CN108097306A - A kind of silica catalysis material of difunctionalization and its preparation and application - Google Patents
A kind of silica catalysis material of difunctionalization and its preparation and application Download PDFInfo
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- CN108097306A CN108097306A CN201611042364.1A CN201611042364A CN108097306A CN 108097306 A CN108097306 A CN 108097306A CN 201611042364 A CN201611042364 A CN 201611042364A CN 108097306 A CN108097306 A CN 108097306A
- Authority
- CN
- China
- Prior art keywords
- silica
- ionic liquid
- difunctionalization
- benzylalcohol
- carbon dioxide
- Prior art date
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000000463 material Substances 0.000 title claims abstract description 64
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 58
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims abstract description 102
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 80
- -1 cyclic carbonate ester Chemical class 0.000 claims abstract description 54
- 239000002608 ionic liquid Substances 0.000 claims abstract description 45
- 235000019445 benzyl alcohol Nutrition 0.000 claims abstract description 41
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 39
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 229960004217 benzyl alcohol Drugs 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 19
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 14
- 150000002924 oxiranes Chemical class 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
- 239000000047 product Substances 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-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
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 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 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 150000003613 toluenes Chemical class 0.000 claims description 3
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical class CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 claims description 2
- MRWHNZBWUFEERI-UHFFFAOYSA-M 1-ethenyl-3-hexylimidazol-3-ium;bromide Chemical class [Br-].CCCCCCN1C=C[N+](C=C)=C1 MRWHNZBWUFEERI-UHFFFAOYSA-M 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004965 Silica aerogel Substances 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 238000007306 functionalization reaction Methods 0.000 claims 1
- 239000001294 propane Substances 0.000 claims 1
- 238000006352 cycloaddition reaction Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 150000002118 epoxides Chemical class 0.000 abstract 2
- 125000000524 functional group Chemical group 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 229960004424 carbon dioxide Drugs 0.000 description 34
- 230000001588 bifunctional effect Effects 0.000 description 23
- 239000012298 atmosphere Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- UJWVKWKGJHCBCX-UHFFFAOYSA-N 1-butyl-1h-imidazol-1-ium;bromide Chemical class [Br-].CCCCN1C=C[NH+]=C1 UJWVKWKGJHCBCX-UHFFFAOYSA-N 0.000 description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000006735 epoxidation reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 239000003863 metallic catalyst Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 239000004425 Makrolon Substances 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 150000001649 bromium compounds Chemical class 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
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000010959 commercial synthesis reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 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
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process 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
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 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
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000001172 regenerating effect Effects 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
- 238000003756 stirring Methods 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
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000010792 warming Methods 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
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- 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
Preparation the present invention relates to a kind of silica catalysis material of ionic liquid/benzylalcohol difunctionalization and its application in catalysis carbon dioxide and the reaction of epoxides synthesizing cyclic carbonate ester.It is to prepare ionic liquid and the silica material of benzylalcohol difunctionalization by Raolical polymerizable containing double-bond functionalized silica material and double bond containing ionic liquid, 4 vinyl benzyl alcohols.Raw material needed for catalyst preparation of the present invention is simple and easy to get, preparation process only needs a step Raolical polymerizable to complete, and the catalyst has high functional group content, high-specific surface area and pore volume, be conducive to the diffusion mass transfer of substrate and product, can efficient catalytic epoxides and carbon dioxide cycloaddition generation cyclic carbonate ester reaction, and the universality with substrate.The catalyst preparation process is simple, economic and environment-friendly, can amplify scale synthesis, have important prospects for commercial application.
Description
Technical field
Preparation and its application field the invention belongs to polymer/silica composite catalyst.More particularly to a kind of double work(
The silica catalysis material of energyization and its preparation and application.
