CN108097306B - Dual-functionalized silicon oxide catalytic material and preparation and application thereof - Google Patents
Dual-functionalized silicon oxide catalytic material and preparation and application thereof Download PDFInfo
- Publication number
- CN108097306B CN108097306B CN201611042364.1A CN201611042364A CN108097306B CN 108097306 B CN108097306 B CN 108097306B CN 201611042364 A CN201611042364 A CN 201611042364A CN 108097306 B CN108097306 B CN 108097306B
- Authority
- CN
- China
- Prior art keywords
- silicon oxide
- ionic liquid
- benzyl alcohol
- dual
- carbon dioxide
- 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.)
- Active
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000000463 material Substances 0.000 title claims abstract description 61
- 229910052814 silicon oxide Inorganic materials 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 12
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims abstract description 99
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000002608 ionic liquid Substances 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 150000005676 cyclic carbonates Chemical class 0.000 claims abstract description 45
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 40
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- 235000019445 benzyl alcohol Nutrition 0.000 claims abstract description 33
- CLECMSNCZUMKLM-UHFFFAOYSA-N (4-ethenylphenyl)methanol Chemical compound OCC1=CC=C(C=C)C=C1 CLECMSNCZUMKLM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 4
- 150000002924 oxiranes Chemical class 0.000 claims description 15
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- 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 5
- 239000003999 initiator Substances 0.000 claims description 5
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- WHNBDXQTMPYBAT-UHFFFAOYSA-N 2-butyloxirane Chemical compound CCCCC1CO1 WHNBDXQTMPYBAT-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 4
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 4
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- ZOAUWMFMEPRJAG-UHFFFAOYSA-N [Br].C(C)N1CN(C=C1)C=C Chemical compound [Br].C(C)N1CN(C=C1)C=C ZOAUWMFMEPRJAG-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 230000009977 dual effect Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 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
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- KBOGIATXPIINBP-UHFFFAOYSA-N [Br].C(=C)N1CN(C=C1)CCCC Chemical compound [Br].C(=C)N1CN(C=C1)CCCC KBOGIATXPIINBP-UHFFFAOYSA-N 0.000 claims description 2
- JXKAKCJODWIVPX-UHFFFAOYSA-N [Br].C(CCCCC)N1CN(C=C1)C=C Chemical compound [Br].C(CCCCC)N1CN(C=C1)C=C JXKAKCJODWIVPX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004964 aerogel Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910021426 porous silicon Inorganic materials 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 2
- 238000006352 cycloaddition reaction Methods 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 150000002118 epoxides Chemical class 0.000 abstract 2
- 230000001588 bifunctional effect Effects 0.000 description 19
- 239000012298 atmosphere Substances 0.000 description 10
- 230000004580 weight loss Effects 0.000 description 9
- 239000000956 alloy Substances 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- XALVOFYVVOAYPO-UHFFFAOYSA-M 1-butyl-3-ethenylimidazol-1-ium;bromide Chemical compound [Br-].CCCCN1C=C[N+](C=C)=C1 XALVOFYVVOAYPO-UHFFFAOYSA-M 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IYHLUGVVUPPBEJ-UHFFFAOYSA-N 1-butyl-3-ethenyl-1,2-dihydroimidazol-1-ium;bromide Chemical compound [Br-].CCCC[NH+]1CN(C=C)C=C1 IYHLUGVVUPPBEJ-UHFFFAOYSA-N 0.000 description 1
- PREZSYXZLYLHNH-UHFFFAOYSA-M 1-ethenyl-3-ethylimidazol-3-ium;bromide Chemical compound [Br-].CCN1C=C[N+](C=C)=C1 PREZSYXZLYLHNH-UHFFFAOYSA-M 0.000 description 1
- MRWHNZBWUFEERI-UHFFFAOYSA-M 1-ethenyl-3-hexylimidazol-3-ium;bromide Chemical compound [Br-].CCCCCCN1C=C[N+](C=C)=C1 MRWHNZBWUFEERI-UHFFFAOYSA-M 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 239000004965 Silica aerogel Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000004693 imidazolium salts Chemical class 0.000 description 1
- 150000002576 ketones Chemical group 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Images
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
-
- B01J35/613—
-
- B01J35/615—
-
- B01J35/617—
-
- 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
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)
Abstract
The invention relates to preparation of an ionic liquid/benzyl alcohol dual-functionalized silicon oxide catalytic material and application of the ionic liquid/benzyl alcohol dual-functionalized silicon oxide catalytic material in catalyzing reaction of carbon dioxide and epoxide to synthesize cyclic carbonate. The silicon oxide material with double-bond functionalization, the ionic liquid with double bonds and the 4-vinyl benzyl alcohol are used for preparing the silicon oxide material with double-bond functionalization of the ionic liquid and the benzyl alcohol through free radical polymerization reaction. The catalyst has the advantages of simple and easily obtained raw materials, high functional group content, high specific surface area and pore volume, contribution to diffusion and mass transfer of a substrate and a product, capability of efficiently catalyzing the cycloaddition of an epoxide and carbon dioxide to generate cyclic carbonate, and universality of the substrate. The catalyst has simple preparation process, is economic and environment-friendly, can be synthesized on a large scale, and has important industrial application prospect.
