CN116375677A - 一种杂环非均相催化剂的合成及应用 - Google Patents
一种杂环非均相催化剂的合成及应用 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
本发明涉及一种复合材料负载杂环季鏻离子液体催化制备环状碳酸酯的方法,其特征在于使用有机或无机复合材料为载体,对杂原子或杂环取代的季鏻类离子液体进行负载,用于催化CO2与环氧化合物合成环状碳酸酯的反应。该催化剂可以在最优反应条件下高效催化CO2转化为环状碳酸酯,收率可达99%。相比于传统非均相催化剂,该类催化剂具有更好的催化效果,制备方法简单,循环性能好,使用寿命长且具有简单易分离的优点,具有工业应用前景。
Description
技术领域
本发明涉及催化环状化合物技术领域,具体涉及一种基于复合材料负载杂环离子液体催化合成环状碳酸酯的方法。
背景技术
二氧化碳(CO2)是一种温室气体,同时又是取之不竭的C1资源,其有效固定转化已经成为本世纪最具挑战性的课题之一,而利用CO2合成环状碳酸酯就是其中一种很好的固定转化途径。环状碳酸酯是一种多用途的重要的化工产品,它具有低毒、可生物降解、沸点高等特性,被广泛应用在动力电池电解液、也可用作有机合成中间体,用于生产碳酸二甲酯、乙二醇等产品用于聚碳酸酯、医药、涂料等领域。
目前,CO2与环氧化物环加成反应所用的催化剂主要包括金属有机骨架(MOF)(CN111454434A、CN105481821A)、过渡金属络合物(CN107827857A、CN107827858A、CN111215148A)以及复配催化剂(CN111393402A、CN107715918B)等催化剂,虽然部分催化剂具有较高的催化活性,但需使用毒性强的有机溶剂,给产物的分离提纯以及产品质量造成困难。同时上述均相催化剂由于催化剂与产物不易分离、催化剂寿命短等问题,造成其使用成本偏高,制约其进一步工业化的应用。
离子液体(CN111362901A)作为一种新兴介质受到了广泛关注。其中,负载型离子液体作为非均相催化剂可以有效解决催化剂与产物的分离问题。负载型离子液体催化剂按照其负载方式分为物理负载及化学负载,物理负载采用的是物理吸附方式,催化剂稳定性相对较差,易流失,而化学负载是通过离子液体和载体间形成的化学键连结,在保证一定的催化活性的同时,具备了较高的稳定性。CN107537564B公开了一种用于催化CO2与环氧化合物制备环状碳酸酯的非均相催化剂,该催化剂由含有烯烃基的有机膦配体和含有烯烃基的季鏻盐共聚后所得共聚物与路易斯酸性金属盐配位形成,该方法所得催化剂可形成多功能性质的双活化模式,但其共聚物的活性组分难以确定且加入金属盐使得催化剂的成本增加。CN104974128A公开了一种负载型催化剂制备环状碳酸酯的方法,该催化剂对甲氧基苯基膦进行负载,但文中就其活性组分的负载量及负载率没有进一步的测定,整体催化活性有待提高。
本发明设计开发复合材料负载杂环或杂原子取代的季鏻离子液体催化CO2合成环状碳酸酯,利用杂环或杂原子增强季鏻离子液体的亲核-亲电效应,同时设计合成的复合树脂材料增强了树脂的热学和力学性能,负载率高、活性好用于催化CO2和环氧化合物合成环状碳酸酯,实现羰基化反应的高效稳定转化。
发明内容
本发明的目的是提供一种复合材料负载杂环或杂原子取代的季鏻类离子液体催化剂催化环氧化合物和二氧化碳环加成制备环状碳酸酯的方法。
本发明的反应通式为:
当R2表示H时,通式中所用环氧化合物的结构为:
其中m=l、2、3或4,n=0、l、2、3或4。
当R2不为H时,所用环氧化合物的结构为:
一种负载型离子液体制备环状碳酸酯的方法,其特征在于使用复合材料负载杂环或杂原子取代的季鏻类离子液体作为催化剂,催化剂用量为环氧化合物的0.1-2.0mol%(以离子液体含量计算),在反应压力为0.1-10.0MPa,反应温度为50-150℃,反应时间为0.5-10小时的条件下,催化环氧化合物和二氧化碳环加成合成相应的环状碳酸酯。该合成方法具有催化剂活性高,成本低,使用寿命长,产物分离和催化剂回收容易等特点。
本发明涉及到的复合材料负载离子液体的结构如下:
优选的阳离子结构如下,
X为如***离子中的任意一种:
其中R为C1-C6的烷基、C4-C10的环烷基和C4-C10的芳基中的任意一种。
