CN116920939A - Polyion liquid-loaded silicon dioxide catalyst and preparation method and application thereof - Google Patents
Polyion liquid-loaded silicon dioxide catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN116920939A CN116920939A CN202311193867.9A CN202311193867A CN116920939A CN 116920939 A CN116920939 A CN 116920939A CN 202311193867 A CN202311193867 A CN 202311193867A CN 116920939 A CN116920939 A CN 116920939A
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- divinyl
- liquid
- silicon dioxide
- vinylimidazole
- 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.)
- Granted
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 149
- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 72
- 229920000831 ionic polymer Polymers 0.000 title claims abstract description 50
- 239000007788 liquid Substances 0.000 title claims abstract description 38
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 48
- 150000005676 cyclic carbonates Chemical class 0.000 claims abstract description 32
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 24
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 24
- 239000004593 Epoxy Substances 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 7
- 239000002608 ionic liquid Substances 0.000 claims description 66
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 54
- JBLNCBDNFKLARF-UHFFFAOYSA-N 4,5-bis(ethenyl)-1h-imidazole Chemical compound C=CC=1N=CNC=1C=C JBLNCBDNFKLARF-UHFFFAOYSA-N 0.000 claims description 40
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 37
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- -1 tetrafluoroborate Chemical compound 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000003999 initiator Substances 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 18
- 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 16
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 239000012046 mixed solvent Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- GLISZRPOUBOZDL-UHFFFAOYSA-N 3-bromopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCBr GLISZRPOUBOZDL-UHFFFAOYSA-N 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 claims description 4
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 claims description 4
- NILZGRNPRBIQOG-UHFFFAOYSA-N 3-iodopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCI NILZGRNPRBIQOG-UHFFFAOYSA-N 0.000 claims description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 150000008282 halocarbons Chemical class 0.000 claims description 4
- 150000005826 halohydrocarbons Chemical class 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 claims description 3
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 claims description 3
- OVISMSJCKCDOPU-UHFFFAOYSA-N 1,6-dichlorohexane Chemical compound ClCCCCCCCl OVISMSJCKCDOPU-UHFFFAOYSA-N 0.000 claims description 3
- QLIMAARBRDAYGQ-UHFFFAOYSA-N 1,6-diiodohexane Chemical compound ICCCCCCI QLIMAARBRDAYGQ-UHFFFAOYSA-N 0.000 claims description 3
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 3
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 claims description 3
- 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 description 2
- GBBZLMLLFVFKJM-UHFFFAOYSA-N 1,2-diiodoethane Chemical compound ICCI GBBZLMLLFVFKJM-UHFFFAOYSA-N 0.000 claims description 2
- KJDRSWPQXHESDQ-UHFFFAOYSA-N 1,4-dichlorobutane Chemical compound ClCCCCCl KJDRSWPQXHESDQ-UHFFFAOYSA-N 0.000 claims description 2
- ROUYUBHVBIKMQO-UHFFFAOYSA-N 1,4-diiodobutane Chemical compound ICCCCI ROUYUBHVBIKMQO-UHFFFAOYSA-N 0.000 claims description 2
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 229910004298 SiO 2 Inorganic materials 0.000 description 17
- 238000006116 polymerization reaction Methods 0.000 description 15
- 238000001291 vacuum drying Methods 0.000 description 15
- 239000007787 solid Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 239000011258 core-shell material Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- 108010002352 Interleukin-1 Proteins 0.000 description 3
- 108010002350 Interleukin-2 Proteins 0.000 description 3
- 108010002386 Interleukin-3 Proteins 0.000 description 3
- 108090000978 Interleukin-4 Proteins 0.000 description 3
- 108010002616 Interleukin-5 Proteins 0.000 description 3
- 108090001005 Interleukin-6 Proteins 0.000 description 3
- 108090001007 Interleukin-8 Proteins 0.000 description 3
- 238000007036 catalytic synthesis reaction Methods 0.000 description 3
- 238000006352 cycloaddition reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 108010002586 Interleukin-7 Proteins 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- AZUHIVLOSAPWDM-UHFFFAOYSA-N 2-(1h-imidazol-2-yl)-1h-imidazole Chemical group C1=CNC(C=2NC=CN=2)=N1 AZUHIVLOSAPWDM-UHFFFAOYSA-N 0.000 description 1
- 239000013177 MIL-101 Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000013310 covalent-organic framework Substances 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J31/0278—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 nitrogen as cationic centre
- B01J31/0281—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 nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—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 nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
-
- 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
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
Abstract
The invention provides a polyion liquid-loaded silicon dioxide catalyst, a preparation method and application thereof. Compared with the prior art, the catalyst has the advantages of no metal, multiple active sites and low cost, and the preparation process is simple. The catalyst is used as a heterogeneous catalyst in a system for synthesizing the cyclic carbonate by using carbon dioxide and an epoxy compound, and has the advantages of high catalytic activity, no need of solvent and cocatalyst.
Description
Technical Field
The invention belongs to the field of green catalytic synthesis, and particularly relates to a polyion liquid-supported silicon dioxide catalyst, and a preparation method and application thereof.
Background
Carbon dioxide (CO) 2 ) As a major greenhouse gas, a key factor responsible for global warming, the recycling principle of "near zero emission" can be realized by converting "waste carbon" into "activated carbon" through carbon capture and utilization (CCS) technology to enhance carbon recycling, and is receiving extensive attention worldwide. CO 2 As a carbon feedstock for fuels and chemicals, is a non-toxic, economical, abundant and renewable C1 resource. CO is processed by 2 The epoxy compound is converted into cyclic carbonate, the atom utilization rate can reach 100%, and the product has wide application, thus being a CO with great application potential 2 Transformation path. However, CO 2 Is a thermodynamically stable and kinetically inert molecule, which makes CO 2 Which turns into a very challenging task.