Description
Technical Field
The invention belongs to the field of preparation and application of polymer/silicon oxide composite catalysts. In particular to a dual-functional silicon oxide catalytic material and preparation and application thereof.
Background
Carbon dioxide is an important C1 resource which is cheap, nontoxic and recyclable, but with the rapid development of global industry and the destruction of surface vegetation, the emission of carbon dioxide in the atmosphere is increased day by day and is a main factor causing greenhouse effect, so that the capture and application of carbon dioxide are research hotspots of scientists, and the conversion of carbon dioxide into green chemicals with high economic value can realize the effective utilization of carbon resources, reduce the influence on greenhouse effect and slow down the pace of global warming. The conversion and utilization of carbon dioxide have been rapidly developed, and chemicals such as urea, carbonate, polycarbonate, formic acid, polyurethane and the like can be synthesized by using carbon dioxide as a raw material. Among them, the reaction of carbon dioxide and epoxide to synthesize cyclic carbonate is particularly important, and cyclic carbonate is an important precursor and solvent of biological medicine, and has low toxicity, biodegradability and wide application. As early as 1943, german researchers used n-tetraethylammonium bromide to catalyze the reaction of epoxy compounds with carbon dioxide to synthesize cyclic carbonates. Subsequently, many homogeneous catalysts for catalyzing the reaction have been reported, such as ionic liquids, organic bases, metal salts, metal complexes, etc., and the homogeneous reaction system has disadvantages in that the subsequent separation and recycling of the catalyst are required, and a large amount of a cocatalyst such as tetrabutylammonium bromide, etc., is often required. Therefore, the synthesis of the catalyst which does not need a cocatalyst and can catalyze the synthesis of cyclic carbonate from carbon dioxide and epoxide with good activity and cycling stability is a research hotspot in the field and has good industrial application prospect.
Recently, a series of bifunctional catalysts have been reported which catalyze the synthesis of cyclic carbonates from carbon dioxide and epoxides. Seung Uk Son et al report a microporous organic framework material T-IM containing imidazolium salt, which is used for catalyzing cycloaddition reaction of propylene oxide and carbon dioxide to generate cyclic carbonate, the reaction is carried out for 10 hours at 150 ℃ under the pressure of 1MPa, the yield is 87%, and the TOF value can reach 134h-1[Chem.Commun.2011,47,917-919]. Von Ware et al reported a metal organic framework material, which was post-modified to introduce quaternary ammonium salt to obtain a bifunctional catalyst for catalyzing the cycloaddition reaction of propylene oxide and carbon dioxide to form cyclic carbonate, the reaction was carried out at 80 ℃ under 2MPa for 8 hours with a yield of 99% [ J.Mater.chem.A2015,3,23136-]. The bifunctional catalysts utilized in the above documents are microporous organic polymers or metal organic framework materials, and the preparation process thereof is complicated, the monomers are expensive, and even expensive metal catalysts are required. The silicon oxide material is relatively simple in preparation process, has high specific surface area and pore volume, is beneficial to diffusion and mass transfer of substrates and products, and can be grafted with organic functional groups such as ionic liquid and benzyl alcohol through simple double-bond free radical polymerization reaction. The material can catalyze the cycloaddition reaction of an epoxide and carbon dioxide to form a cyclic carbonate. The preparation process of the catalyst is simple to operate, economic and environment-friendly, can be synthesized on a large scale, and has industrial application value.