根据权利要求1所述,载体为有机聚合物,如碳材料复合聚苯乙烯、壳聚糖、纤维素中的任意一种。
所述的负载季鏻盐催化剂是按照以下步骤制备得到的:
1)载体的前处理:向含有250mL二甲基乙酰胺的烧瓶中加入40g的无水氯化锂,然后70-100℃下搅拌2h使其溶解为均相溶液,冷却至室温,加入10g纤维素后升温至70-100℃搅拌过夜,再冷却至室温,搅拌直至溶解。向上述溶液中加入二倍摩尔当量等体积比的三乙胺和二甲基乙酰胺的混合溶液,冷却至8℃,滴加一倍摩尔当量的对甲苯磺酰氯和30-60mL二甲基乙酰胺的混合溶液,反应溶液搅拌20-40h。反应混合物缓慢倒入大量冰水中,产品析出。搅拌,过滤,大量乙醇洗,30-60℃下真空干燥,得产品纤维素对甲苯磺酸酯;
2)离子液体的制备:在250mL的四口烧瓶中,加入5-10g 4-氯-1-丁醇以及50-100mL乙腈,氮气保护,升温至40-50℃时缓慢加入二倍摩尔当量的叔膦化合物,然后继续升温至60-90℃搅拌反应24-48h。停止反应后,旋蒸得到均相离子液体,然后用乙酸乙酯洗涤至无叔膦化合物,在50-75℃下真空干燥12-24h后得到季鏻类离子液体;
3)负载氯代离子液体的制备:在250mL的四口烧瓶中,加入3)步骤中所得改性纤维素载体10-20g、50-100mL乙腈以及二倍摩尔当量的2)步骤中所得的离子液体,氮气保护升温至60-90℃搅拌反应24-48h。停止反应后,旋蒸得到均相离子液体,然后用乙酸乙酯洗涤,在50-75℃下真空干燥12-24h后得到季鏻类离子液体;
4)季鏻类负载离子液体的阴离子交换:取3)步骤中所得负载催化剂10g以及二倍摩尔当量的KX加入到三口烧瓶中,然后加入150ml甲醇,氮封,打开恒温加热搅拌器将烧瓶中的混合物加热到75℃,回流反应24h。反应完毕后将混合物静置冷却至室温,去除上层清液,取出负载催化剂,后用去离子水洗至清夜中不含无机盐KX,在50-75℃下真空干燥12-24h后得到相应阴离子季鏻类负载催化剂。
5)季鏻类负载离子液体负载量的测定:取3)或4)步骤所的离子液体进行XRF测定其中P元素含量并计算可知其负载量范围为88%-100%
优选地,本发明所述的环状碳酸酯选自碳酸乙烯酯、碳酸丙烯酯、环氧氯丙烯酯、环氧环己烯酯、碳酸苯烯酯中的至少一种或两种组合。
优选地,离子液体加入量与环氧化合物的摩尔比为0.5-1.5%,例如可以是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%等,优选为0.5-1.5%。
优选地,催化反应的操作压力为1-5MPa,例如可以是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或10.0MPa等,优选为1-5MPa。
优选地,催化反应的操作温度为80-160℃,例如可以是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℃或220℃等,优选为80-160℃。优选地,催化反应的反应时间为2-5h,例如可以是0.25h、0.5h、1.0h、1.5h、2.0h、2.5h、3.0h、3.5h、4.0h、4.5h、5.0h、5.5h、6.0h、8.0h、10.0h、12.0h、14.0h、16.0h、18.0h、20.0h、22.0h或24.0h等,优选为2-5h。
反应结束后停止搅拌,待反应釜内温度冷却至室温再拆开釜,吸取上层液体即为所需环状碳酸酯产品。
具体实施方式
本发明用以下实施例说明,但本发明并不限于下述实施例,在不脱离前后所述宗旨的范围下,变化实施都包含在本发明的技术范围内。
实施例1
实施方法:在15ml不锈钢高压釜中,依次加入纤维素负载的三苯基溴化磷(结构式中X=Br)0.3g(以离子液体的含量计为0.5mmol,与环氧化合物的摩尔比为0.5mol%,以下同)7ml环氧丙烷(la)(0.1mol),于室温下充入适量CO2,关闭反应器通气阀门;将反应釜放入自动温控加热炉,将反应釜的压力先调至1MPa,为了防止起始阶段羰基化反应过于剧烈,待温度达至目标温度120℃之后,保持15分钟左右,调节反应釜压力至2.5MPa,120℃下反应2h,反应结束后将反应釜冷却至室温,缓慢放出未反应的CO2,过滤分离出催化剂后,取出微量的反应液用Agilent 8890进行转化率和选择性分析,产物碳酸丙烯酯选择性为99.7%,转化率为99.8%。
