CN109382128A - The method and catalyst of catalytically synthesizing cyclic carbonate ester - Google Patents
The method and catalyst of catalytically synthesizing cyclic carbonate ester Download PDFInfo
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- CN109382128A CN109382128A CN201811271719.3A CN201811271719A CN109382128A CN 109382128 A CN109382128 A CN 109382128A CN 201811271719 A CN201811271719 A CN 201811271719A CN 109382128 A CN109382128 A CN 109382128A
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
- B01J27/26—Cyanides
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- 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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
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- 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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- 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
- C07D317/42—Halogen atoms or nitro radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J2231/72—Epoxidation
Abstract
The present invention discloses a kind of catalyst and application thereof, especially a kind of for being catalyzed CO2The catalyst of synthesizing annular carbonate.Catalyst of the invention is the Fe for accumulating pore structure4 Ⅲ(Fe(CN)6)3Or KM4(FeⅢ(CN)6)3, wherein M is Co or Ni or Zn.Catalyst of the invention can normal pressure, solvent-free condition by the reaction substrate of epoxides, be combined to cyclic carbonate.
Description
Technical field
The present invention relates to a kind of method of catalytically synthesizing cyclic carbonate ester and its catalyst.
Background technique
Carbon dioxide (CO2) it is a kind of gas that colorless and odorless is nontoxic.In recent years, in atmosphere carbon dioxide content increasing
The problem of causing global warming is added to cause the extensive concern [1,2] of researcher.Although carbon dioxide easily causes greenhouse effect
Answer, but it still have the advantages that it is cheap, be easy to get (referring to X.Wang, Y.Zhou, Z.Guo, G.Chen, J.Li, Y.Shi,
Y.Liu, J.Wang, Chem.Sci.6 (2015) 6916-6924., J.Langanke, A.Wolf, J.Hofmann, K.M.A.Subhani,T.E.Müller,W.Leitner,C.Gürtler, Green Chem.16(2014)1865-
1870.).] carbon dioxide can be used as 1 Material synthesis of carbon such as formamide (referring to S.W.Klankermayer,
Kassem Beydoun, and, W.Leitner*, Angew. Chem.Int.Ed.55 (2016) 7296-7343), methanol (ginseng
See: S.G.Jadhav, P.D.Vaidya, B.M. Bhanage, J.B.Joshi, Chem.Eng.Res.Des.92 (2014)
2557-2567.), formic acid (referring to: it is C.A. Huff, M.S.Sanford, ACS Catal.3 (2013) 2412-2416) and cyclic annular
The important chemical products such as carbonic ester (referring to: J.W.Comerford, I.D.V.Ingram, M.North, X.Wu, Green
Chem.17 (2015) 1966-1987., V.Laserna, E.Martin, E.C.Escudero-Ad á n, A.W.Kleij, ACS
Catal.7 (2017)5478-5482.).Cyclic carbonate can be used as aprotic polar solvent, while also in synthetic plastic, doctor
Medicine etc. has a wide range of applications (referring to C.J.Whiteoak, N.Kielland, V.Laserna, E.C. Escudero-
Ad á n, E.Martin, A.W.Kleij, J.Am.Chem.Soc.135 (2013) 1228-1231., B.F.S.P.Verevkin,A.Chem.Rev.110 (2010) 4554-4581., C.M.Alder,
J.D.Hayler,R.K.Henderson,A.M.Redman,L.Shukla, L.E.Shuster,H.F.Sneddon,Green
Chem.18(2016)3879-3890.)。
It is that an efficient green has absolutely atom benefit by CO2 and the direct synthesizing annular carbonate of epoxides
With the route (C.Mart í n, G.Fiorani, A.W.Kleij, ACS Catal.5 (2015) 1353-1370.) of rate.Currently, closing
The heterogeneous catalysis system of cyclization dress carbonic ester is mainly ionic liquid, salt etc. (referring to: X.Wang, Y.Zhou, Z.Guo,
G.Chen, J.Li, Y.Shi, Y.Liu, J.Wang, Chem.Sci. 6 (2015) 6916-6924., L.-N.He, H.Yasuda,
T.Sakakura, Green Chem.5 (2003) 92-94., A.Sibaouih, P.Ryan, M.B.Rieger,
T.Repo, Appl.Catal.A-Gen. 365 (2009) 194-198., A.-L.Girard, N.Simon, M.Zanatta,
S.Marmitt,P.J. Dupont, Green Chem.16 (2014) 2815-2825., S.Zhang,
Y.Chen,F.Li,X.Lu,W. Dai,R.Mori,Catal.Today 115(2006)61-69.).In addition, there are also a large amount of metals
The heterogeneous catalysis such as salt, metal oxide and metal organic framework (MOFs) be catalyzed the reaction progress (referring to:
A.Decortes, M.Martinez Belmonte,J.Benet-Buchholz,A.W.Kleij,Chem.Commun.46
(2010) 4580-4582, J.-Q.Wang, W.-G.Cheng, J.Sun, T.-Y.Shi, X.-P.Zhang, S.-J.Zhang,
RSCAdv.4 (2014) 2360-2367., C.Maeda, T.Taniguchi, K.Ogawa, T.Ema, Angew.