Disclosure of Invention
The invention aims to provide an ionic liquid/benzyl alcohol dual-functionalized silicon oxide material and a preparation method thereof.
It is another object of the present invention to provide the use of such an ionic liquid/benzyl alcohol dual functionalized silica material as described above as a catalyst for catalyzing the reaction of carbon dioxide and an epoxide to form a cyclic carbonate.
The ionic liquid/benzyl alcohol dual-functional silicon oxide catalytic material is characterized in that the specific surface area of the material is 10-1000 m2/g。
The ionic liquid/benzyl alcohol dual-functionalized silicon oxide catalytic material provided by the invention comprises the following specific preparation steps and conditions:
adding a silicon oxide material and 3-trimethoxy silane propyl acrylate into 20-50 m L anhydrous toluene in a 250m L reaction bottle according to the proportion of 1g of silicon oxide to 1-2 mmol of 3-trimethoxy silane propyl acrylate, refluxing for 12-48 hours in a nitrogen atmosphere, cooling a reaction system to room temperature, filtering, washing a solid product with 10-50 m L ethanol for 2-5 times, and vacuum-drying at 40-80 ℃ for 12-24 hours to obtain a double-bond functionalized silicon oxide material, adding 1g of the material, double-bond-containing ionic liquid (1-2 mmol) and 4-vinyl benzyl alcohol (1-4 mmol) into 25-100 m L chloroform and/or N, N-dimethylformamide, adding an initiator of azobisisobutyronitrile (1-5% of the total mass of the double-bond monomers), refluxing the mixture for 12-36 hours, cooling the reaction system to room temperature, filtering, washing a product with 10-50 m L ethanol twice, and vacuum-drying at 40-80 ℃ for 12-24 hours to obtain the ionic liquid and the bifunctional silicon oxide catalytic material.
The silicon oxide material can be one or more of porous silicon oxide, silicon oxide aerogel, SBA-15, SBA-16, FDU-12 or MCM-41, preferably SBA-15.
The double bond-containing ionic liquid can be one or more than two of 1-vinyl-3-ethylimidazole bromine salt, 1-vinyl-3-butylimidazole bromine salt or 1-vinyl-3-hexylimidazole bromine salt, and 1-vinyl-3-ethylimidazole bromine salt is preferred.
The steps for catalyzing the reaction of carbon dioxide and epoxide to form cyclic carbonate are as follows:
r ═ methyl, chloromethyl, ethyl, butyl, and ketone(CH2)4-or phenyl
Adding 1-3 g of epoxy compound and 90-150 mg of catalyst (the ionic liquid and benzyl alcohol dual-functional silicon oxide catalytic material prepared by the invention) into a 10-50 m L high-pressure reaction kettle, introducing carbon dioxide gas into the kettle under the pressure of 0.5-3 MPa, controlling the temperature of an oil bath at 80-150 ℃ to react for 1-6 hours, cooling the reaction kettle to room temperature, releasing residual carbon dioxide, filtering the residual liquid to remove the catalyst, and analyzing the yield of the cyclic carbonate by using gas chromatography.
The epoxide can be one or more than two of ethylene oxide, propylene oxide, epichlorohydrin, 1, 2-epoxybutane, 1, 2-epoxyhexane, cyclohexene oxide or styrene oxide.