实施例2
实施例3
同实施例1,所用催化剂为纤维素负载三苯基氯化磷(结构式中,X=Cl,R=Ph)0.1g(约0.5mmol),其他条件不变,得到(2a)选择性99.7%,转化率为99.3%。
实施例4
同实施例1,所用催化剂为树脂负载三苯基氯化磷,添加剂为苯酚钠,温度为80℃,其他不变,得到(2a)选择性99.7%,转化率为99.4%。
实施例5
同实施例1,温度为80℃,其他不变,得到(2a)选择性99.7%,转化率为89.4%。
实施例6
同实施例1,温度为160℃,其他不变,得到(2a)选择性99.7%,转化率为99.8%。
实施例7
同实施例1,反应时间为3.5小时,其他不变,得到(2a)选择性99.7%,转化率为95.5%。
实施例8
同实施例1,反应时间为5小时,其他不变,得到(2a)选择性99.7%,转化率为99.6%。
实施例9
同实施例1,催化剂用量为0.6g(与环氧化合物的摩尔比为1.0mol%),反应温度为140℃,反应时间为4.0小时,其他不变,得到(2a)选择性99.7%,转化率为99.7%。
实施例10
同实施例1,催化剂用量为1.2g(与环氧化合物的摩尔比为1.5mol%),反应温度为120℃,反应时间为2.0小时,其他不变,得到(2a)选择性99.7%,转化率为99.9%。
实施例11
同实施例1,反应压力为1.0MPa,其他不变,得到(2a)选择性99.7%,转化率为97.5%。
实施例12
同实施例1,反应压力为5.0MPa,其他不变,得到(2a)选择性99.6%,转化率为99.3%。
实施例13
同实施例1,催化剂使用8次后,得到(2a)选择性99.4%,转化率为97.1%。
实施例14
同实施例1,所用环氧化合物为环氧乙烷(1b),其他不变,得到(2b)选择性99.2%,转化率为98.9%。
实施例15
同实施例1,所用环氧化合物为环氧乙烷(1b),催化剂用量为0.6g(与环氧化合物的摩尔比为1.0mol%),其他条件不变,得到(2b)选择性99.5%,转化率为99.4%。
实施例16
同实施例1,所用环氧化合物为环氧氯丙烷(1c),其他条件不变,得到(2c)选择性93.7%,转化率为99.7%。
实施例17
同实施例1,所用环氧化合物为环氧苯乙烯(1d),其他条件不变,得到(2d)选择性98.0%,转化率为99.3%。
实施例18
同实施例1,所用环氧化合物为苯氧基环氧乙烷(1e),其他条件不变,得到(2e)选择性97.8%,转化率为99.1%。
实施例19
同实施例1,所用环氧化合物为环氧环己烷(lf),反应温度为140℃,压力为5MPa,时间为8小时,其他条件不变,得到(2f)选择性99.0%,转化率为99.6%。
实施例20
同实施例1,所用环氧化合物为烯丙基环氧乙烷(lg),催化剂用量为环氧化合物的2.0mol%,其他条件不变,得到(2g)选择性99.0%,转化率为99.5%。
Claims (10)
1.一种基于复合材料负载杂环离子液体催化CO2合成环状碳酸酯的方法,其特征在于使用有机或无机复合材料负载杂环或杂原子取代的季鏻类离子液体作为催化剂,或添加微量添加剂,以CO2为原料合成环状碳酸酯。
3.根据权利要求1所述,载体为有机或无机复合材料,有机复合材料优选纤维素、聚乙二醇、木质素、壳聚糖、碳材料复合聚苯乙烯中的任意一种;无机化合物优选MCM-41、SAB-15、ZSM-5中的任意一种。
6.根据权利要求4所述的方法,其特征在于,所述催化剂离子液体的加入量与环氧化合物的摩尔比为0.1-10.0%,优选为0.5-1.5%。
7.根据权利要求4-5所述的方法,优选地,所述环氧化合物选自环氧乙烷、环氧丙烷、环氧氯丙烷、环氧环己烷、氧化苯乙烯等中的至少一种。
8.根据权利要求4-6所述的方法,其特征在于,所述催化反应的操作压力为0.1-10MPa,优选1-5MPa。
9.根据权利要求4-7所述的方法,其特征在于,所述催化反应的操作温度为60-220℃,优选为80-160℃。