Chem.Int.Ed.Engl.54 (2015) 134-138., M.H.Beyzavi, R.C.Klet, S.Tussupbayev, J.
Borycz,N.A.Vermeulen,C.J.Cramer,J.F.Stoddart,J.T.Hupp,O.K.Farha,J.Am.
Chem.Soc.136 (2014) 15861-15864., Y.Xie, T.T.Wang, X.H.Liu, K.Zou, W.Q. Deng,
Nat.Commun.4(2013)1960.).Compared to homogeneous catalyst, heterogeneous catalysis have it is easily separated, catalysis it is at low cost
The advantages that.The catalytic efficiency of heterogeneous catalysis is relatively low, therefore the catalytic activity for promoting heterogeneous catalysis is that catalysis is ground
One of the person's of studying carefully facing challenges.
Summary of the invention
The present invention provides the preparation side of a kind of catalyst that can be used for catalytically synthesizing cyclic carbonate ester and this catalyst
Method, while the method for being synthetically prepared cyclic carbonate with this catalyst being provided.
Catalyst for catalytically synthesizing cyclic carbonate ester of the invention is the Fe for accumulating pore structure4 Ⅲ(Fe(CN)6)3, or
Person is the KM for accumulating pore structure4(FeⅢ(CN)6)3, wherein M is Co or Ni or Zn.
Catalyst Fe of the present invention4 Ⅲ(Fe(CN)6)3Preparation method is: by FeCl2·4H2O and K3[Fe
(CN)6]·6H2O distinguishes in molten distilled water, and both the above solution is mixed under stiring, then mixture is heated 12 at 80 DEG C
Hour, by the solid being centrifugally separating to obtain, it is dried and obtains at 80 DEG C after solid obtained by sufficiently being washed with high purity water
The catalyst.
Catalyst KM of the present invention4(FeⅢ(CN)6)3Preparation method is: by FeCl2·4H2O (Co(NO3)2·
6H2O,Ni(NO3)26H2O, ZnCl2) and K3[Fe(CN)6]·6H2O distinguishes in molten distilled water, and both the above solution is existed
The lower mixing of stirring, then mixture is heated 12 hours at 80 DEG C, by the solid being centrifugally separating to obtain, sufficiently washed with high purity water
It is dried at 80 DEG C after solid obtained by washing and obtains the catalyst.
The method of catalytically synthesizing cyclic carbonate ester of the invention is: the reaction bottom of epoxides being added in the reaction vessel
Object, with the catalyst Fe4 Ⅲ(Fe(CN)6)3Or KM4(FeⅢ(CN)6)3And co-catalyst, exist under normal pressure and by reaction system
It is stirred to react in 60~100 DEG C of oil baths, product-cyclic carbonate, total catalysis used is collected by filtration after the reaction was completed
Agent is any quaternary ammonium salt.
Preferably, it is TBAB that the method for catalytically synthesizing cyclic carbonate ester of the invention, which is co-catalyst used,.
Preferably, it is TBAC that the method for catalytically synthesizing cyclic carbonate ester of the invention, which is co-catalyst used,.
Preferably, it is TBAI that the method for catalytically synthesizing cyclic carbonate ester of the invention, which is co-catalyst used,.
In the method for catalytically synthesizing cyclic carbonate ester of the present invention, substrate used can be styrene oxide, ring
Any of oxygen chloropropane, methyl-prop ethylene oxidic ester, n-butyl glycidyl ether, cyclohexene oxide or phenyl glycidyl ether
Kind.