In recent years, ionic liquids are widely applied to the field of carbon dioxide cycloaddition due to the inherent advantages of Lewis acid-base sites, adjustable structure, high thermal stability, environmental friendliness and the like. The Chinese patent document with publication number of CN102060837A discloses a preparation method of cyclic carbonate, which uses benzimidazole ionic liquid to synthesize cyclic carbonate through cycloaddition reaction, and the catalyst has the advantages of low cost, mild reaction condition, high selectivity and the like. However, ionic liquids are used as homogeneous catalysts, and often have the problems of difficult product separation, difficult catalyst recovery and utilization, and the like. If the ionic liquid is loaded on the carrier, the problem that the catalyst is difficult to recycle can be effectively solved, and the cost is reduced. Common carriers include: metal organic frameworks, covalent organic frameworks, molecular sieves, and the like. Such as Meili Ding et al, article Incorporation of Imidazolium-Based Poly (ionic liquid) s intoa Metal-Organic Framework for CO 2 Capture and Conversion (ACS Catal., 2018, 8, 3194-3201) discloses an in situ polymerization method for encapsulating a polyionic liquid into MIL-101, and the prepared composite catalyst catalyzes CO under the conditions of 0.1 MPa, 70 ℃, 24h and solvent acetonitrile 2 And epichlorohydrin, the yield of the cyclic carbonate can reach 94%, but the solvent is added in the reaction process, and the monomer size is not required to be excessively large. Chenyen Tsai et al, uniform Core-Shell Microspheres of SiO 2 @MOF for CO 2 Cycloaddition Reactions (Inorg Chem, 2022, 61, 2724-2732) discloses a method of loading MOF material onto SiO 2 Is successfully synthesized on the surface of a plurality of types of SiO 2 @MOF core-shell microspheres. Wherein SiO is 2 Under the conditions of 2 MPa, 80 ℃, 24 and h and a cocatalyst tetrabutylammonium bromide, the catalyst can catalyze carbon dioxide and propylene oxide, the yield of the cyclic carbonate can reach 97 percent, however, the cocatalyst is added in the reaction process, the synthesis process is complex, and the cost is high. The Chinese patent document with publication number CN101318949A discloses a method for synthesizing cyclic carbonate by catalyzing immobilized ionic liquid catalyst, which adopts mesoporous molecular sieve as carrier, and imidazole ionic liquid is loaded on the surface of the mesoporous molecular sieve to prepare catalystThe highest yield of the synthesized cyclic carbonate can reach 92%, but the active sites are few, the catalytic efficiency is low, and the stability is poor. The Chinese patent document with publication number of CN112844473A discloses an alumina-supported polyion liquid catalyst, a preparation method and application thereof, wherein an ionic liquid is supported on the surface of a carrier through a silane coupling agent and hydroxyl on the surface of alumina, and the prepared catalyst has a highest conversion rate of 54.7% in the catalytic synthesis of cyclic carbonate, however, fewer active sites and low catalytic efficiency. The Chinese patent document with publication number of CN114433228A discloses a method for synthesizing cyclic carbonate by catalyzing core-shell type polymeric ionic liquid, which adopts imidazole ionic liquid monomer to polymerize on the surface of inorganic carrier silicon dioxide to form a core-shell type polymeric ionic liquid catalyst for catalyzing CO 2 And epoxy compounds are used for efficiently synthesizing the cyclic carbonate, the yield can reach 97.2% at most, but the active sites are fewer, and the reaction conditions are more severe. Therefore, the heterogeneous catalyst loaded by the current ionic liquid has the defects of few active sites, low catalytic efficiency, poor stability, need of adding a solvent or a cocatalyst, complex synthesis process and the like. Therefore, how to provide a catalyst with low cost, high catalytic activity and good stability is a problem to be solved.
Disclosure of Invention
The invention aims to provide a polyion liquid-loaded silicon dioxide catalyst which can realize the efficient catalytic synthesis of cyclic carbonate under the conditions of no solvent and cocatalyst, high temperature and high pressure, and has simple preparation process, high stability and higher industrial application value.
To achieve the purpose, the structure of the polyionic liquid-supported silica catalyst is as follows:
wherein m=2, 4 or 6, n is an integer and 2.ltoreq.n.ltoreq.500, X - Is Cl - 、Br - 、I - Any one of Y - Is Cl - 、Br - 、I - 、BF 4 - Any one of the following.
The invention provides a preparation method of a polyion liquid-supported silicon dioxide catalyst, which is characterized by comprising the following steps:
(1) Y in the polyionic liquid-supported silica catalyst - Is Cl - 、Br - 、I - In one of the above steps, 1-vinyl imidazole and halogenated hydrocarbon are added into a first organic solvent to react under inert atmosphere for 24-48 h at 60-90 ℃; after the reaction is finished, separating the solvent, washing and drying the ionic liquid to obtain the divinyl imidazole ionic liquid;
alternatively, Y in the polyionic liquid supported silica catalyst - For BF 4 - Dissolving the divinyl imidazole ionic liquid in deionized water, adding sodium fluoborate, stirring at normal temperature for 12-24 h, decompressing, distilling to remove water, drying, dissolving in a mixed solvent, filtering to remove salt, decompressing, distilling to remove the mixed solvent, and drying to obtain the divinyl imidazole ionic liquid with the counter ion of tetrafluoroborate;
(2) Adding spherical silicon dioxide and a silane coupling agent into a second organic solvent together, stirring 12-48 h, dropwise adding 1-vinylimidazole, reacting in an inert atmosphere for 12-48 h at 60-80 ℃, centrifuging, washing and drying to obtain 1-vinylimidazole modified silicon dioxide;
(3) Adding the obtained 1-vinylimidazole modified silicon dioxide, an initiator azodiisobutyronitrile, a divinyl imidazole ionic liquid or a divinyl imidazole ionic liquid with counter ions of tetrafluoroborate into a third organic solvent, reacting in an inert atmosphere for 24-48 h at 70-80 ℃, centrifuging, washing and drying to obtain the polyion liquid-loaded silicon dioxide catalyst.
Preferably, in the step (1), the molar ratio of the 1-vinyl imidazole to the halogenated hydrocarbon is 2-2.4:1; the halohydrocarbon is one of 1, 2-dibromoethane, 1, 2-dichloroethane, 1, 2-diiodoethane, 1, 4-dibromobutane, 1, 4-dichlorobutane, 1, 4-diiodobutane, 1, 6-dibromohexane, 1, 6-dichlorohexane or 1, 6-diiodohexane; the molar concentration of the halohydrocarbon in the first organic solvent is 0.5-1 mol/L, and the first organic solvent comprises one of toluene or acetonitrile; the mol ratio of the divinyl imidazole ionic liquid to the sodium fluoborate is 0.5-0.52:1; the molar concentration of the divinyl imidazole ionic liquid in deionized water is 1-1.5 mol/L; the molar concentration of the divinyl imidazole ionic liquid in the mixed solvent is 1-1.5 mol/L; the mixed solvent comprises anhydrous methanol and dichloromethane, and the volume ratio is 1-1.2:1.