The existing bifunctional catalysts for catalyzing epoxides and carbon dioxide to form cyclic carbonates have some disadvantages, such as: the molecular catalyst is difficult to separate from the product and recycle, the preparation process of the microporous organic polymer or metal organic framework material is complicated and tedious, the monomer is expensive, and even an expensive metal catalyst is needed. The preparation process of the ionic liquid and benzyl alcohol dual-functional silicon oxide catalytic material provided by the invention is relatively simple, organic functional groups such as ionic liquid and benzyl alcohol can be grafted onto a silicon oxide material through simple double-bond free radical polymerization reaction, the monomer synthesis steps are few, the price is low, the large-scale production can be realized, and the material has high specific surface area and pore volume, and is beneficial to the diffusion and mass transfer of substrates and products. Can efficiently catalyze the cycloaddition reaction of epoxide and carbon dioxide to generate cyclic carbonate. The invention is expected to be widely applied in the field of industrial synthesis of cyclic carbonate.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of the ionic liquid/benzyl alcohol dual-functionalized silicon oxide material SBA15-1 obtained in example 1;
FIG. 2 is a Transmission Electron Microscope (TEM) photograph of the ionic liquid/benzyl alcohol dual-functionalized silicon oxide material SBA15-1 obtained in example 1;
FIG. 3 is a thermogravimetric plot of the ionic liquid/benzyl alcohol dual functionalized silica material SBA15-1 obtained in example 1;
FIG. 4 is an infrared spectrum of the ionic liquid/benzyl alcohol dual-functionalized silica material SBA15-1 obtained in example 1;
FIG. 5 is a nitrogen absorption and desorption graph of the ionic liquid/benzyl alcohol dual-functionalized silicon oxide material SBA15-1 obtained in example 1;
FIG. 6 is a distribution diagram of the pore size of the ionic liquid/benzyl alcohol dual-functionalized silicon oxide material SBA15-1 obtained in example 1.
Detailed Description
Example 1: preparation of ionic liquid/benzyl alcohol dual-functionalized silicon oxide material SBA15-1
Adding 1g of silicon oxide material SBA15 and 0.248g (1mmol) of 3-trimethoxy silane acrylic propyl ester into a 250m L reaction bottle, adding 20m L of anhydrous toluene into the reaction bottle, fully stirring and refluxing for 24 hours under the nitrogen atmosphere, cooling the reaction system to room temperature, filtering, washing a product twice with 25m L of ethanol, carrying out vacuum drying for 12 hours at 60 ℃ to obtain a double-bond functionalized silicon oxide material Allyl-SBA15, adding 1g of double-bond functionalized silicon oxide material Allyl-SBA15 into a 250m L reaction bottle, adding 50m L N, N-dimethylformamide, stirring and dispersing, adding 232mg (1mmol) of double-bond-containing ionic liquid 1-vinyl-3-butyl imidazole bromide and 536mg (4mmol) of 4-vinyl benzyl alcohol into the reaction system, replacing nitrogen, adding 20mg of initiator azobisisobutyronitrile after replacing nitrogen, carrying out oil bath reaction for 36 hours at 80 ℃, cooling the reaction system to room temperature, filtering the product, carrying out double-function washing with 50m ethanol for twice, and drying SBA at 60 ℃ to obtain SBA at 15.
Carrying out infrared spectrum analysis on the ionic liquid and benzyl alcohol dual-functionalized silicon oxide material SBA15-1 by using a Fourier infrared spectrum analyzer (Nicolet Nexus 470 IR): at 3390cm-1The broad peak of (A) is the stretching vibration peak of hydroxyl in benzyl alcohol, and is 1630cm-1The peak is the stretching vibration peak of carbonyl at 1075cm-1The stronger peak at (a) is attributed to the Si-O bond.
The shape and size of the silicon oxide material SBA15-1 with ionic liquid and benzyl alcohol double functionalization are detected by a scanning electron microscope (FEI Quanta 200F) and a transmission electron microscope (HITACHI 7700), and the result shows that the polymer has a random block shape, and the straight hole structure of the material can be clearly seen by the transmission electron microscope.
50mg of ionic liquid and benzyl alcohol dual-functionalized silicon oxide material SBA15-1 are taken to be dried in vacuum at 100 ℃ for 24 hours, and then a specific surface area analyzer (Micromeritics ASAP2020) is utilized to test to obtain a sample with the specific surface area of 271m2And/g, the weight loss of the sample in the air atmosphere at the temperature of 200-800 ℃ is measured to be 34.9 wt% by using a thermogravimetric analyzer (NETZSCH STA 449F 3).
Example 2: preparation of ionic liquid/benzyl alcohol dual-functionalized silicon oxide material SBA15-2
This example is essentially the same as example 1 except that 470mg (2mmol) of 1-vinyl-3-butylimidazolium bromide salt as the double bond-containing ionic liquid was added and 269mg (2mmol) of 4-vinylbenzyl alcohol was added. The specific surface area was found to be 160m2The weight loss of the alloy is 41.0 wt% in an air atmosphere at the temperature of 200-800 ℃.