It is relevant experiments have shown that, catalyst of the invention is under the conditions of normal pressure, solvent-free to catalysis carbon dioxide and ring
The oligomer of oxide shows higher catalytic activity, can be used with repetitive cycling, and preparation method is very simple, one
Kind is efficient, green iron complex catalyst.It can in a mild condition (solvent-free and 100 DEG C) using method of the invention
High conversion obtains product with selectivity.In addition, catalyst of the invention can be very good after the completion of reaction with substrate into
Row separation, facilitates the recycling of catalyst；Solvent is not needed in reaction process of the invention, is eliminated after reaction
The separating step of solvent, and pressure carbon dioxide is normal pressure in reaction process, therefore additional pressurization is also no longer needed to set
It is standby.
Detailed description of the invention
Attached drawing 1 is Fe of the present invention4 Ⅲ(Fe(CN)6)3Electronic Speculum, the energy spectrum diagram of catalyst.Wherein: it (a) is transmission electron microscope picture,
(b) it is its energy dispersion x-ray light map, is (c) comparative catalyst FeⅢ 4(Fe(CN)6)3The transmission electron microscope picture of-cube, (d)
Wide-angle annular dark field scanning transmission electron microscope, (e-h) are FeⅢ 4(Fe(CN)6)3Distribution diagram of element.
Attached drawing 2 is FeⅢ 4(Fe(CN)6)3Nitrogen inhales de- and pore volume curve, in which: (a) FeⅢ 4(Fe(CN)6)3And FeⅢ 4
(Fe(CN)6)3- cube nitrogen adsorption desorption curve, (b) FeⅢ 4(Fe(CN)6)3And FeⅢ 4(Fe(CN)6)3The pore volume of-cube.
Attached drawing 3 is FeⅢ 4(Fe(CN)6)3X diffraction spectrogram and fine diffraction spectrogram, in which: (a) all elements FeⅢ 4(Fe
(CN)6)3XPS compose entirely, (b) XPS of Fe element is finely composed.
Attached drawing 4 is FeⅢ 4(Fe(CN)6)3X diffraction pattern and raman spectrum, in which: (a) is X diffraction pattern, is (b) drawing
Graceful spectrogram.
Attached drawing 5 is FeⅢ 4(Fe(CN)6)3Recycle the relation curve of rear conversion ratio and selectivity.
Specific embodiment
The present invention is explained with reference to embodiments.
One, the preparation of catalyst
1, the preparation of catalyst
1.1 FeⅢ 4(Fe(CN)6)3Preparation
By FeCl2·4H2O (1mmol) and K3[Fe(CN)6]·6H2O (0.5mmol) is dissolved in respectively in 20mL distilled water.
Both the above solution is mixed under magnetic stirring, mixture is transferred in the stainless steel autoclave of polytetrafluoroethyllining lining
And it is heated 12 hours at 80 DEG C.Finally, drying by the solid that is centrifugally separating to obtain high-purity water washing 3 times and at 80 DEG C
12 hours, obtain FeⅢ 4(Fe(CN)6)3。
1.2 KM4(FeⅢ(CN)6)3(Fe(CN)6)3The preparation of-cube
By Co (NO3)2·6H2O, 6H2O (1mmol) and K3[Fe(CN)6]·6H2O (0.5mmol) is dissolved in 20mL respectively
In distilled water.Both the above solution is mixed under magnetic stirring, mixture is transferred to the stainless steel of polytetrafluoroethyllining lining
It is heated 12 hours in autoclave and at 80 DEG C.Finally, by the solid that is centrifugally separating to obtain high-purity water washing 3 times and 80
It is 12 hours dry at DEG C, obtain KCo4(FeⅢ(CN)6)3。
By ZnCl2·6H2O (1mmol) and K3[Fe(CN)6]·6H2O (0.5mmol) is dissolved in respectively in 20mL distilled water.
Both the above solution is mixed under magnetic stirring, mixture is transferred in the stainless steel autoclave of polytetrafluoroethyllining lining
And it is heated 12 hours at 80 DEG C.Finally, drying by the solid that is centrifugally separating to obtain high-purity water washing 3 times and at 80 DEG C
12 hours, obtain KZn4(FeⅢ(CN)6)3。
By Ni (NO3)2·6H2O (1mmol) and K3[Fe(CN)6]·6H2O (0.5mmol) is dissolved in 20 mL distilled water respectively
In.Both the above solution is mixed under magnetic stirring, mixture is transferred to the stainless steel autoclave of polytetrafluoroethyllining lining
In and 80 DEG C heat 12 hours.Finally, by the solid that is centrifugally separating to obtain high-purity water washing 3 times and dry at 80 DEG C
Dry 12 hours, obtain (KNi4(FeⅢ(CN)6。
1.3 Fe(CN)6)3The preparation of-cube
Aftermentioned (the Fe (CN) of the present invention6)3The preparation of-cube can be found in L.Zhang, H.B.Wu, X.W.Lou, J.