Preferably, in the step (2), the molar ratio of the 1-vinylimidazole to the spherical silicon dioxide is 0.5-1:1; the silane coupling agent is 5% -10% of the spherical silicon dioxide in mass; the silane coupling agent is one of 3-bromopropyl trimethoxy silane, 3-chloropropyl trimethoxy silane or 3-iodopropyl trimethoxy silane; the mole concentration of the spherical silicon dioxide in the second organic solvent is 0.4-1 mol/L, and the second organic solvent comprises one of ethanol or acetonitrile.
Preferably, in the step (3), the molar ratio of the divinyl imidazole ionic liquid or the divinyl imidazole ionic liquid with tetrafluoroborate as the counter ion to the 1-vinyl imidazole modified silica is 0.5-2.5:1; the initiator azodiisobutyronitrile is divinyl imidazole ionic liquid or the counter ion is 3% -5% of the sum of the mass of the divinyl imidazole ionic liquid of tetrafluoroborate and the mass of the silicon dioxide modified by 1-vinyl imidazole; the molar concentration of the 1-vinylimidazole modified silicon dioxide in the third organic solvent is 0.4-1 mol/L, and the third organic solvent comprises one of ethanol or methanol.
The invention also provides application of the polyion liquid-loaded silicon dioxide catalyst in synthesizing cyclic carbonate from carbon dioxide and an epoxy compound.
Preferably, in the application, the epoxy compound is any one of propylene oxide, epichlorohydrin, 1, 2-butylene oxide, cyclohexene oxide or styrene oxide.
Preferably, in said application, CO 2 The pressure is 1-3 MPa, the reaction temperature is 80-120 ℃, and the reaction time is 2-h-12 h.
Preferably, in the application, the mass ratio of the epoxy compound to the polyionic liquid supported silica catalyst is 14.4-24:1.
Compared with the prior art, the invention has the following advantages:
(1) According to the catalyst provided by the invention, the polyion liquid is loaded on the surface of spherical silicon dioxide by adopting a grafting and free radical copolymerization method, so that the core-shell catalyst with multiple active sites is formed, the contact of a reaction substrate and the active sites of the catalyst is facilitated, and the defect of insufficient utilization rate of the active sites of the catalyst is overcome.
(2) The catalyst provided by the invention takes spherical silicon dioxide as a carrier, and introduces a divinyl imidazole ionic liquid with multiple active sites, wherein the ionic liquid has a bisimidazole ring and counter ions, and N on the imidazole ring is used as Lewis alkaline site to activate CO 2 The counter ion can be used as a nucleophilic reagent to accelerate the ring opening of the epoxy compound, has more catalytic active sites, and solves the defect that the current catalyst has fewer catalytic active sites of the epoxy compound.
(3) The catalyst provided by the invention adopts silicon dioxide as a carrier, and has low cost; the catalyst is used for synthesizing the cyclic carbonate from the carbon dioxide and the epoxy compound, has the advantages of stability, difficult decomposition and flexible and controllable structure, solves the problem of difficult recovery and separation of the current homogeneous ionic liquid, does not contain metal ions, and cannot cause environmental pollution due to loss of the metal ions.
Drawings
FIG. 1 is a spherical SiO of example 1 2 And Scanning Electron Microscope (SEM) pictures of SPIL-1;
FIG. 2 is a spherical SiO of example 1 2 、im-SiO 2 -1 and spll-1 infrared (FT-IR) spectra;
FIG. 3 is a spherical SiO of example 1 2 、im-SiO 2 -1 and SPIL-1 under nitrogen atmosphereA thermogravimetric graph;
FIG. 4 is a graph showing the nitrogen adsorption and desorption of the polyionic liquid supported silica catalysts obtained in examples 1 to 7 at 77℃ 77K.
The specific embodiment is as follows:
the invention is further illustrated, but not limited, by the following examples.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are commercially available products.
Example 1
A polyionic liquid supported silica catalyst has the structural formula shown as follows:
wherein m=4, n is an integer and 2.ltoreq.n.ltoreq.500, X - Is Br - ，Y - Is Br - ，
The preparation method comprises the following steps:
(1) 0.11 mol of 1-vinylimidazole and 0.05mol of 1, 4-dibromobutane were added to 75mL of toluene and reacted under a nitrogen atmosphere for 24. 24h at 90 ℃. After the reaction was completed, the solvent was separated, the ionic liquid was washed 3 times with ethyl acetate, unreacted 1-vinylimidazole was removed, and dried under vacuum at 40℃for 12h to obtain a divinylimidazole ionic liquid designated IL-1.
(2) 0.02mol of spherical silicon dioxide and 7% 3-bromopropyl trimethoxy silane are added into 30 mL ethanol together, after stirring for 24h, 0.015mol of 1-vinylimidazole is added dropwise, and the reaction is carried out under nitrogen atmosphere for 24h and at 70 ℃. After the reaction, centrifuging, washing the solid with ethanol for 3 times, removing unreacted silane coupling agent and 1-vinylimidazole, and vacuum drying at 70deg.C for 24 hr to obtain 1-vinylimidazole modified silica, designated im-SiO 2 -1。
(3) The 0.02 molim-SiO obtained above was then treated 2 -1 and 0.03molILAdding-1 into 30 mL ethanol, and adding initiator azodiisobutyronitrile, which is IL-1 and im-SiO 2 4% of the sum of-1), the polymerization was carried out under a nitrogen atmosphere for a reaction time of 36 h at a reaction temperature of 70℃and a polymerization degree of n. After the reaction is finished, centrifuging, washing the solid with ethanol for 3 times, removing unreacted divinyl imidazole ionic liquid and an initiator, and vacuum drying at 70 ℃ for 12 hours to obtain the polyion liquid-supported silicon dioxide catalyst, namely SPIL-1. The specific surface area was measured to be 82m 2 /g。
Example 2
A polyionic liquid supported silica catalyst has the structural formula shown as follows:
wherein m=2, n is an integer, 2.ltoreq.n.ltoreq.500, X - Is Br - ，Y - Is Cl - ，
(1) 0.10 mol of 1-vinylimidazole and 0.05mol of 1, 2-dichloroethane were added to 50 g mL of toluene and reacted under nitrogen atmosphere for 36 g h g at 60 ℃. After the reaction, the solvent was separated, the ionic liquid was washed 3 times with ethyl acetate, unreacted 1-vinylimidazole was removed, and dried under vacuum at 40℃for 12h to give a divinylimidazole ionic liquid designated IL-2.