Background technology
Carbon dioxide is a kind of important cheap, nontoxic, recyclable regenerative C1 resources, but at full speed with global industry
Development and the destruction of surface vegetation, the CO2 emissions in air are growing day by day, be cause greenhouse effects it is main because
Element, therefore the capture of carbon dioxide and the research hotspot that application is scientists, are high economic value by carbon dioxide conversion
Green chemical can realize the influence for efficiently using and reducing to greenhouse effects of carbon resource, the step of slowing global warming
It cuts down.The conversion and utilization of carbon dioxide have been achieved for developing rapidly, and can be Material synthesis such as urea, carbonic acid with carbon dioxide
The chemicals such as ester, makrolon, formic acid, polyurethane.Wherein, the reaction of carbon dioxide and epoxides synthesizing cyclic carbonate ester is particularly
Important, cyclic carbonate ester is the presoma and solvent of important biological medicine, and toxicity is relatively low and can biodegradable, purposes ten
Divide extensive.Early in nineteen forty-three, German researchers just close object using positive tetraethylammonium bromide catalysis epoxidation and carbon dioxide is anti-
Answer synthesizing cyclic carbonate ester.Subsequent many homogeneous catalysts are reported in succession for being catalyzed the reaction, such as ionic liquid, organic
Alkali, metal salt, metal complex etc., homogeneous reaction system are disadvantageous in that subsequent catalyst separation and recycling,
And it usually needs to add in substantial amounts of co-catalyst, such as tetrabutylammonium bromide.Therefore, synthesize without co-catalyst and can
The catalyst of catalysis carbon dioxide and epoxides synthesizing cyclic carbonate ester with excellent activity and cyclical stability is the field
Research hotspot, and with good industrial applications prospect.
Recently, a series of bifunctional catalyst of catalysis carbon dioxide and epoxides synthesizing cyclic carbonate ester is reported.
Seung Uk Son et al. report a kind of micropore organic framework material T-IM containing imidazole salts, for being catalyzed propylene oxide and two
Carbonoxide cycloaddition reaction generates cyclic carbonate ester, when the reaction is under 1MPa pressure, reaction 10 is small at 150 DEG C, yield 87%,
TOF values are up to 134h-1[Chem.Commun.2011,47,917-919].Feng keeps China et al. and reports a kind of metal organic framework
Material obtains bifunctional catalyst, for being catalyzed propylene oxide and carbon dioxide cycloaddition introducing quaternary ammonium salt by rear modification
Reaction generation cyclic carbonate ester, when the reaction is under 2MPa pressure, reaction 8 is small at 80 DEG C, yield is 99% [J.Mater.Chem.A
2015,3,23136-23142].The bifunctional catalyst utilized in above-mentioned document is micropore organic polymer or the organic bone of metal
Frame material, preparation process complexity is cumbersome, monomer costly or even needs to use expensive metallic catalyst.And silica
Material preparation process is relatively easy and with high-specific surface area and high pore volume, is conducive to the diffusion mass transfer of substrate and product, leads to
Crossing simple double bond Raolical polymerizable can be grafted onto the organo-functional groups such as ionic liquid, benzylalcohol on silica material.
The material can generate cyclic carbonate ester with catalysis epoxidation object and carbon dioxide cycloaddition reaction.Catalyst preparation process operation letter
It is single, economic and environment-friendly, scale synthesis can be amplified, there is industrial applications value.
The content of the invention
Silica material and its preparation side it is an object of the invention to provide a kind of ionic liquid/benzylalcohol difunctionalization
Method.
Another object of the present invention is to provide for the above-mentioned this silica material with ionic liquid/benzylalcohol difunctionalization
The purposes of material uses it for catalysis carbon dioxide and the catalyst of epoxides synthesizing cyclic carbonate ester reaction.