Example 3: preparation of ionic liquid/benzyl alcohol dual-functionalized silicon oxide material SBA15-3
This example is essentially the same as example 1 except that 370mg (1.6mmol) of 1-vinyl-3-butylimidazolium bromide salt as the double bond-containing ionic liquid was added and 430mg (3.2mmol) of 4-vinylbenzyl alcohol was added. The specific surface area was measured to be 161m2The weight loss of the alloy is 35.5 wt% in the range of 200-800 ℃ under the air atmosphere.
Example 4: preparation of ionic liquid/benzyl alcohol dual-functionalized silicon oxide material SBA15-4
This example is essentially the same as example 1 except that 464mg (2mmol) of 1-vinyl-3-butylimidazolium bromide salt was added as the double bond-containing ionic liquid and 1070mg (8mmol) of 4-vinylbenzyl alcohol was added. The specific surface area was found to be 17m2The weight loss of the alloy is 53.3 wt% in the range of 200-800 ℃ under the air atmosphere.
Example 5: preparation of ionic liquid/benzyl alcohol dual-functionalized silicon oxide material SBA15-5
This example is essentially the same as example 1, except that the double bond containing ionic liquid added is 1-vinyl-3-ethylimidazolium bromide, having a mass of 204mg (1 mmol). The specific surface area was found to be 259m2The weight loss of the alloy is 37.1 wt% in an air atmosphere at the temperature of 200-800 ℃.
Example 6: preparation of ionic liquid/benzyl alcohol dual-functionalized silicon oxide material SBA15-6
This example is essentially the same as example 1, except that the double bond containing ionic liquid added is 1-vinyl-3-hexylimidazolium bromide, with a mass of 260mg (1 mmol). The specific surface area was found to be 189m2The weight loss of the alloy is 35.6 wt% in the range of 200-800 ℃ under the air atmosphere.
Example 7: preparation of ionic liquid/benzyl alcohol dual-functionalized silicon oxide material FDU12-1
This example is substantially the same as example 1 except that the added silicon oxide material is FDU 12. The specific surface area was found to be 212m2The weight loss of the alloy is 38.9 wt% in an air atmosphere at the temperature of 200-800 ℃.
Example 8: preparation of ionic liquid/benzyl alcohol dual-functionalized silicon oxide material SBA16-1
This example is substantially the same as example 1 except that the added silicon oxide material is SBA 16. The specific surface area was measured to be 195m2The weight loss of the alloy is 42.1 wt% in the range of 200-800 ℃ under the air atmosphere.
Example 9: preparation of ionic liquid/benzyl alcohol dual-functionalized silicon oxide material FumeSilica-1
This example is substantially the same as example 1 except that the silica material added is a silica aerogel. The specific surface area was found to be 39m2The weight loss of the alloy is 24.5 wt% in an air atmosphere at the temperature of 200-800 ℃.
Example 10: SBA15-5 is used as a bifunctional catalyst to catalyze the reaction of carbon dioxide and propylene oxide to synthesize cyclic carbonate
1.32g (22.7mmol) of propylene oxide and 150mg of catalyst SBA15-5 are added into a 25m L high-pressure reaction kettle, 2MPa of carbon dioxide gas is filled, the temperature of an oil bath is controlled at 130 ℃ for reaction for 5 hours, the residual carbon dioxide is released after the reaction is cooled to room temperature, the catalyst is removed by filtering the residual liquid, the cyclic carbonate is obtained, and the yield of the cyclic carbonate is 94% by utilizing gas chromatography analysis.
Example 11: SBA15-1 is used as a bifunctional catalyst to catalyze the reaction of carbon dioxide and propylene oxide to synthesize cyclic carbonate
This example is essentially the same as example 10 except that the dual-function catalyst added is SBA15-1 with a mass of 150 mg. The yield of cyclic carbonate was found to be 82%.
Example 12: SBA15-2 is used as a bifunctional catalyst to catalyze the reaction of carbon dioxide and propylene oxide to synthesize cyclic carbonate
This example is essentially the same as example 10 except that the dual-function catalyst added is SBA15-2 with a mass of 90 mg. The yield of cyclic carbonate was measured to be 72%.