Am.Chem.Soc.135 (2013) 10664-10672., i.e. ,] by 0.5mmol K under constant magnetic agitation4Fe(CN)6·
3H2O is added to stirring in HCl solution (0.1M, 50mL) and after ten minutes, obtains clear solution.Then mixture is transferred to poly-
It is heated 12 hours in the stainless steel autoclave of tetrafluoroethene liner and at 80 DEG C.Finally by resulting solid is collected by centrifugation
And with milli-Q water 3 times, 12h is then dried at 80 DEG C.
2, catalyst characterization
Pattern and microstructure to preceding prepared catalyst carry out transmission electron microscope (TEM) characterization, referring to attached drawing 1.
FeⅢ4(Fe(CN)6)3TEM image (Fig. 1 a) show the catalyst be cluster pattern.In order to study FeⅢ 4(Fe
(CN)6)3Elemental redistribution, wide-angle annular dark field scanning transmission electron microscope (HAADF-STEM) has been carried out to catalyst,
Referring to Fig. 1 d, the element contained by catalyst is respectively carbon, nitrogen, iron.Distribution diagram of element 1b is analysis shows catalyst in catalyst
Middle C, N, K and Fe are uniformly distributed, and also provided is the molar fraction of element in catalyst (C 83.55%, N 10.50%, K
0.33% and Fe 3.39%).Fig. 1 c shows FeⅢ 4(Fe(CN)6)3- cube is cubic structure.Fig. 1 e- of mapping map
The Elemental redistribution that Fig. 1 h shows catalyst is more uniform.
In order to characterize the specific surface area of catalyst, the present invention carries out BET test to catalyst, referring to attached drawing 2.
It can be seen that adsorption desorption curve meets IV type adsorption isotherm by Fig. 2 a, show the catalyst for accumulation pore structure
[24]。FeⅢ 4(Fe CN)6)3Specific surface area and pore volume be respectively 296.3m2/ g and 0.23cm3/g.High surface area and hole body
Product can provide more exposed active site [25,26] for catalyst. FeⅢ 4(Fe(CN)6)3The adsorption desorption curve table of-cube
The bright catalyst does not have meso-hole structure. FeⅢ 4(Fe(CN)6)3The surface area and pore volume of-cube is respectively 10.0m2/ g and
0.018cm3/g.Small specific surface area and pore volume shows FeⅢ 4(Fe(CN)6)3- cube catalyst is solid cube knot
Structure, the architectural characteristic are unfavorable for contact of the active site with substrate.
In order to characterize catalyst element valence distribution, to catalyst carry out XPS test, referring to attached drawing 3 and Fig. 4.
Compose (Fig. 3 a) entirely from XPS and clearly show that have on catalyst surface C1s (284.6eV), N1s (397.9 eV) and
Fe 2p (708.5 and 721.8eV) element.The fine spectrogram (Fig. 3 b) of Fe 2p is made of four main peaks, in conjunction with can be respectively
And 724.3eV 708.5,711.5,721.4.The peak of 708.5 and 724.3eV corresponds to [FeII(CN)6] Fe 2p3/2And Fe
2p1/2, the combination of 711.5 and 721.4eV can correspond to FeⅢ4(Fe(CN)6)3In FeⅢ2p3/2With III 2p of Fe1/2。
From Fig. 4 a it is found that the XRD spectrum of the catalyst of lattice plane is shown in 17.3 °, 24.6 °, 35.2 °, 39.4 °,
(200) of 43.4 °, 50.5 °, 53.9 ° and 57.0 ° 8 characteristic peaks for catalyst, (220), (400), (420), (422),
(440), (600) and (620) crystal face.Fig. 4 b show Raman spectrum, in 2091 and 2130 cm-1Two three keys of Qiang Fengwei carbon nitrogen
Stretching vibration.In addition, in 264 and 534cm-1The flexible and flexural vibrations peak that the bands of a spectrum at place are Fe-C ≡ N-Fe.