The silica catalysis material of the ionic liquid/benzylalcohol difunctionalization, it is characterised in that its specific surface area is 10
~1000m2/g。
Its specific preparation process of the silica catalysis material of ionic liquid of the present invention/benzylalcohol difunctionalization and item
Part is：
In 250mL reaction bulbs, by silica material and 3- trimethoxy silanes the third fat of acrylic acid according to 1g silica：1
The ratio of~2mmol 3- trimethoxy silanes the third fat of acrylic acid is added in 20~50mL dry toluenes, is returned in a nitrogen atmosphere
When stream 12~48 is small, reaction system filters after being cooled to room temperature, and solid product washs 2~5 times with 10~50mL ethyl alcohol, and 40~80
Double-bond functionalized silica material is obtained when vacuum drying 12~24 is small at DEG C.By material 1g and double bond containing ionic liquid
(1~2mmol), 4- vinyl benzyl alcohols (1~4mmol) are added in 25~100mL chloroforms and/or n,N-Dimethylformamide,
And initiator azodiisobutyronitrile (the 1~5% of double bond monomer gross mass) is added in, when said mixture reflux 12~36 is small, instead
System is answered to be filtered after being cooled to room temperature, product is washed twice with 10~50mL ethyl alcohol, and it is small that 12~24 are dried in vacuo at 40~80 DEG C
When obtain ionic liquid and the silica catalysis material of benzylalcohol difunctionalization.
The silica material, can be porous silica, silica aerogel, SBA-15, SBA-16, FDU-12 or
More than one or both of MCM-41, preferably SBA-15.
The double bond containing ionic liquid can be 1- vinyl -3- ethyl imidazol(e)s bromide, 1- vinyl -3- butyl
It is more than one or both of imidazoles bromide or 1- vinyl -3- hexyl imidazolium bromides, preferred 1- vinyl -3- ethyl imidazol(e) bromines
Salt.
The step of being catalyzed carbon dioxide and the reaction of epoxides synthesizing cyclic carbonate ester is as follows：
R=methyl, chloromethyl, ethyl, butyl ,-(CH2)4- or phenyl
Epoxide 1g~3g and catalyst 90mg~150mg (present invention are added in 10~50mL autoclaves
The ionic liquid of preparation and the silica catalysis material of benzylalcohol difunctionalization), be filled with carbon dioxide, pressure for 0.5~
3MPa when oil bath control 80~150 DEG C of reactions 1~6 of temperature are small, discharges remaining carbon dioxide, raffinate after being cooled to room temperature
Body passes through Filtration of catalyst, you can obtains cyclic carbonate ester.The yield of cyclic carbonate ester is analyzed using gas-chromatography.
Epoxides described above can be ethylene oxide, propylene oxide, epoxychloropropane, 1,2- epoxy butanes, 1,
It is more than one or both of 2- oxepanes, 7-oxa-bicyclo[4.1.0 or styrene oxide.
There are some disadvantages for the existing bifunctional catalyst for catalysis epoxidation object and carbon dioxide generation cyclic carbonate ester
End, such as：Molecular catalyst hardly possible is separated with product, difficult recycling, prepared by micropore organic polymer or metal-organic framework materials
Process complexity is cumbersome, monomer costly or even needs to use expensive metallic catalyst.And ionic liquid provided by the invention
With the silica catalysis material preparation process of benzylalcohol difunctionalization it is relatively easy, by simple double bond Raolical polymerizable just
Can will contain the organo-functional groups such as ionic liquid, benzylalcohol to be grafted onto on silica material, monomer synthesis step is few, it is relatively inexpensive, can be real
Now amplify large-scale production, and the material has high-specific surface area and pore volume, is conducive to the diffusion mass transfer of substrate and product.It can
Efficient catalytic epoxides generates cyclic carbonate ester with carbon dioxide cycloaddition reaction.This invention is expected in commercial synthesis ring carbon acid
It is used widely in ester field.