Example 13: SBA15-3 is used as a bifunctional catalyst to catalyze the reaction of carbon dioxide and propylene oxide to synthesize cyclic carbonate
This example is essentially the same as example 10 except that the dual-function catalyst added is SBA15-3 with a mass of 140 mg. The yield of cyclic carbonate was found to be 75%.
Example 14: SBA15-4 is used as a bifunctional catalyst to catalyze the reaction of carbon dioxide and propylene oxide to synthesize cyclic carbonate
This example is essentially the same as example 10 except that the dual-function catalyst added is SBA15-4 with a mass of 120 mg. The yield of cyclic carbonate was found to be 77%.
Example 15: SBA15-5 is used as a bifunctional catalyst to catalyze the reaction of carbon dioxide and propylene oxide to synthesize cyclic carbonate
This example is essentially the same as example 10 except that the pressure of the carbon dioxide gas fed to the reaction was 1 MPa. The yield of cyclic carbonate was measured to be 65%.
Example 16: SBA15-5 is used as a bifunctional catalyst to catalyze the reaction of carbon dioxide and propylene oxide to synthesize cyclic carbonate
This example is essentially the same as example 10 except that the reaction temperature is 120 ℃. The yield of cyclic carbonate was found to be 86%.
Example 17: SBA15-5 is used as a bifunctional catalyst to catalyze the reaction of carbon dioxide and epichlorohydrin to synthesize cyclic carbonate
This example is essentially the same as example 10 except that the epoxide added is epichlorohydrin and has a mass of 2.1g (22.7 mmol). The yield of cyclic carbonate was measured to be 95%.
Example 18: SBA15-5 is used as a bifunctional catalyst to catalyze the reaction of carbon dioxide and 1, 2-epoxy hexane for synthesizing cyclic carbonate
This example is essentially the same as example 10 except that the epoxide added is 1, 2-epoxyhexane having a mass of 2.27g (22.7 mmol). The yield of cyclic carbonate was measured to be 92%.
Example 19: SBA15-5 is used as a bifunctional catalyst to catalyze the reaction of carbon dioxide and styrene oxide to synthesize cyclic carbonate
This example is essentially the same as example 10 except that the epoxide added is styrene oxide and has a mass of 2.73g (22.7 mmol). The yield of cyclic carbonate was found to be 73%.
Example 20: SBA15-5 is used as a bifunctional catalyst to catalyze the reaction of carbon dioxide and cyclohexene oxide to synthesize cyclic carbonate
This example is essentially the same as example 10 except that the epoxide added is cyclohexene oxide having a mass of 2.23g (22.7 mmol). The yield of cyclic carbonate was found to be 47%.
Example 21: SBA16-1 is used as a bifunctional catalyst to catalyze the reaction of carbon dioxide and propylene oxide to synthesize cyclic carbonate
This example is essentially the same as example 10 except that the dual-function catalyst added is SBA16-1 with a mass of 120 mg. The yield of cyclic carbonate was found to be 86%.
Example 22: FumeSilica-1 is used as a bifunctional catalyst to catalyze the reaction of carbon dioxide and epoxypropane to synthesize cyclic carbonate
This example is essentially the same as example 10 except that the bifunctional catalyst added is FumeSilica-1, with a mass of 120 mg. The yield of cyclic carbonate was found to be 75%.
Claims (6)
1. A preparation method of a dual-functional silicon oxide catalytic material is characterized by adding a silicon oxide material and 3-trimethoxy silane propyl acrylate into 20-50 m L anhydrous toluene according to the proportion of 1g of silicon oxide to 1-2 mmol of 3-trimethoxy silane propyl acrylate, refluxing for 12-48 hours in a nitrogen atmosphere, cooling a reaction system to room temperature, filtering, washing a solid product with 10-50 m L ethanol for 2-5 times, vacuum drying for 12-24 hours at 40-80 ℃ to obtain a double-bond functionalized silicon oxide material, adding 1g of the double-bond functionalized silicon oxide material, double-bond-containing ionic liquid and 4-vinyl benzyl alcohol into 25-100 m L chloroform and/or N, N-dimethylformamide, adding an initiator azodiisobutyronitrile, refluxing the mixture for 12-36 hours, cooling the reaction system to room temperature, filtering, washing the product with 10-50 m L ethanol twice, vacuum drying for 12-24 hours at 40-80 ℃ to obtain ionic liquid and benzyl alcohol dual-functional silicon oxide catalytic material, wherein the amount of the double-bond-containing ionic liquid is 1-2 mmol of the initiator and the total amount of the added 1-5 mmol of the initiator.