(2) 0.02mol of spherical silicon dioxide and 3-bromopropyl trimethoxy silane with the mass of 5 percent of the silicon dioxide are added into 20 mL ethanol together, after stirring for 12h, 0.01 mol of 1-vinylimidazole is added dropwise, and the reaction is carried out under the nitrogen atmosphere for 12h at the reaction temperature of 70 ℃. After the reaction, centrifuging, washing the solid with ethanol for 3 times, removing unreacted silane coupling agent and 1-vinylimidazole, and vacuum drying at 70deg.C for 24-h to obtain 1-vinylimidazole-modified silica, designated im-SiO 2 -2。
(3) The 0.02 molim-SiO obtained above was then treated 2 -2 and 0.05mol of IL-2 are added to 50 mL ethanol, followed by the addition of the initiator azobisisobutyronitrile, which is IL-2 and im-SiO by mass 2 Sum of-2The polymerization was carried out under a nitrogen atmosphere for a reaction time of 24h at a reaction temperature of 70℃and a polymerization degree of n. After the reaction is finished, centrifuging, washing the solid with ethanol for 3 times, removing unreacted divinyl imidazole ionic liquid and an initiator, and vacuum drying at 70 ℃ for 12 hours to obtain the polyion liquid-supported silicon dioxide catalyst, namely SPIL-2. The specific surface area was found to be 76m 2 /g。
Example 3
A polyionic liquid supported silica catalyst has the structural formula shown as follows:
wherein m=6, n is an integer and 2.ltoreq.n.ltoreq.500, X - Is Br - ，Y - Is I - ，
(1) 0.12 mol of 1-vinylimidazole and 0.05mol of 1, 6-diiodohexane were added to 100 mL toluene and reacted under nitrogen atmosphere for 48h at 90 ℃. After the reaction was completed, the solvent was separated, the ionic liquid was washed 3 times with ethyl acetate, unreacted 1-vinylimidazole was removed, and dried under vacuum at 40℃for 12h to obtain a divinylimidazole ionic liquid designated IL-3.
(2) 0.02mol of spherical silicon dioxide and 3-bromopropyl trimethoxy silane with the mass of 10 percent of the silicon dioxide are added into 50 mL ethanol together, after stirring for 48h, 0.02mol of 1-vinylimidazole is added dropwise, and the reaction is carried out under the nitrogen atmosphere for 48h at the reaction temperature of 70 ℃. After the reaction, centrifuging, washing the solid with ethanol for 3 times, removing unreacted silane coupling agent and 1-vinylimidazole, and vacuum drying at 70deg.C for 24-h to obtain 1-vinylimidazole-modified silica, designated im-SiO 2 -3。
(3) The 0.02 molim-SiO obtained above was then treated 2 Adding-3 and 0.01 mol IL-3 into 20 mL ethanol, and adding azo-diisobutyronitrile as initiator, wherein the mass is IL-3 and im-SiO 2 3% of the sum of 3), the polymerization was carried out under nitrogen atmosphere for a reaction time of 48 and h, at a reaction temperature of 70℃and a polymerization degree of n. ReactionAfter the completion, centrifuging, washing the solid with ethanol for 3 times, removing unreacted divinyl imidazole ionic liquid and an initiator, and vacuum drying at 70 ℃ for 12 hours to obtain the polyion liquid-supported silicon dioxide catalyst, namely SPIL-3. Specific surface area was measured to be 109m 2 /g。
Example 4
A polyionic liquid supported silica catalyst has the structural formula shown as follows:
wherein m=4, n is an integer and 2.ltoreq.n.ltoreq.500, X - Is Cl - ，Y - Is Br - ，
(1) 0.11 mol of 1-vinylimidazole and 0.05mol of 1, 4-dibromobutane were added to 70mL of acetonitrile and reacted under a nitrogen atmosphere for 36. 36 h at a reaction temperature of 80 ℃. After the reaction, the solvent was separated, the ionic liquid was washed 3 times with ethyl acetate, unreacted 1-vinylimidazole was removed, and dried under vacuum at 40℃for 12h to give a divinylimidazole ionic liquid designated IL-4.
(2) 0.02mol of spherical silica and 7% by mass of 3-chloropropyl trimethoxysilane are added into 30 mL acetonitrile together, after stirring for 24h, 0.015mol of 1-vinylimidazole is added dropwise, and the reaction is carried out under nitrogen atmosphere for 24h and at 80 ℃. After the reaction, centrifuging, washing the solid with ethanol for 3 times, removing unreacted silane coupling agent and 1-vinylimidazole, and vacuum drying at 70deg.C for 24-h to obtain 1-vinylimidazole-modified silica, designated im-SiO 2 -4。
(3) The 0.02 molim-SiO obtained above was then treated 2 -4 and 0.03mol of IL-4 are added to 30 mL ethanol, followed by the addition of the initiator azobisisobutyronitrile, which is IL-4 and im-SiO by mass 2 4% of the sum of-4), the polymerization was carried out under a nitrogen atmosphere for a reaction time of 36 h at 80℃and a polymerization degree of n. After the reaction is finished, centrifuging, washing the solid with ethanol for 3 times, and removing unreacted divinyl imidazole ionic liquid and initiator at 70 DEG CAnd (3) drying in vacuum for 12 hours to obtain the polyion liquid-supported silicon dioxide catalyst, namely the SPIL-4. The specific surface area was measured to be 89m 2 /g。
Example 5
A polyionic liquid supported silica catalyst has the structural formula shown as follows:
.
a polyionic liquid supported silica catalyst has the structural formula shown as follows:
wherein m=6, n is an integer and 2.ltoreq.n.ltoreq.500, X - Is I - ，Y - Is Cl - ，
(1) 0.11 mol of 1-vinylimidazole and 0.05mol of 1, 6-dichlorohexane were added to 80mL of acetonitrile and reacted under nitrogen atmosphere for 24. 24h at 60 ℃. After the reaction, the solvent was separated, the ionic liquid was washed 3 times with ethyl acetate, unreacted 1-vinylimidazole was removed, and dried under vacuum at 40℃for 12h to give a divinylimidazole ionic liquid designated IL-5.