10.根据权利要求4-8所述的方法,其特征在于,所述催化反应的操作时间为0.25-24h,优选为2-5h。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310295425.9A CN116375677A (zh) | 2023-03-24 | 2023-03-24 | 一种杂环非均相催化剂的合成及应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310295425.9A CN116375677A (zh) | 2023-03-24 | 2023-03-24 | 一种杂环非均相催化剂的合成及应用 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN116375677A true CN116375677A (zh) | 2023-07-04 |
Family
ID=86968664
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202310295425.9A Pending CN116375677A (zh) | 2023-03-24 | 2023-03-24 | 一种杂环非均相催化剂的合成及应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN116375677A (zh) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102336735A (zh) * | 2011-07-18 | 2012-02-01 | 中国科学院过程工程研究所 | 一种离子液体催化制备环状碳酸酯的方法 |
CN102516220A (zh) * | 2011-12-23 | 2012-06-27 | 中国科学院过程工程研究所 | 一种化学负载型多羟基季铵类离子液体催化制备环状碳酸酯的方法 |
CN102838583A (zh) * | 2012-09-10 | 2012-12-26 | 南昌航空大学 | 一种功能化季鏻盐离子液体制备环状碳酸酯的方法 |
US20130035497A1 (en) * | 2011-08-05 | 2013-02-07 | Horng Shiey-Shiun | Method of manufacturing cyclic carbonate from carbon dioxide |
US20130072727A1 (en) * | 2010-06-07 | 2013-03-21 | Institute Of Process Engineering, Chinese Academy Of Sciences | Process for producing ethylene glycol catalyzed by ionic liquid |
CN104974128A (zh) * | 2015-07-24 | 2015-10-14 | 大连理工大学 | 一种负载型季鏻盐催化剂制备环状碳酸酯的方法 |
-
2023
- 2023-03-24 CN CN202310295425.9A patent/CN116375677A/zh active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130072727A1 (en) * | 2010-06-07 | 2013-03-21 | Institute Of Process Engineering, Chinese Academy Of Sciences | Process for producing ethylene glycol catalyzed by ionic liquid |
CN102336735A (zh) * | 2011-07-18 | 2012-02-01 | 中国科学院过程工程研究所 | 一种离子液体催化制备环状碳酸酯的方法 |
US20130035497A1 (en) * | 2011-08-05 | 2013-02-07 | Horng Shiey-Shiun | Method of manufacturing cyclic carbonate from carbon dioxide |