Description of the drawings
The scanning electricity that Fig. 1 is the silica material SBA15-1 of 1 obtained ionic liquid of embodiment/benzylalcohol difunctionalization
Sub- microscope (SEM) photo；
The transmission electricity that Fig. 2 is the silica material SBA15-1 of 1 obtained ionic liquid of embodiment/benzylalcohol difunctionalization
Sub- microscope (TEM) photo；
The thermogravimetric that Fig. 3 is the silica material SBA15-1 of 1 obtained ionic liquid of embodiment/benzylalcohol difunctionalization is bent
Line chart；
Fig. 4 is the infrared light of the silica material SBA15-1 of 1 obtained ionic liquid of embodiment/benzylalcohol difunctionalization
Spectrogram；
The nitrogen that Fig. 5 is the silica material SBA15-1 of 1 obtained ionic liquid of embodiment/benzylalcohol difunctionalization is inhaled
Desorption curve figure；
The aperture point that Fig. 6 is the silica material SBA15-1 of 1 obtained ionic liquid of embodiment/benzylalcohol difunctionalization
Butut.
Specific embodiment
Embodiment 1：Prepare the silica material SBA15-1 of ionic liquid/benzylalcohol difunctionalization
In 250mL reaction bulbs, 1g silica materials SBA15 and 0.248g (1mmol) 3- trimethoxy silanes third are added in
The third fat of olefin(e) acid, into reaction bulb plus 20mL dry toluenes, be sufficiently stirred and flow back in a nitrogen atmosphere 24 it is small when, reaction system is cold
But to filtering after room temperature, product is washed twice with 25mL ethyl alcohol, be dried in vacuo at 60 DEG C 12 it is small when obtain double-bond functionalized oxygen
Silicon nitride material Allyl-SBA15.The silica material Allyl-SBA15 for taking 1g double-bond functionalized is added in 250mL reaction bulbs,
It adds in 50mL n,N-Dimethylformamide to be dispersed with stirring, by the double bond containing ionic liquid 1- vinyl -3- fourths of 232mg (1mmol)
Base imidazoles bromide, 536mg (4mmol) 4- vinyl benzyl alcohols are added in reaction system, and 20mg initiations are added in after being replaced as nitrogen
Agent azodiisobutyronitrile, which is reacted under 80 DEG C of oil baths 36 it is small when, reaction system filters after being cooled to room temperature, and product is used
50mL ethyl alcohol washes twice, and ionic liquid and the silica material of benzylalcohol difunctionalization are obtained when vacuum drying 12 is small at 60 DEG C
SBA15-1。
With FTIR spectrum analyzer (Nicolet Nexus 470IR) to ionic liquid and benzylalcohol difunctionalization
Silica material SBA15-1 carries out infrared spectrum analysis：In 3390cm-1The broad peak at place is the stretching vibration peak of hydroxyl in benzylalcohol,
In 1630cm-1The peak at place is the stretching vibration peak of carbonyl, in 1075cm-1The stronger peak at place belongs to Si-O keys.
With scanning electron microscope (FEI Quanta 200F) and transmission electron microscope (HITACHI 7700) to ion
The pattern and size of liquid and the silica material SBA15-1 of benzylalcohol difunctionalization are detected, the results showed that the polymer has
There are a kind of random bulk morphologies, and the straight hole structure of the material can be clearly apparent by transmission electron microscope.
50mg ionic liquids and the silica material SBA15-1 of benzylalcohol difunctionalization is taken to be dried in vacuo 24 at 100 DEG C small
Shi Hou, the specific surface area that sample is obtained using specific surface area analysis instrument (Micromeritics ASAP2020) test is 271m2/
G, measure sample using thermogravimetric analyzer (NETZSCH STA 449F3) is in the weightlessness of air atmosphere, 200~800 DEG C of scopes
34.9wt%.
Embodiment 2：Prepare the silica material SBA15-2 of ionic liquid/benzylalcohol difunctionalization
The present embodiment is substantially the same manner as Example 1, the difference is that only add in double bond containing ionic liquid 1- vinyl-
The amount of 3- butyl imidazole bromides is 470mg (2mmol), and the amount for adding in 4- vinyl benzyl alcohols is 269mg (2mmol).Measure its ratio
Surface area is 160m2/ g is 41.0wt% in the weightlessness of air atmosphere, 200~800 DEG C of scopes.