Two, the assessment of catalyst
The test of agent catalytic performance carries out in 25mL three neck round bottom flask under normal pressure.Add in three neck round bottom flask
Enter epoxides (5mmol), catalyst (10mg) and co-catalyst (Bu4NBr or other) 2.5mol%, and by reaction system
It is stirred in oil bath with the revolving speed of 600rpm/min, the reaction time is 0.25-5 hours.Production is collected by filtration after reaction
Object, and by gas chromatography mass spectrometer (GC-MS, Agilent 6,890N/5,937N) and1HNMR (uses CDCl3As solvent
Varian Inova 400,400MHz) detect conversion ratio, selectivity and product yield.
The activity of catalyst calculates are as follows: conversion ratio %=100 × ([C0-C1]/[C0]), selective %=100 × [C "]/
[C '] and yield %=100 × [C "]/[C0], [C0] it is initial substrate concentration, [C1] it is concentration of substrate at the end of reaction, [C ']
Production concentration [C "] is the concentration of target product.
With styrene oxide and CO2Cycloaddition generates styrene carbonic ester and assesses as model reaction catalyst,
Catalytic result is as shown in table 1.
When reaction carries out under conditions of not using co-catalyst (table 1, the 1st) or in 100 DEG C and 1atm CO2Pressure
When TBAB (table 1, the 2nd) being used only under power, only a small amount of product.The process shows catalyst and co-catalyst for ring
Addition reaction is essential.The 3-9 different types of catalyst of display have different catalytic activity.FeⅢ 4(Fe
(CN)6)3Catalyst has conversion ratio in the presence of co-catalyst (TBAB) and selectivity is all 99% good catalytic effect.
Fe when using TBAC (the 8th) or TBAI (the 9th) as co-catalystⅢ 4(Fe(CN)6)3Catalytic effect cannot reach the former
Good result.By being studied above it can be concluded that lewis acid and nucleopilic reagent are the necessary conditions of the reaction in the reaction.Three
The difference of kind co-catalyst is the difference of halide ion, therefore co-catalyst is mainly halide ion to cycloaddition reaction
It influences.Activity presses TBAB > TBAI > TBAC decreasing order as shown in Table 1, this is attributed to the nucleophilic property of halide anions
(Cl->Br->I-) and leaving capability (I->Br->Cl-).It can be found that influence of the temperature to cycloaddition reaction from 3,10-13
It is larger.With the reduction of temperature, conversion ratio and selectivity can also be decreased.Lower reaction temperature can generate more pair
Product, therefore, higher temperature are advantageously implemented better yield.
The result that 1 styrene oxide of table and CO2 are reacted with different catalysts
Reaction condition: styrene oxide (5mmol), 2.5mol% co-catalyst, catalyst (10mg), CO2Pressure
(1atm), reaction time (3h), GC-MS measure conversion ratio and selectivity.
For the broad spectrum activity of Study of Catalyst, the present invention is to other kinds of epoxides at 1atm pressure and 100 DEG C
Carry out cycloaddition reaction.Different types of epoxides is converted into relevant product and conversion ratio, selectivity referring to table 2.By table
Most of substrate suffers from good conversion ratio and selectivity known to 2.In the presence of TBAB and catalyst, epoxychloropropane
Conversion ratio and selectivity are all 99%, the mainly progress of the electron-withdrawing ability of the chlorine atom reaction.Cyclohexene oxide turns
Change effect is bad, this may be as caused by steric hindrance.
2 epoxides of table and CO2Cycloaddition reaction
A reaction condition: measuring epoxides (5mmol) by GC-MS, 2.5mol% catalyst, catalyst (10mg), CO
2 pressure (1atm), reaction time (3h), conversion ratio and selectivity.The b reaction time (5 hours)
Three, catalyst recycling and reusing
Three, catalyst recycling and reusing
One good catalyst will not only have good catalytic activity, should also have good recuperability reusing.This
Carbon dioxide and styrene oxide of the invention to the cyclicity of catalyst in atmospheric pressure make 100 DEG C of nothings of co-catalyst in TBAB
The condition of solvent carries out, catalyst is collected by centrifugation after the reaction was completed and with ethanol washing three times, then vacuum drying is urged
Agent is to be reused for next secondary response.The Repeatability of catalyst is as shown in Figure 5, it can be seen that after five circulations,
The catalytic performance of catalyst has reduction slightly.This is the result shows that the catalyst has good recuperability reusing.
Finally, we detect the catalyst after circulation five times with ICP, it is found that the content of Fe drops to from 37.39%
33.92%.
Claims (9)
1. a kind of catalyst of catalytically synthesizing cyclic carbonate ester, it is characterized in that catalyst is the Fe for accumulating pore structure4 III(Fe
(CN)6)3。
2. a kind of catalyst of catalytically synthesizing cyclic carbonate ester, it is characterized in that catalyst is the KM for accumulating pore structure4(FeIII
(CN)6)3, wherein M is Co or Ni or Zn.
3. the preparation method of catalyst described in claim 1, it is characterised in that by FeCl2·4H2O and K3[Fe(CN)6]·6H2O
Respectively in molten distilled water, both the above solution is mixed under stiring, then mixture is heated 12 hours at 80 DEG C, passes through centrifugation
Isolated solid is dried the catalyst described in obtaining after sufficiently washing acquired solid with high purity water at 80 DEG C.
4. the preparation method of catalyst described in claim 2, it is characterised in that by FeCl2·4H2O(Co(NO3)26H2O, Ni
(NO3)26H2O, ZnCl2) and K3[Fe(CN)6]·6H2O distinguishes in molten distilled water, and both the above solution is mixed under stiring
It closes, then mixture is heated 12 hours at 80 DEG C, it is solid obtained by sufficiently being washed with high purity water by the solid being centrifugally separating to obtain
It is dried at 80 DEG C after body and obtains the catalyst.
5. a kind of method of catalytically synthesizing cyclic carbonate ester, it is characterized in that be added in reaction vessel the reaction substrate of epoxides,
Catalyst and co-catalyst of any of claims 1 or 2 stir in 60~100 DEG C of oil baths anti-under normal pressure and by reaction system
It answers, product-cyclic carbonate is collected by filtration after the reaction was completed, co-catalyst used is any quaternary ammonium salt.
6. the method for catalytically synthesizing cyclic carbonate ester according to claim 5, it is characterized in that co-catalyst used is
TBAB。
7. the method for catalytically synthesizing cyclic carbonate ester according to claim 5, it is characterized in that co-catalyst used is
TBAC。
8. the method for catalytically synthesizing cyclic carbonate ester according to claim 5, it is characterized in that co-catalyst used is
TBAI。
9. according to the method for the catalytically synthesizing cyclic carbonate ester any in claim 5 to 8, its substrate of feature is oxidation
Styrene, epoxychloropropane, methyl-prop ethylene oxidic ester, n-butyl glycidyl ether, cyclohexene oxide or phenyl glycidyl
Ether it is any.
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| US5935380A (en) * | 1996-03-08 | 1999-08-10 | 3M Innovative Properties Company | Adsorbent for metal ions and method of making and using |
| CN101704536A (en) * | 2009-11-25 | 2010-05-12 | 华东师范大学 | Novel Prussian blue mesocrystals and preparation method thereof |
| CN102671703A (en) * | 2012-04-26 | 2012-09-19 | 南京工业大学 | Metal complex catalyzer and application thereof for synthesizing cyclic carbonate |
| CN104327036A (en) * | 2014-10-10 | 2015-02-04 | 中国科学院长春应用化学研究所 | Preparation method of cyclic carbonate |
| CN107973771A (en) * | 2017-12-06 | 2018-05-01 | 河南工程学院 | A kind of method that cobalt-base catalyst chemical recycling of carbon dioxide prepares cyclic carbonate |
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| US5935380A (en) * | 1996-03-08 | 1999-08-10 | 3M Innovative Properties Company | Adsorbent for metal ions and method of making and using |
| CN101704536A (en) * | 2009-11-25 | 2010-05-12 | 华东师范大学 | Novel Prussian blue mesocrystals and preparation method thereof |
| CN102671703A (en) * | 2012-04-26 | 2012-09-19 | 南京工业大学 | Metal complex catalyzer and application thereof for synthesizing cyclic carbonate |
| CN104327036A (en) * | 2014-10-10 | 2015-02-04 | 中国科学院长春应用化学研究所 | Preparation method of cyclic carbonate |
| CN107973771A (en) * | 2017-12-06 | 2018-05-01 | 河南工程学院 | A kind of method that cobalt-base catalyst chemical recycling of carbon dioxide prepares cyclic carbonate |
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