CN102516220A (zh) * | 2011-12-23 | 2012-06-27 | 中国科学院过程工程研究所 | 一种化学负载型多羟基季铵类离子液体催化制备环状碳酸酯的方法 |
CN102838583A (zh) * | 2012-09-10 | 2012-12-26 | 南昌航空大学 | 一种功能化季鏻盐离子液体制备环状碳酸酯的方法 |
CN104974128A (zh) * | 2015-07-24 | 2015-10-14 | 大连理工大学 | 一种负载型季鏻盐催化剂制备环状碳酸酯的方法 |
Non-Patent Citations (1)
Title |
---|
张文林,张 宾,闫佳伟,史紫微,张佳莉,李春利: "离子液体用于催化 CO2环加成反应的研究进展", 离子液体用于催化 CO2环加成反应的研究进展, vol. 43, no. 3, 31 December 2018 (2018-12-31), pages 104 - 110 * |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101318949B (zh) | 一种固载离子液体催化剂催化合成环状碳酸酯的方法 | |
Dai et al. | Cross-linked polymer grafted with functionalized ionic liquid as reusable and efficient catalyst for the cycloaddition of carbon dioxide to epoxides | |
CN112341394B (zh) | 一种氢键供体功能化的聚合离子液体催化制备环状碳酸酯的方法 | |
CN101531725B (zh) | α-二亚胺镍配合物烯烃聚合催化剂及其制备方法与制备支化聚乙烯的方法 | |
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 (zh) | 碱性离子液体催化一步法制备碳酸二甲酯的方法 | |
CN106040296B (zh) | 氯化1-氨基聚丙醚-3-甲基咪唑离子液体催化剂的制备方法 | |
CN105732566B (zh) | 一种制备碳酸乙烯酯的方法 | |
CN109776480A (zh) | 一种用于合成环状碳酸酯的催化剂、制备方法以及环状碳酸酯的制备方法 | |
CN108636450B (zh) | 一种聚离子液体复合材料及其制备方法和应用 | |
CN106279094B (zh) | 一种硫脲类离子液体催化制备环状碳酸酯的方法 | |
CN101474576A (zh) | 一种用于合成环状碳酸酯的催化体系 | |
CN113788793B (zh) | 磺酸功能化的咪唑离子液体催化剂及其制备方法和应用 | |
CN112409190B (zh) | 胺盐类离子液体高效催化合成环状碳酸酯的方法 | |
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 (zh) | 一种咪唑离子液体功能化的锌卟啉及其应用 | |
CN111909094A (zh) | 多活性中心离子液体、制备方法以及利用其催化合成环状碳酸酯的方法 | |
CN111233816B (zh) | 一种环状碳酸酯的制备方法 | |
CN104707652A (zh) | 一种端羧基聚醚离子液体催化剂及其制备方法 | |
CN109810091B (zh) | 用于环氧烷烃和二氧化碳制备碳酸亚烷基酯的方法 | |
CN110078702A (zh) | 一种聚离子液体框架催化剂制备环状碳酸酯的方法 | |
CN114276322A (zh) | 一种光引发聚合离子液体材料催化制备环状碳酸酯的方法 | |
CN114011459A (zh) | 一种钛系双酸型离子液体催化剂及制备方法与应用 | |
CN113117747A (zh) | 一种用于二氧化碳合成环状碳酸酯的界面离子液体负载型催化剂 | |
CN106256845A (zh) | 一种高分子量脂肪族聚碳酸酯的制备方法 |
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 |