Embodiment 3：Prepare the silica material SBA15-3 of ionic liquid/benzylalcohol difunctionalization
The present embodiment is substantially the same manner as Example 1, the difference is that only add in double bond containing ionic liquid 1- vinyl-
The amount of 3- butyl imidazole bromides is 370mg (1.6mmol), and the amount for adding in 4- vinyl benzyl alcohols is 430mg (3.2mmol).It measures
Its specific surface area is 161m2/ g is 35.5wt% in the weightlessness of air atmosphere, 200~800 DEG C of scopes.
Embodiment 4：Prepare the silica material SBA15-4 of ionic liquid/benzylalcohol difunctionalization
The present embodiment is substantially the same manner as Example 1, the difference is that only add in double bond containing ionic liquid 1- vinyl-
The amount of 3- butyl imidazole bromides is 464mg (2mmol), and the amount for adding in 4- vinyl benzyl alcohols is 1070mg (8mmol).Measure its ratio
Surface area is 17m2/ g is 53.3wt% in the weightlessness of air atmosphere, 200~800 DEG C of scopes.
Embodiment 5：Prepare the silica material SBA15-5 of ionic liquid/benzylalcohol difunctionalization
The present embodiment is substantially the same manner as Example 1, and the double bond containing ionic liquid that the difference is that only addition is 1- second
Alkenyl -3- ethyl imidazol(e) bromides, quality are 204mg (1mmol).Its specific surface area is measured as 259m2/ g, air atmosphere, 200~
The weightlessness of 800 DEG C of scopes is 37.1wt%.
Embodiment 6：Prepare the silica material SBA15-6 of ionic liquid/benzylalcohol difunctionalization
The present embodiment is substantially the same manner as Example 1, and the double bond containing ionic liquid that the difference is that only addition is 1- second
Alkenyl -3- hexyl imidazolium bromides, quality are 260mg (1mmol).Its specific surface area is measured as 189m2/ g, air atmosphere, 200~
The weightlessness of 800 DEG C of scopes is 35.6wt%.
Embodiment 7：Prepare the silica material FDU12-1 of ionic liquid/benzylalcohol difunctionalization
The present embodiment is substantially the same manner as Example 1, and the silica material that the difference is that only addition is FDU12.It measures
Its specific surface area is 212m2/ g is 38.9wt% in the weightlessness of air atmosphere, 200~800 DEG C of scopes.
Embodiment 8：Prepare the silica material SBA16-1 of ionic liquid/benzylalcohol difunctionalization
The present embodiment is substantially the same manner as Example 1, and the silica material that the difference is that only addition is SBA16.It measures
Its specific surface area is 195m2/ g is 42.1wt% in the weightlessness of air atmosphere, 200~800 DEG C of scopes.
Embodiment 9：Prepare the silica material FumeSilica-1 of ionic liquid/benzylalcohol difunctionalization
The present embodiment is substantially the same manner as Example 1, and the silica material that the difference is that only addition is silica airsetting
Glue.Its specific surface area is measured as 39m2/ g is 24.5wt% in the weightlessness of air atmosphere, 200~800 DEG C of scopes.
Embodiment 10：Carbon dioxide is catalyzed as bifunctional catalyst using SBA15-5 and propylene oxide synthesizing cyclic carbonate ester is anti-
It should
1.32g (22.7mmol) propylene oxide and 150mg catalyst SBA15-5 are added in 25mL autoclaves, is filled
Enter carbon dioxide 2MPa, when oil bath control 130 DEG C of reactions 5 of temperature are small, remaining carbon dioxide discharged after being cooled to room temperature,
Remaining liq passes through Filtration of catalyst, obtains cyclic carbonate ester, the yield of cyclic carbonate ester is obtained using chromatographic
For 94%.
Embodiment 11：Carbon dioxide is catalyzed as bifunctional catalyst using SBA15-1 and propylene oxide synthesizing cyclic carbonate ester is anti-
It should
The present embodiment is substantially the same manner as Example 10, the difference is that only the bifunctional catalyst of addition as SBA15-1,
Quality is 150mg.The yield for measuring cyclic carbonate ester is 82%.
Embodiment 12：Carbon dioxide is catalyzed as bifunctional catalyst using SBA15-2 and propylene oxide synthesizing cyclic carbonate ester is anti-
It should
The present embodiment is substantially the same manner as Example 10, the difference is that only the bifunctional catalyst of addition as SBA15-2,
Quality is 90mg.The yield for measuring cyclic carbonate ester is 72%.
Embodiment 13：Carbon dioxide is catalyzed as bifunctional catalyst using SBA15-3 and propylene oxide synthesizing cyclic carbonate ester is anti-
It should
The present embodiment is substantially the same manner as Example 10, the difference is that only the bifunctional catalyst of addition as SBA15-3,
Quality is 140mg.The yield for measuring cyclic carbonate ester is 75%.
Embodiment 14：Carbon dioxide is catalyzed as bifunctional catalyst using SBA15-4 and propylene oxide synthesizing cyclic carbonate ester is anti-
It should
The present embodiment is substantially the same manner as Example 10, the difference is that only the bifunctional catalyst of addition as SBA15-4,
Quality is 120mg.The yield for measuring cyclic carbonate ester is 77%.
Embodiment 15：Carbon dioxide is catalyzed as bifunctional catalyst using SBA15-5 and propylene oxide synthesizing cyclic carbonate ester is anti-
It should
The present embodiment is substantially the same manner as Example 10, the difference is that only that the pressure that reaction is filled with carbon dioxide is
1MPa.The yield for measuring cyclic carbonate ester is 65%.
Embodiment 16：Carbon dioxide is catalyzed as bifunctional catalyst using SBA15-5 and propylene oxide synthesizing cyclic carbonate ester is anti-
It should
The present embodiment is substantially the same manner as Example 10, and the difference is that only reaction temperature is 120 DEG C.Measure cyclic carbonate ester
Yield be 86%.
Embodiment 17：Carbon dioxide and epoxychloropropane synthesizing cyclic carbonate ester are catalyzed by bifunctional catalyst of SBA15-5
Reaction
The present embodiment is substantially the same manner as Example 10, the difference is that only the epoxides of addition as epoxychloropropane,
Quality is 2.1g (22.7mmol).The yield for measuring cyclic carbonate ester is 95%.
Embodiment 18：Carbon dioxide is catalyzed as bifunctional catalyst using SBA15-5 and 1,2- oxepane synthesize ring carbon acid
Ester reacts
The present embodiment is substantially the same manner as Example 10, the difference is that only the epoxides of addition for 1,2- epoxies oneself
Alkane, quality are 2.27g (22.7mmol).The yield for measuring cyclic carbonate ester is 92%.
Embodiment 19：Carbon dioxide and styrene oxide synthesizing cyclic carbonate ester are catalyzed by bifunctional catalyst of SBA15-5
Reaction
The present embodiment is substantially the same manner as Example 10, the difference is that only the epoxides of addition as styrene oxide,
Quality is 2.73g (22.7mmol).The yield for measuring cyclic carbonate ester is 73%.
Embodiment 20：Carbon dioxide and 7-oxa-bicyclo[4.1.0 synthesizing cyclic carbonate ester are catalyzed by bifunctional catalyst of SBA15-5
Reaction
The present embodiment is substantially the same manner as Example 10, the difference is that only the epoxides of addition as 7-oxa-bicyclo[4.1.0,
Quality is 2.23g (22.7mmol).The yield for measuring cyclic carbonate ester is 47%.
Embodiment 21：Carbon dioxide is catalyzed as bifunctional catalyst using SBA16-1 and propylene oxide synthesizing cyclic carbonate ester is anti-
It should
The present embodiment is substantially the same manner as Example 10, the difference is that only the bifunctional catalyst of addition as SBA16-1,
Quality is 120mg.The yield for measuring cyclic carbonate ester is 86%.
Embodiment 22：Carbon dioxide is catalyzed as bifunctional catalyst using FumeSilica-1 and propylene oxide synthesizes ring carbon acid
Ester reacts
The present embodiment is substantially the same manner as Example 10, and the bifunctional catalyst that the difference is that only addition is
FumeSilica-1, quality 120mg.The yield for measuring cyclic carbonate ester is 75%.
Claims (6)
1. a kind of preparation method of the silica catalysis material of difunctionalization, it is characterised in that：By silica material and 3- front threes
The third fat of oxysilane acrylic acid is according to 1g silica：The ratio of 1~2mmol3- trimethoxy silanes the third fat of acrylic acid is added to 20
In~50mL dry toluenes, when reflux 12~48 is small in a nitrogen atmosphere, reaction system filters after being cooled to room temperature, solid product
It is washed with 10~50mL ethyl alcohol when vacuum drying 12~24 is small at 2~5 times, 40~80 DEG C and obtains double-bond functionalized silica material
Material；By double-bond functionalized silica material 1g and double bond containing ionic liquid (1~2mmol), 4- vinyl benzyl alcohols (1~
It 4mmol) is added in 25~100mL chloroforms and/or n,N-Dimethylformamide, and it is (double to add in initiator azodiisobutyronitrile
The 1~5% of key monomer gross mass)；When said mixture reflux 12~36 is small, reaction system filters after being cooled to room temperature, product
It is washed twice with 10~50mL ethyl alcohol, ionic liquid and benzylalcohol difunctionalization is obtained when vacuum drying 12~24 is small at 40~80 DEG C
Silica catalysis material.
2. by preparation method described in claim 1, it is characterised in that：The silica material can be porous silica,
One or two or more kinds in silica aerogel, SBA-15, SBA-16, FDU-12 or MCM-41.
3. by preparation method described in claim 1, it is characterised in that：The double bond containing ionic liquid can be 1- ethylene
Base -3- ethyl imidazol(e)s bromide, 1- vinyl -3- butyl imidazoles bromide or one kind in 1- vinyl -3- hexyl imidazolium bromides or
Two kinds or more.
4. a kind of silica for ionic liquid/benzylalcohol difunctionalization that any preparation method of claims 1 to 3 prepares
Material.
5. a kind of silica material of ionic liquid/benzylalcohol difunctionalization described in claim 4 is in catalysis carbon dioxide and ring
Application in the reaction of oxide synthesizing cyclic carbonate ester, it is characterised in that：Epoxide 1g~3g and ionic liquid/benzylalcohol is double
Silica material 90mg~150mg of functionalization is added in autoclave, is filled with carbon dioxide, pressure 0.5
~3MPa when 80~150 DEG C of reactions 1~6 are small, discharges remaining carbon dioxide, remaining liq passed through after being cooled to room temperature
Filter out catalyst, you can obtain cyclic carbonate ester.
6. the application as described in claim 5, which is characterized in that epoxides can be ethylene oxide, propylene oxide, epoxy chlorine
One or two or more kinds in propane, 1,2- epoxy butanes, 1,2- oxepanes, 7-oxa-bicyclo[4.1.0 or styrene oxide.
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| CN112121853A (en) * | 2020-09-08 | 2020-12-25 | 重庆邮电大学 | Mesoporous hollow silica nanosphere loaded with prolinol catalyst and preparation method and application thereof |
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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112121853A (en) * | 2020-09-08 | 2020-12-25 | 重庆邮电大学 | Mesoporous hollow silica nanosphere loaded with prolinol catalyst and preparation method and application thereof |
| 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 |
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