2. The process according to claim 1, wherein: the silicon oxide material is one or more than two of porous silicon oxide, silicon oxide aerogel, SBA-15, SBA-16, FDU-12 or MCM-41.
3. The process according to claim 1, wherein: the double-bond-containing ionic liquid is one or more than two of 1-vinyl-3-ethylimidazole bromine salt, 1-vinyl-3-butylimidazole bromine salt or 1-vinyl-3-hexylimidazole bromine salt.
4. An ionic liquid/benzyl alcohol dual-functionalized silicon oxide material prepared by the preparation method of any one of claims 1 to 3.
5. Use of the ionic liquid/benzyl alcohol dual functionalized silicon oxide material of claim 4 in catalyzing the reaction of carbon dioxide and epoxide to form cyclic carbonate, wherein: adding 1-3 g of epoxy compound and 90-150 mg of silicon oxide material with ionic liquid/benzyl alcohol dual-functionalization into a high-pressure reaction kettle, introducing carbon dioxide gas with the pressure of 0.5-3 MPa, reacting at 80-150 ℃ for 1-6 hours, cooling to room temperature, releasing residual carbon dioxide, and filtering residual liquid to remove a catalyst to obtain the cyclic carbonate.
6. Use according to claim 5, wherein the epoxide is one or more of ethylene oxide, propylene oxide, epichlorohydrin, 1, 2-butylene oxide, 1, 2-hexylene oxide, cyclohexene oxide or styrene oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611042364.1A CN108097306B (en) | 2016-11-24 | 2016-11-24 | Dual-functionalized silicon oxide catalytic material and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611042364.1A CN108097306B (en) | 2016-11-24 | 2016-11-24 | Dual-functionalized silicon oxide catalytic material and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108097306A CN108097306A (en) | 2018-06-01 |
| CN108097306B true CN108097306B (en) | 2020-07-21 |
Family
ID=62204720
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611042364.1A Active CN108097306B (en) | 2016-11-24 | 2016-11-24 | Dual-functionalized silicon oxide catalytic material and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108097306B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112121853B (en) * | 2020-09-08 | 2023-03-28 | 重庆邮电大学 | Mesoporous hollow silica nanosphere loaded with prolinol catalyst as well as preparation method and application of mesoporous hollow silica nanosphere |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009183864A (en) * | 2008-02-06 | 2009-08-20 | National Institute Of Advanced Industrial & Technology | Acid catalyst for dehydration containing phytic acid as efficacious component and manufacturing method of ester or ether using catalyst thereof |
| CN102399376A (en) * | 2010-09-09 | 2012-04-04 | 中国科学院化学研究所 | Silicon dioxide with organic functional molecules grafted on surface, preparation method thereof, and purpose thereof |
| KR101505423B1 (en) * | 2013-10-16 | 2015-03-25 | 고려대학교 산학협력단 | Multifunctional Nanoparticle Colloids Based Fluid and Method for Preparing Thereof |
| CN104530845A (en) * | 2014-12-25 | 2015-04-22 | 常州大学 | Waterborne single-component transparent anti-corrosion coating based on dual-functionalized nano-SiO2 and preparation method of coating |
| CN104867679A (en) * | 2015-05-27 | 2015-08-26 | 中国科学院化学研究所 | Functional nanoparticle and preparation method and application thereof |
| CN105801615A (en) * | 2014-12-31 | 2016-07-27 | 中国科学院兰州化学物理研究所 | Silica immobilized double-acid functionalized ionic liquid, preparation method and application thereof |
-
2016
- 2016-11-24 CN CN201611042364.1A patent/CN108097306B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009183864A (en) * | 2008-02-06 | 2009-08-20 | National Institute Of Advanced Industrial & Technology | Acid catalyst for dehydration containing phytic acid as efficacious component and manufacturing method of ester or ether using catalyst thereof |
| CN102399376A (en) * | 2010-09-09 | 2012-04-04 | 中国科学院化学研究所 | Silicon dioxide with organic functional molecules grafted on surface, preparation method thereof, and purpose thereof |
| KR101505423B1 (en) * | 2013-10-16 | 2015-03-25 | 고려대학교 산학협력단 | Multifunctional Nanoparticle Colloids Based Fluid and Method for Preparing Thereof |
| CN104530845A (en) * | 2014-12-25 | 2015-04-22 | 常州大学 | Waterborne single-component transparent anti-corrosion coating based on dual-functionalized nano-SiO2 and preparation method of coating |
| CN105801615A (en) * | 2014-12-31 | 2016-07-27 | 中国科学院兰州化学物理研究所 | Silica immobilized double-acid functionalized ionic liquid, preparation method and application thereof |
| CN104867679A (en) * | 2015-05-27 | 2015-08-26 | 中国科学院化学研究所 | Functional nanoparticle and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108097306A (en) | 2018-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112341394B (en) | Method for preparing cyclic carbonate ester by catalysis of hydrogen bond donor functionalized polymeric ionic liquid | |
| Cho et al. | Synthesis of glycerol carbonate from ethylene carbonate and glycerol using immobilized ionic liquid catalysts | |
| CN107537569B (en) | Ionic covalent organic framework catalyst, preparation method and catalytic application | |
| CN107537575B (en) | Imidazolium salt organic polymer catalyst and preparation method and application thereof | |
| CN114669332B (en) | Preparation method of ionic ultrahigh crosslinked porous organic polymer supported cobalt catalyst | |
| US10195599B2 (en) | Synthesis of functionalized carbon microspheres and their catalyst activity in C—O and C—N bond formation reactions | |
| CN111138591B (en) | N-heterocyclic carbene/CO2Adduct functionalized organic porous polymer, preparation method and application | |
| CN108440488B (en) | Organic porous copolymer multifunctional bionic heterogeneous catalyst and preparation method thereof | |
| CN107537563B (en) | Quaternary phosphonium salt organic polymer catalyst and preparation method and application thereof | |
| Jiang et al. | Controlled immobilization of methyltrioxorhenium (VII) based on SI-ATRP of 4-vinyl pyridine from halloysite nanotubes for epoxidation of soybean oil | |
| Shi et al. | Conversion of CO2 into organic carbonates over a fiber-supported ionic liquid catalyst in impellers of the agitation system | |
| Jayakumar et al. | Cocatalyst‐Free Hybrid Ionic Liquid (IL)‐Based Porous Materials for Efficient Synthesis of Cyclic Carbonates through a Cooperative Activation Pathway | |
| CN112121853B (en) | Mesoporous hollow silica nanosphere loaded with prolinol catalyst as well as preparation method and application of mesoporous hollow silica nanosphere | |
| CN108097306B (en) | Dual-functionalized silicon oxide catalytic material and preparation and application thereof | |
| CN106423280A (en) | Preparation of cationic organic polymer and method for catalyzing fixation of carbon dioxide | |
| Duan et al. | Propylene oxide cycloaddition with carbon dioxide and homopolymerization: Application of commercial beta zeolites | |
| Li et al. | Bifunctionalized polyacrylonitrile fibers as highly efficient and selective heterogeneous catalysts for cycloaddition of CO2 with epichlorohydrin under mild conditions | |
| CN110090664B (en) | Acidic ionic liquid @ COF material and preparation method and application thereof | |
| CN106256845A (en) | A kind of preparation method of high-molecular aliphatic polycarbonate | |
| Liu et al. | Polymeric ionic liquid membranes for the absorption-conversion of CO2 and epoxides into cyclic carbonates | |
| CN104841486A (en) | Applying porous organic polymer to epoxidation of olefin on basis of Salen-Mn | |
| CN111454455B (en) | Porous hybrid polymer rich in POSS (polyhedral oligomeric silsesquioxane) derived silicon hydroxyl and preparation method and catalytic application thereof | |
| CN109453812B (en) | Organic nitrogen-containing polymer carrier loaded Rh-based catalyst and preparation and application thereof | |
| CN105778062A (en) | Polymer and preparing method thereof | |
| CN106431926B (en) | The method for synthesizing 3- hydroxy propionate |
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 |