(2) 0.02mol of spherical silica and 3-iodopropyl trimethoxy silane with the mass of 5% of the silica are added into 40 mL acetonitrile together, after stirring for 24h, 0.015mol of 1-vinylimidazole is added dropwise, and the reaction is carried out under nitrogen atmosphere for 24h and at 60 ℃. After the reaction, centrifuging, washing the solid with ethanol for 3 times, removing unreacted silane coupling agent and 1-vinylimidazole, and vacuum drying at 70deg.C for 24-h to obtain 1-vinylimidazole-modified silica, designated im-SiO 2 -5。
(3) The 0.02 molim-SiO obtained above was then treated 2 -5 and 0.03mol of IL-5 are added to 40 mL methanol, followed by the addition of the initiator azobisisobutyronitrile, which is IL-5 and im-SiO by mass 2 5% of the sum of-5), the polymerization was carried out under nitrogen atmosphere for a reaction time of 36 h and at a reaction temperature of 70℃and a polymerization degree of n. After the reaction is finished, centrifuging, washing the solid with methanol for 3 times, removing unreacted divinyl imidazole ionic liquid and initiator, vacuum drying at 60 ℃ for 12 hours,the polyionic liquid-loaded silicon dioxide catalyst, namely the SPIL-5, is obtained. The specific surface area was found to be 98m 2 /g。
Example 6
A polyionic liquid supported silica catalyst has the structural formula shown as follows:
wherein m=4, n is an integer and 2.ltoreq.n.ltoreq.500, X - Is I - ，Y - For BF 4 - ，
(1) 0.03mol of IL-1 from example 1 was dissolved in 30 mL deionized water, 0.06 mol of sodium fluoroborate was added thereto, and the mixture was stirred at room temperature for 12: 12h. After the reaction is finished, reduced pressure distillation is carried out to remove water, and vacuum drying is carried out for 24 hours at 80 ℃. Dissolving the obtained ionic liquid in a mixed solvent of 30 mL anhydrous methanol and dichloromethane, wherein the volume ratio is 1:1, filtering to remove salt, removing the mixed solvent by reduced pressure distillation, and drying in vacuum at 60 ℃ for 12 hours, and repeating the salt removal for multiple times until no sodium bromide is generated, thereby obtaining the divinyl imidazole ionic liquid with tetrafluoroborate as counter ion, which is named as IL-6.
(2) 0.02mol of spherical silica and 7% by mass of 3-iodopropyl trimethoxy silane are added into 30 mL ethanol together, after stirring for 36 h, 0.015mol of 1-vinylimidazole is added dropwise, and the reaction is carried out under nitrogen atmosphere for 36 h and at 60 ℃. After the reaction, centrifuging, washing the solid with ethanol for 3 times, removing unreacted silane coupling agent and 1-vinylimidazole, and vacuum drying at 70deg.C for 24-h to obtain 1-vinylimidazole-modified silica, designated im-SiO 2 -6。
(3) The 0.02 molim-SiO obtained above was then treated 2 -6 and 0.03mol of IL-6 are added to 30 mL ethanol, followed by the addition of the initiator azobisisobutyronitrile, which is IL-6 and im-SiO by mass 2 4% of the sum of 6), the polymerization was carried out under nitrogen atmosphere for a reaction time of 36 h, at a reaction temperature of 75℃and a degree of polymerization of n. After the reaction was completed, the solid was centrifuged and washed with ethanol 3 times to remove unreacted reactionAnd (3) carrying out vacuum drying for 12 hours at 70 ℃ on the divinyl imidazole ionic liquid with tetrafluoroborate ions and an initiator to obtain the silicon dioxide catalyst loaded by the polyion liquid, namely the SPIL-6. The specific surface area was measured to be 72m 2 /g。
Example 7
A polyionic liquid supported silica catalyst has the structural formula shown as follows:
wherein m=2, n is an integer, 2.ltoreq.n.ltoreq.500, X - Is Cl - ，Y - For BF 4 - ，
(1) 0.10 mol of 1-vinylimidazole and 0.05mol of 1, 2-dibromoethane were added to 50 toluene mL, and reacted under a nitrogen atmosphere for 24h at a reaction temperature of 70 ℃. After the reaction was completed, the solvent was separated, the ionic liquid was washed 3 times with ethyl acetate, unreacted 1-vinylimidazole was removed, and dried under vacuum at 40℃for 12h to obtain a divinylimidazole ionic liquid designated IL-7. 0.03mol of IL-7 is dissolved in 20 mL deionized water, 0.058 mol of sodium fluoborate is added, and the mixture is stirred at normal temperature for 24h. After the reaction is finished, reduced pressure distillation is carried out to remove water, and vacuum drying is carried out for 24 hours at 80 ℃. Dissolving the obtained ionic liquid in a mixed solvent of 20 mL anhydrous methanol and dichloromethane, wherein the volume ratio is 1.2:1, filtering to remove salt, removing the mixed solvent by reduced pressure distillation, and drying at 60 ℃ in vacuum for 12 hours, and repeating the salt removal for multiple times until no sodium bromide is generated, thereby obtaining the divinyl imidazole ionic liquid with tetrafluoroborate as a counter ion, which is named as IL-8.
(2) 0.02mol of spherical silicon dioxide and 3-chloropropyl trimethoxysilane with the mass of 10 percent of the silicon dioxide are added into 30 mL ethanol together, after 36 h of stirring, 0.015mol of 1-vinylimidazole is added dropwise for reaction under nitrogen atmosphere, the reaction time is 36 h, and the reaction temperature is 70 ℃. After the reaction, centrifuging, washing the solid with ethanol for 3 times, removing unreacted silane coupling agent and 1-vinylimidazole, and vacuum drying at 70deg.C for 24-h to obtain 1-vinylimidazole modified silicaNamed im-SiO 2 -7。
(3) 0.02mol of im-SiO obtained above 2 7 and 0.03mol of IL-8 are added to 30 mL methanol, and then the initiator azobisisobutyronitrile, which is the mass of IL-8 and im-SiO, is added 2 3% of the sum of 7), the polymerization was carried out under nitrogen atmosphere for a reaction time of 24h at a reaction temperature of 70℃and a polymerization degree of n. After the reaction is finished, centrifuging, washing the solid with ethanol for 3 times, removing the unreacted divinyl imidazole ionic liquid with counter ions of tetrafluoroborate and the initiator, and vacuum drying at 70 ℃ for 12 hours to obtain the silicon dioxide catalyst loaded by the polyion liquid, namely the SPIL-8. The specific surface area was found to be 67m 2 /g。
Application example 1
0.1 g catalyst, using the SPIL-1 of example 1, and 1.66g propylene oxide, was charged into a 20 mL stainless steel autoclave equipped with a magnet, and reacted under stirring at 1.5 MPa and 100℃for 4h. After the reaction is finished, the autoclave is cooled to below 10 ℃ to release redundant CO 2 Centrifuging, and analyzing the supernatant by nuclear magnetism to obtain the cyclic carbonate with the yield of 93.5%.
Application example 2
The difference from application example 1 was only that the catalyst was SPIL-2 of example 2, and the other conditions were unchanged, to obtain a cyclic carbonate yield of 75.2%.
Application example 3
The difference from application example 1 was only that the catalyst was SPIL-3 of example 3, and the other conditions were not changed, and the cyclic carbonate yield was 82.4%.
Application example 4
The difference from application example 1 was only that the catalyst was SPIL-4 of example 4, and the other conditions were unchanged, to give a cyclic carbonate yield of 85.7%.
Application example 5
The difference from application example 1 was only that the catalyst was SPIL-5 of example 5, and the other conditions were unchanged, to give a cyclic carbonate yield of 80.3%.
Application example 6
The difference from application example 1 was only that the catalyst was SPIL-6 of example 6, and the other conditions were unchanged, to give a cyclic carbonate yield of 67.8%.
Application example 7
The difference from application example 1 was only that the catalyst was SPIL-8 of example 7, and the other conditions were unchanged, to give a cyclic carbonate yield of 59.5%.
Application example 8
The difference from application example 1 was that 1.66g of propylene oxide was adjusted to 1.85g of epichlorohydrin, the pressure was 1 MPa, the temperature was 80℃and the reaction time was 2h, and the other conditions were unchanged, to give a cyclic carbonate yield of 78.4%.
Application example 9
The difference from application example 1 was that 1.66g of propylene oxide was adjusted to 1.44g of 1, 2-butylene oxide, the pressure was 2 MPa, the temperature was 100℃and the reaction time was 6 h, and other conditions were unchanged, to obtain a cyclic carbonate yield of 87.5%.
Application example 10
The difference from application example 1 was that 1.66g of propylene oxide was adjusted to 1.96g of cyclohexene oxide, the pressure was 3 MPa, the temperature was 120℃and the reaction time was 12h, and the other conditions were unchanged, to give a cyclic carbonate yield of 43.7%.
Application example 11
The difference from application example 1 was that 1.66g of propylene oxide was adjusted to 2.4g of styrene oxide, the pressure was 3 MPa, the temperature was 120℃and the reaction time was 8h, and other conditions were unchanged, to give a cyclic carbonate yield of 58.1%.
Comparative example 1
The difference from application example 1 was only that spherical silica of example 1 was used as the catalyst, and the other conditions were unchanged, to obtain a cyclic carbonate yield of 8.2%.
Comparative example 2
The only difference from application example 1 is that the catalyst employs im-SiO of example 1 2 -1, the other conditions being unchanged, yields of cyclic carbonate of 28.5% are obtained.
Table 1 shows im-SiO as in example 1 2 -Elemental Analysis (EA) of 1 and spll-1 and calculating the content of ionic liquid contained based on the test results.
For spherical SiO in example 1 2 SEM characterization of SPIL-1 (FIG. 1), which shows that SiO 2 The polymer is smooth and spherical, and the SPIL-1 is spherical with a rough surface, which indicates that the polyion liquid is successfully loaded on the surface of spherical silicon dioxide.
For spherical SiO in example 1 2 、im-SiO 2 FT-IR characterization of-1 and SPIL-1 (FIG. 2) revealed 1572 cm -1 The stretching vibration peak of C=N bond on the ionic liquid is shown, which further indicates that the polyionic liquid is successfully introduced into the silicon dioxide carrier.
For spherical SiO in example 1 2 、im-SiO 2 -1 and spll-1 were subjected to thermogravimetric tests (figure 3) under nitrogen atmosphere, and before 200 ℃ the material was stable and not decomposed, indicating a better thermal stability of the material.
The polyionic liquid-supported silica catalysts obtained in examples 1 to 7 were subjected to a nitrogen adsorption/desorption test (FIG. 4) at 77K, the nitrogen adsorption/desorption isotherm being a type II curve and the specific surface area being 67 to 109m 2 And/g, illustrating that the reaction substrate is contacted with the surface active site of the polyionic liquid-supported silica catalyst, and the catalytic activity mainly depends on the high active site of the polyionic liquid supported on the surface of the catalyst.
It is obvious to those skilled in the art that the present invention can be practiced with equivalent arrangements or equivalent alternatives, which are within the purview of the appended claims.
Claims (9)
1. A polyionic liquid supported silica catalyst characterized by the structural formula:
,
wherein m=2, 4 or 6, n is an integer and2≤n≤500，X - is Cl - 、Br - 、I - Any one of Y - Is Cl - 、Br - 、I - 、BF 4 - Any one of the following.
2. The method for preparing a polyionic liquid supported silica catalyst according to claim 1, comprising the steps of:
(1) Y in the polyionic liquid-supported silica catalyst - Is Cl - 、Br - 、I - In one of the above steps, 1-vinyl imidazole and halogenated hydrocarbon are added into a first organic solvent to react under inert atmosphere for 24-48 h at 60-90 ℃; after the reaction is finished, separating the solvent, washing and drying the ionic liquid to obtain the divinyl imidazole ionic liquid;
alternatively, Y in the polyionic liquid supported silica catalyst - For BF 4 - Dissolving a divinyl imidazole ionic liquid in deionized water, adding sodium fluoborate, stirring for 12-24 hours at normal temperature, distilling under reduced pressure to remove water, drying, dissolving in a mixed solvent, filtering to remove salt, distilling under reduced pressure to remove the mixed solvent, and drying to obtain the divinyl imidazole ionic liquid with tetrafluoroborate as counter ion;
(2) Adding spherical silicon dioxide and a silane coupling agent into a second organic solvent together, stirring 12-48 h, dropwise adding 1-vinylimidazole, reacting for 12-48 hours in an inert atmosphere at the reaction temperature of 60-80 ℃, centrifuging, washing and drying to obtain 1-vinylimidazole modified silicon dioxide;
(3) Adding the obtained 1-vinylimidazole modified silicon dioxide, an initiator azodiisobutyronitrile, a divinyl imidazole ionic liquid or a divinyl imidazole ionic liquid with counter ions of tetrafluoroborate into a third organic solvent, reacting in an inert atmosphere for 24-48 h at 70-80 ℃, centrifuging, washing and drying to obtain the polyion liquid-loaded silicon dioxide catalyst.
3. The method for preparing a polyionic liquid supported silica catalyst according to claim 2, wherein in the step (1), the molar ratio of 1-vinylimidazole to halogenated hydrocarbon is 2-2.4:1; the halohydrocarbon is one of 1, 2-dibromoethane, 1, 2-dichloroethane, 1, 2-diiodoethane, 1, 4-dibromobutane, 1, 4-dichlorobutane, 1, 4-diiodobutane, 1, 6-dibromohexane, 1, 6-dichlorohexane or 1, 6-diiodohexane; the molar concentration of the halohydrocarbon in the first organic solvent is 0.5-1 mol/L, and the first organic solvent comprises one of toluene or acetonitrile; the mol ratio of the divinyl imidazole ionic liquid to the sodium fluoborate is 0.5-0.52:1; the molar concentration of the divinyl imidazole ionic liquid in deionized water is 1-1.5 mol/L; the molar concentration of the divinyl imidazole ionic liquid in the mixed solvent is 1-1.5 mol/L; the mixed solvent comprises anhydrous methanol and dichloromethane, and the volume ratio is 1-1.2:1.
4. The method for preparing a polyionic liquid supported silica catalyst according to claim 2, wherein in the step (2), the molar ratio of 1-vinylimidazole to spherical silica is 0.5-1:1; the silane coupling agent is 5% -10% of the spherical silicon dioxide in mass; the silane coupling agent is one of 3-bromopropyl trimethoxy silane, 3-chloropropyl trimethoxy silane or 3-iodopropyl trimethoxy silane; the mole concentration of the spherical silicon dioxide in the second organic solvent is 0.4-1 mol/L, and the second organic solvent comprises one of ethanol or acetonitrile.
5. The method for preparing a polyionic liquid supported silica catalyst according to claim 2, wherein in the step (3), the molar ratio of the divinyl imidazole ionic liquid or the divinyl imidazole ionic liquid with tetrafluoroborate as the counter ion to the 1-vinyl imidazole modified silica is 0.5-2.5:1; the initiator azodiisobutyronitrile is divinyl imidazole ionic liquid or the counter ion is 3% -5% of the sum of the mass of the divinyl imidazole ionic liquid of tetrafluoroborate and the mass of the silicon dioxide modified by 1-vinyl imidazole; the molar concentration of the 1-vinylimidazole modified silicon dioxide in the third organic solvent is 0.4-1 mol/L, and the third organic solvent comprises one of ethanol or methanol.
6. Use of the polyionic liquid supported silica catalyst of claim 1 in the synthesis of cyclic carbonates from carbon dioxide and epoxy compounds.
7. The use of the polyionic liquid supported silica catalyst according to claim 6 in the synthesis of cyclic carbonates from carbon dioxide and an epoxy compound, wherein the epoxy compound is any one of propylene oxide, epichlorohydrin, 1, 2-butylene oxide, cyclohexene oxide or styrene oxide.
8. Use of the polyionic liquid supported silica catalyst according to claim 6 or 7 for the synthesis of cyclic carbonates from carbon dioxide and an epoxide compound, comprising the steps of: adding a polyionic liquid-supported silica catalyst, an epoxy compound and carbon dioxide into the reaction, and adding CO 2 The pressure is 1-3 MPa, the reaction temperature is 80-120 ℃, and the reaction time is 2 h-12 h, thus obtaining the cyclic carbonate.
9. The application of the polyion liquid supported silica catalyst in synthesizing cyclic carbonate from carbon dioxide and an epoxy compound according to claim 8, wherein the mass ratio of the epoxy compound to the polyion liquid supported silica catalyst is 14.4-24:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311193867.9A CN116920939B (en) | 2023-09-15 | 2023-09-15 | Polyion liquid-loaded silicon dioxide catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311193867.9A CN116920939B (en) | 2023-09-15 | 2023-09-15 | Polyion liquid-loaded silicon dioxide catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116920939A true CN116920939A (en) | 2023-10-24 |
| CN116920939B CN116920939B (en) | 2023-12-29 |
Family
ID=88386457
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311193867.9A Active CN116920939B (en) | 2023-09-15 | 2023-09-15 | Polyion liquid-loaded silicon dioxide catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116920939B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101049575A (en) * | 2007-04-27 | 2007-10-10 | 陕西师范大学 | Solid carried multilaminar ion liquid, preparation method and application |
| CN105688993A (en) * | 2016-03-04 | 2016-06-22 | 河北科技大学 | Load type polymeric acidic ionic liquid catalyst and preparation method and application thereof |
| CN109939731A (en) * | 2019-03-20 | 2019-06-28 | 合肥学院 | One kind being used for normal pressure CO2The mesoporous poly ion liquid catalyst of cycloaddition reaction, preparation method and application |
| US20190217281A1 (en) * | 2016-12-29 | 2019-07-18 | Jiangnan University | Preparation and Application of Magnetic Metallic Oxide Cross-Linked Acidic Polyionic Liquid |
| CN111068779A (en) * | 2019-12-16 | 2020-04-28 | 东南大学 | Preparation of noble metal magnetic nano catalyst based on polymerized ionic liquid loading |
| CN114433228A (en) * | 2022-02-10 | 2022-05-06 | 惠州市绿色能源与新材料研究院 | Method for synthesizing cyclic carbonate ester by catalyzing core-shell type polymeric ionic liquid |
| CN114505098A (en) * | 2020-11-16 | 2022-05-17 | 中国科学院过程工程研究所 | Imidazole type polyion liquid catalyst and preparation method and application thereof |
| CN115092897A (en) * | 2022-07-21 | 2022-09-23 | 河北工业大学 | Method for preparing hydroxylamine by catalyzing cyclohexanone oxime hydrolysis through vinyl modified silicon dioxide grafted acidic polymerization ionic liquid |
| CN116574214A (en) * | 2023-05-09 | 2023-08-11 | 山东瑞博龙化工科技股份有限公司 | Polyion liquid catalyst and preparation method and application thereof |
-
2023
- 2023-09-15 CN CN202311193867.9A patent/CN116920939B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101049575A (en) * | 2007-04-27 | 2007-10-10 | 陕西师范大学 | Solid carried multilaminar ion liquid, preparation method and application |
| CN105688993A (en) * | 2016-03-04 | 2016-06-22 | 河北科技大学 | Load type polymeric acidic ionic liquid catalyst and preparation method and application thereof |
| US20190217281A1 (en) * | 2016-12-29 | 2019-07-18 | Jiangnan University | Preparation and Application of Magnetic Metallic Oxide Cross-Linked Acidic Polyionic Liquid |
| CN109939731A (en) * | 2019-03-20 | 2019-06-28 | 合肥学院 | One kind being used for normal pressure CO2The mesoporous poly ion liquid catalyst of cycloaddition reaction, preparation method and application |
| CN111068779A (en) * | 2019-12-16 | 2020-04-28 | 东南大学 | Preparation of noble metal magnetic nano catalyst based on polymerized ionic liquid loading |
| CN114505098A (en) * | 2020-11-16 | 2022-05-17 | 中国科学院过程工程研究所 | Imidazole type polyion liquid catalyst and preparation method and application thereof |
| CN114433228A (en) * | 2022-02-10 | 2022-05-06 | 惠州市绿色能源与新材料研究院 | Method for synthesizing cyclic carbonate ester by catalyzing core-shell type polymeric ionic liquid |
| CN115092897A (en) * | 2022-07-21 | 2022-09-23 | 河北工业大学 | Method for preparing hydroxylamine by catalyzing cyclohexanone oxime hydrolysis through vinyl modified silicon dioxide grafted acidic polymerization ionic liquid |
| CN116574214A (en) * | 2023-05-09 | 2023-08-11 | 山东瑞博龙化工科技股份有限公司 | Polyion liquid catalyst and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| LI AO ET AL.: "Poly(ionic liquid)s based nano core-shell catalyst SiO2@V-PIL for efficient oxidative desulfurization of diesel", 《APPLIED CATALYSIS A-GENERAL》, vol. 616, pages 118096 * |
| YANG CHAOKUN ET AL.: "Phase-controllable polymerized ionic liquids for CO2 fixation into cyclic carbonates", 《SUSTAINABLE ENERGY & FUELS》, vol. 51, no. 4, pages 1026 - 1033 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116920939B (en) | 2023-12-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112341394B (en) | Method for preparing cyclic carbonate ester by catalysis of hydrogen bond donor functionalized polymeric ionic liquid | |
| CN107433205B (en) | Covalent organic framework supported cobalt catalyst and preparation and application thereof | |
| CN108440485B (en) | Production method of cyclic carbonate | |
| CN108440488B (en) | Organic porous copolymer multifunctional bionic heterogeneous catalyst and preparation method thereof | |
| CN111138591B (en) | N-heterocyclic carbene/CO2Adduct functionalized organic porous polymer, preparation method and application | |
| CN111135871A (en) | Imidazole ionic liquid functionalized zinc porphyrin and application thereof | |
| Ye et al. | Simple carbonaceous-material-loaded mesoporous SiO2 composite catalyst for epoxide-CO2 cycloaddition reaction | |
| CN112169836A (en) | Porous ionic polymer heterogeneous catalyst and method for catalytically synthesizing N-formamide by using same | |
| CN114832858A (en) | Preparation process of ILs @ CTF composite material and catalytic performance of carbon dioxide cycloaddition reaction | |
| CN111454455B (en) | Porous hybrid polymer rich in POSS (polyhedral oligomeric silsesquioxane) derived silicon hydroxyl and preparation method and catalytic application thereof | |
| CN116920939B (en) | Polyion liquid-loaded silicon dioxide catalyst and preparation method and application thereof | |
| CN103638970A (en) | Ion liquid catalyst and preparation method thereof as well as preparation method of cyclic carbonate | |
| CN113117747A (en) | Interfacial ionic liquid supported catalyst for synthesizing cyclic carbonate from carbon dioxide | |
| CN113637163A (en) | Triazine-based polyion liquid and synthesis method and application thereof | |
| CN108246363A (en) | A kind of preparation and its application of modified nanometer cellulose support type Mn (III)-Salen (N-N) catalyst | |
| CN112619705A (en) | Catalyst for addition reaction of alkylene oxide and its application | |
| CN105967981A (en) | Method for catalytically synthesizing propylene glycol monomethyl ether by using solid base catalyst [Smim]X/SBA-15 | |
| CN110586194A (en) | Preparation method and application of metal-organic framework material loaded polyacid site ionic liquid catalyst | |
| KR101430259B1 (en) | Method for preparation of five-membered cyclic carbonate by using immobilized ionic liquid on a biopolymer cellulose as catalyst | |
| CN114433228A (en) | Method for synthesizing cyclic carbonate ester by catalyzing core-shell type polymeric ionic liquid | |
| CN110201717B (en) | Preparation method and application of copper-based metal organic polyhedral composite material | |
| CN116920941B (en) | Silica-based catalyst loaded with ionic liquid and preparation method and application thereof | |
| Li et al. | Synthesis of hypercrosslinked polymers with a spherical shell structure for highly effective cycloaddition of CO 2 under ambient conditions | |
| CN108097306B (en) | Dual-functionalized silicon oxide catalytic material and preparation and application thereof | |
| CN112844473A (en) | Alumina-supported polyion liquid catalyst and preparation method and application thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |