratio of the catalyst ionic liquid to the epoxy compound is 0.1-10.0%, preferably 0.5-1.5%.
7. The method according to claims 4-5, preferably, the epoxy compound is selected from at least one of ethylene oxide, propylene oxide, epichlorohydrin, cyclohexane oxide, styrene oxide, and the like.
8. The method according to claims 4-6, characterized in that the catalytic reaction is operated at a pressure of 0.1-10MPa, preferably 1-5MPa.
9. The method according to claims 4-7, characterized in that the catalytic reaction is operated at a temperature of 60-220 ℃, preferably 80-160 ℃.
10. The method according to claims 4-8, characterized in that the catalytic reaction is operated for a time period of 0.25-24 hours, preferably 2-5 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310295425.9A CN116375677A (en) | 2023-03-24 | 2023-03-24 | Synthesis and application of heterocyclic heterogeneous catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310295425.9A CN116375677A (en) | 2023-03-24 | 2023-03-24 | Synthesis and application of heterocyclic heterogeneous catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116375677A true CN116375677A (en) | 2023-07-04 |
Family
ID=86968664
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310295425.9A Pending CN116375677A (en) | 2023-03-24 | 2023-03-24 | Synthesis and application of heterocyclic heterogeneous catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116375677A (en) |
-
2023
- 2023-03-24 CN CN202310295425.9A patent/CN116375677A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Dai et al. | Cross-linked polymer grafted with functionalized ionic liquid as reusable and efficient catalyst for the cycloaddition of carbon dioxide to epoxides | |
| CN101531725B (en) | Alpha-nickel diimine compound olefin polymerization catalyst and preparation method thereof, and method for preparing branched polyethylene | |
| CN112341394B (en) | Method for preparing cyclic carbonate ester by catalysis of hydrogen bond donor functionalized polymeric ionic liquid | |
| Elhaj et al. | Functionalized quaternary ammonium salt ionic liquids (FQAILs) as an economic and efficient catalyst for synthesis of glycerol carbonate from glycerol and dimethyl carbonate | |
| CN111423326B (en) | Method for preparing dimethyl carbonate by alkaline ionic liquid catalysis one-step method | |
| CN105732566B (en) | A method of preparing ethylene carbonate | |
| CN106040296B (en) | The preparation method of the poly- propyl ether -3- methylimidazole ionic-liquid catalyst of chlorination 1- amino | |
| CN109776480A (en) | A kind of preparation method for the catalyst of synthesizing annular carbonate, preparation method and cyclic carbonate | |
| CN108636450B (en) | Polyion liquid composite material and preparation method and application thereof | |
| CN106279094B (en) | A kind of method of Thiourea preparing cyclic carbonate by catalyzing with ionic liquid | |
| CN101474576A (en) | Catalytic system for synthesizing annular carbonic acid ester | |
| CN113788793B (en) | Sulfonic acid functionalized imidazole ionic liquid catalyst and preparation method and application thereof | |
| CN112409190B (en) | Method for efficiently synthesizing cyclic carbonate by using amine salt ionic liquid as catalyst | |
| Deng et al. | Bis-ammonium immobilized polystyrenes with co-catalyzing functional end groups as efficient and reusable heterogeneous catalysts for synthesis of cyclic carbonate from CO 2 and epoxides | |
| CN111135871A (en) | Imidazole ionic liquid functionalized zinc porphyrin and application thereof | |
| CN111909094A (en) | Multi-active center ionic liquid, preparation method and method for catalytically synthesizing cyclic carbonate by using multi-active center ionic liquid | |
| CN104707652A (en) | Carboxyl-terminated polyether ionic liquid catalyst and preparation method thereof | |
| CN109810091B (en) | Process for the preparation of alkylene carbonate from alkylene oxide and carbon dioxide | |
| CN110078702A (en) | A kind of method of poly ion liquid frame catalyst preparation cyclic carbonate | |
| CN112250656B (en) | Method for catalytically synthesizing cyclic carbonate based on multi-active-center ionic liquid | |
| CN114011459A (en) | Titanium series double-acid type ionic liquid catalyst, preparation method and application | |
| CN113117747A (en) | Interfacial ionic liquid supported catalyst for synthesizing cyclic carbonate from carbon dioxide | |
| CN106256845A (en) | A kind of preparation method of high-molecular aliphatic polycarbonate | |
| CN109867654B (en) | Method for preparing alkylene carbonate from alkylene oxide and carbon dioxide | |
| CN105665022B (en) | A kind of CO2Bifunctional catalyst of cyclic carbonate ester and preparation method thereof is prepared with epoxide cycloaddition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |