CN106831698A - A kind of method of heterogeneous catalysis synthesizing annular carbonate - Google Patents
A kind of method of heterogeneous catalysis synthesizing annular carbonate Download PDFInfo
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- C07—ORGANIC CHEMISTRY
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- 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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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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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
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/31—Aluminium
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
- B01J2531/72—Manganese
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
Abstract
The invention discloses a kind of method of heterogeneous catalysis synthesizing annular carbonate, by the use of carbon dioxide and epoxides as raw material, with super crosslink metallic porphyrin porous material as heterogeneous catalyst, quaternary salt is co-catalyst, it is 15 ~ 100% in gas concentration lwevel, pressure be 0.1 MPa ~ 3.0 MPa, temperature be 25 ~ 100 DEG C under conditions of, realize efficient high selectivity catalytically synthesizing cyclic carbonate ester.The major advantage of the method is catalyst activity high, stable performance, and preparation method is simple, low cost, easily reclaims, and reaction condition is gentle, it is not necessary to add any solvent.Additionally, the present invention can be raw material using carbon dioxide in industrial waste gas, cyclic carbonate, great industrial application value are catalytically conveted under normal temperature and pressure conditionses.
Description
Technical field
The present invention relates to a kind of synthetic method of cyclic carbonate.
Background technology
With the continuous quickening of global industry process, the consumption of fossil energy increasingly increases so that people both faced
The problem of resource exhaustion, also faces its environmental problem brought.CO2It is a kind of rich reserves and the cheap resource of carbon one,
Realize CO2Effectively trapping and Efficient Conversion have turned into the study hotspot of domestic and international association area.Meanwhile, to alleviate environment and the energy
Crisis provides a kind of available strategy.Wherein, CO2Have Atom economy, height additional with epoxides synthesizing annular carbonate
The characteristics of being worth and be environment-friendly.Cyclic carbonate is used as a kind of aprotic solvent, synthetic intermediate and the raw material of industry, extensive use
In fields such as medicine, agricultural chemicals, coating and electronic chemical products.
At present, with CO2It is raw material with cyclic carbonate, in the reaction system of synthesizing annular carbonate, has been developed
A series of catalyst, such as quaternary ammonium salt, quaternary alkylphosphonium salts, organic base, ionic liquid, metal oxide, metal complex, feature are organic
Polymeric material and metalloporphyrin etc..Wherein, metalloporphyrin shows efficiently as a kind of quasi-enzyme catalytic agent in catalytic reaction
Property, selectivity, high selectivity and the characteristics of mild condition, and its synthetic method is simple, structure easy-regulating, therefore, receive
The extensive concern of researcher.Early in nineteen eighty-three, it is double with N- methylimidazoles composition that the Inoue of Japan etc. has just reported aluminium porphyrin
Component catalyst system is catalyzed CO2With the cycloaddition reaction of expoxy propane, and achieve better effects [J.Am.Chem.Soc.,
1983,105(5),1304].2015, the report such as Wang Xianhong by after optimization, aluminium porphyrin consumption be only 0.001mol% and
Double-(dihalotriphenylphosphoranes base) ammonium chloride (PPNCl) of 1.2mol%, under the conditions of 3.0MPa and 120 DEG C, expoxy propane is substantially complete
Full conversion, TOF values up to 1.85 × 105h-1[Green Chem.,2015,17(5),2853].In addition to aluminium porphyrin, also zinc
Porphyrin [J.CO2UTIL., 2016,16,264], chromium porphyrin [J.Org.Chem., 1995,60 (3), 725] and Cob altporphyrin [Green
Chem., 2016,18,3567] etc. also it is widely reported for CO2With the cycloaddition reaction of epoxides.
Function organic polymer materials as the emerging catalyst of a class, with selective absorption gas, good stability
And it is easily separated the features such as, be developed rapidly in recent years, increasing researcher be applied to catalysis CO2With ring
Oxide is synthesized in the reaction of cyclic carbonate.2013, Deng etc. with salen Al/Co and three ethynylbenzenes as monomer,
By Sonogashira coupling reactions, microporous polymer catalyst Al-CMP and Co-CMP are prepared for, are taken in the reaction system
Preferable catalytic effect was obtained, although and preferable result is also obtained under normal temperature and pressure conditionses, the reaction time is more long
[Nat.Commun.,2013,4,1-7].2014, the seminar prepared catalyst Z n-CMP using same strategy,
In the reaction system, TOF values are up to 11600h-1, but when the reaction is catalyzed under being applied to normal temperature and pressure conditionses, efficiency is still
It is relatively low.2016, Xiao Fengshou etc., by the method for radical polymerization, was obtained catalyst Co/ with tetravinyl Cob altporphyrin as monomer
POP-TPP, at 29 DEG C, when pressure is 0.1MPa, reacts 24h, achieves satisfied result, and catalyst can be reused effectively
More than 20 times, and creatively by low concentration CO2As research object, with certain industrial application value [J.Catal.,
2016,338,202]。
In the reaction system, still there is a problem that inefficient under temperate condition.Therefore, it is high with reference to quasi-enzyme catalytic agent
Effect, it is gentle the features such as and the good stability of function organic polymer materials and it is easily separated the features such as, construct with stability and high efficiency
Heterogeneous catalyst, and be applied under normal temperature and pressure conditionses, so with industrial waste gas CO2Source, realizes CO2First capture and urge again
Change is converted into cyclic carbonate, great commercial application potentiality.
The content of the invention
The purpose of the present invention is directed to the technological deficiency that the current reaction system has activity, there is provided it is a kind of it is simple efficiently,
The heterogeneous catalyst that stabilization is easily reclaimed, under normal temperature and pressure, condition of no solvent, or even with industrial waste gas CO2Source, realizes CO2First catch
Obtain and be catalytically conveted to cyclic carbonate again.
Technical scheme is as follows：
A kind of method of heterogeneous catalysis synthesizing annular carbonate, with carbon dioxide and epoxides as raw material, with logical
The super crosslink metallic porphyrin porous material of formula (I) structure is catalyst, with quaternary salt as co-catalyst, is in gas concentration lwevel
15~100%, initial pressure be 0.1MPa~3.0MPa, temperature be 25~100 DEG C under conditions of, react 1~6h, in high yield
Synthesizing annular carbonate, catalyst can reclaim, and can realize repeatedly using by simple filtration, washing.
The super crosslink metallic porphyrin porous material be with metalloporphyrin as monomer, with formal as crosslinking agent,
With anhydrous FeCl3Catalyst, is reacted by Friedel-Crafts and prepared, its structure such as logical formula (I)：
In logical formula (I), the metallic atom M is Al, Zn, Co, Cu, Fe, Mn and Cr one of which, and X is halogen, R1And R2
It is respectively selected from H, Me, Br and OCH3。
The structure of described super crosslink metallic porphyrin porous material catalyst is selected from logical formula (I).
Described co-catalyst selected from the one kind in logical formula (II)：
In logical formula (II), the R3Selected from Me, Et,nBu and Ph, Y are halogen.
Described epoxides is selected from logical formula (III)：
The concentration of preferred carbon dioxide is 15~100%, and pressure is 0.1~3.0MPa, and reaction temperature is 25~100
℃。
The present invention uses super crosslink metallic porphyrin porous material and quaternary salt as dual-component catalyst, realizes normal temperature normal
Under the conditions of pressure, efficient high selectivity is catalyzed CO2With epoxides synthesizing annular carbonate, its principle is using the porous of catalyst
Property and to CO2The characteristics of selective absorption, by CO2Be trapped in around abundant metal center (Lewis), so with duct in pass through
Metal center and the epoxides of quaternary salt collaboration activation react, and quickly generate corresponding cyclic carbonate.
Advantage of the invention and have the beneficial effect that：
1st, reaction process process is simple, and condition is very gentle, simple operation, safe and efficient；
2nd, the catalyst can efficient catalytic industry gas in low concentration CO2Cyclic carbonate is converted into, with commercial Application
Value；
3rd, the method for preparing catalyst is simple, raw material is cheap and easy to get；
4th, any organic solvent, environmental protection need not be added；
5th, product and catalyst are easily separated, and catalyst repeatedly can be reused effectively.
Specific embodiment
The present invention is further described in the examples below, but the merely illustrative purposes of discussion of these embodiments, should not
It is interpreted implementation limitation of the invention.
Embodiment 1
In to the stainless steel autoclave of 10mL, 6.0 × 10 are sequentially added-4(M is the catalyst of mmol in logical formula (I)
Al, R1And R2All it is H), 12mmol epoxidations propane and 0.12mmol co-catalysts (lead to R in formula (II)3It is normal-butyl, Y is
Br), being passed through carbon dioxide makes its initial pressure for 3.0MPa, under the conditions of being 100 DEG C in temperature, after stirring 2h, is immediately placed in cold
Room temperature is cooled in water, continuation is cooled down in being subsequently placed at frozen water, after slowly discharging remaining carbon dioxide, filters to isolate catalysis
Agent, taking appropriate filtrate carries out gas chromatographic analysis, and the yield of gained cyclic carbonate is 99%, is reacted the starting stage, and TOF values are high
Up to 15000h-1。
Embodiment 2
In to the stainless steel autoclave of 10mL, 7.5 × 10 are sequentially added-3(M is the catalyst of mmol in logical formula (I)
Al, R1And R2All it is H), 3mmol epoxidations propane and 0.06mmol co-catalysts (lead to R in formula (II)3It is normal-butyl, Y is Br),
It is passed through carbon dioxide and keeps pressure for 0.1MPa, under the conditions of being 25 DEG C in temperature, after stirring 5h, be placed in frozen water and cool down, delays
After the remaining carbon dioxide of On The Drug Release, catalyst is filtered to isolate, taking appropriate filtrate carries out gas chromatographic analysis, gained ring-type carbon
The yield of acid esters is 99%.
Embodiment 3
In to the stainless steel autoclave of 10mL, sequentially add 0.015mmol catalyst (M is Al in logical formula (I),
R1And R2All it is H), 6mmol epoxidations propane and 0.12mmol co-catalysts (lead to R in formula (II)3It is normal-butyl, Y is Br), lead to
Entering carbon dioxide makes its initial pressure for 1.0MPa, under the conditions of being 40 DEG C in temperature, after stirring 1h, is placed in frozen water and cools down, and delays
After the remaining carbon dioxide of On The Drug Release, catalyst is filtered to isolate, taking appropriate filtrate carries out gas chromatographic analysis, gained ring-type carbon
The yield of acid esters is 99%.
Embodiment 4
In to the stainless steel autoclave of 10mL, 7.5 × 10 are sequentially added-3(M is the catalyst of mmol in logical formula (I)
Al, R1And R2All it is H), 3mmol styrene oxides and 0.06mmol co-catalysts (lead to R in formula (II)3It is normal-butyl, Y is Br),
Being passed through carbon dioxide makes its initial pressure for 1.0MPa, under the conditions of being 40 DEG C in temperature, after stirring 6h, is placed in frozen water and cools down,
After slowly discharging remaining carbon dioxide, catalyst is filtered to isolate, taking appropriate filtrate carries out gas chromatographic analysis, gained ring-type
The yield of carbonic ester is 91%.
Embodiment 5
In to the stainless steel autoclave of 10mL, 7.5 × 10 are sequentially added-3(M is the catalyst of mmol in logical formula (I)
Al, R1And R2All it is H), 1, the 2- octylene oxides and 0.06mmol co-catalysts of 3mmo (lead to R in formula (II)3It is normal-butyl, Y is
Br), being passed through carbon dioxide makes its initial pressure for 1.0MPa, under the conditions of being 40 DEG C in temperature, after stirring 6h, is placed in cold in frozen water
But, after slowly discharging remaining carbon dioxide, catalyst is filtered to isolate, taking appropriate filtrate carries out gas chromatographic analysis, gained
The yield of cyclic carbonate is 91%.
Embodiment 6
In to the stainless steel autoclave of 10mL, 7.5 × 10 are sequentially added-3(M is the catalyst of mmol in logical formula (I)
Al, R1 and R2 are H), (R3 is positive fourth in logical formula (II) for the allyl glycidyl ether and 0.015mmol co-catalysts of 3mmol
Base, Y is Br), being passed through carbon dioxide makes its initial pressure for 1.0MPa, under the conditions of being 40 DEG C in temperature, after stirring 6h, is placed in ice
Cooled down in water, after slowly discharging remaining carbon dioxide, filter to isolate catalyst, taking appropriate filtrate carries out gas-chromatography point
Analysis, the yield of gained cyclic carbonate is 99%.
Embodiment 7
In to the stainless steel autoclave of 10mL, 7.5 × 10 are sequentially added-3(M is the catalyst of mmol in logical formula (I)
Al, R1And R2All it is H), the 7-oxa-bicyclo[4.1.0 and 0.12mmol co-catalysts of 3mmol (lead to R in formula (II)3It is normal-butyl, Y is
Br), being passed through carbon dioxide makes its initial pressure for 1.0MPa, under the conditions of being 40 DEG C in temperature, after stirring 24h, is placed in frozen water
Cooling, after slowly discharging remaining carbon dioxide, filters to isolate catalyst, and taking appropriate filtrate carries out gas chromatographic analysis, institute
The yield for obtaining cyclic carbonate is 82%.
Embodiment 8
In to the stainless steel autoclave of 10mL, 7.5 × 10 are sequentially added-3(M is the catalyst of mmol in logical formula (I)
Mn, R1And R2All it is H), the expoxy propane and 0.12mmol co-catalysts of 3mmol (lead to R in formula (II)3It is normal-butyl, Y is Br),
Being passed through carbon dioxide makes its initial pressure for 1.0MPa, under the conditions of being 40 DEG C in temperature, after stirring 15h, is placed in frozen water and cools down,
After slowly discharging remaining carbon dioxide, catalyst is filtered to isolate, taking appropriate filtrate carries out gas chromatographic analysis, gained ring-type
The yield of carbonic ester is 90%.
Embodiment 9
In to the stainless steel autoclave of 10mL, 7.5 × 10 are sequentially added-3(M is the catalyst of mmol in logical formula (I)
Co, R1And R2All it is H), the expoxy propane and 0.12mmol co-catalysts of 3mmol (lead to R in formula (II)3It is normal-butyl, Y is Br),
Being passed through carbon dioxide makes its initial pressure for 1.0MPa, under the conditions of being 40 DEG C in temperature, after stirring 10h, is placed in frozen water and cools down,
After slowly discharging remaining carbon dioxide, catalyst is filtered to isolate, taking appropriate filtrate carries out gas chromatographic analysis, gained ring-type
The yield of carbonic ester is 95%.
Embodiment 10
In to the stainless steel autoclave of 10mL, 7.5 × 10 are sequentially added-3(M is the catalyst of mmol in logical formula (I)
Zn, R1And R2All it is H), 3mmol expoxy propane and 0.12mmol co-catalysts (lead to R in formula (II)3It is normal-butyl, Y is Br), lead to
Entering carbon dioxide makes its initial pressure for 1.0MPa, under the conditions of being 40 DEG C in temperature, after stirring 2h, is placed in frozen water and cools down, and delays
After the remaining carbon dioxide of On The Drug Release, catalyst is filtered to isolate, taking appropriate filtrate carries out gas chromatographic analysis, gained ring-type carbon
The yield of acid esters is 99%.
Embodiment 11
In to the stainless steel autoclave of 10mL, 7.5 × 10 are sequentially added-3(M is the catalyst of mmol in logical formula (I)
Cr, R1And R2All it is H), the expoxy propane and 0.12mmol co-catalysts of 3mmol (lead to R in formula (II)3It is normal-butyl, Y is Br),
Being passed through carbon dioxide makes its initial pressure for 1.0MPa, under the conditions of being 40 DEG C in temperature, after stirring 3h, is placed in frozen water and cools down,
After slowly discharging remaining carbon dioxide, catalyst is filtered to isolate, taking appropriate filtrate carries out gas chromatographic analysis, gained ring-type
The yield of carbonic ester is 99%.
Embodiment 12
In to the stainless steel autoclave of 10mL, sequentially add 0.015mmol catalyst (M is Al in logical formula (I),
R1It is Br, R2It is H), the expoxy propane and 0.12mmol co-catalysts of 6mmol (lead to R in formula (II)3It is normal-butyl, Y is Br), lead to
Entering carbon dioxide makes its initial pressure for 1.0MPa, under the conditions of being 40 DEG C in temperature, after stirring 2h, is placed in frozen water and cools down, and delays
After the remaining carbon dioxide of On The Drug Release, catalyst is filtered to isolate, taking appropriate filtrate carries out gas chromatographic analysis, gained ring-type carbon
The yield of acid esters is 99%.
Embodiment 13
In to the stainless steel autoclave of 10mL, sequentially add 0.015mmol catalyst (M is Al in logical formula (I),
R1It is H, R2It is OCH3), the expoxy propane and 0.12mmol co-catalysts of 12mmol (lead to R in formula (II)3It is normal-butyl, Y is
Br), being passed through carbon dioxide makes its initial pressure for 1.0MPa, under the conditions of being 40 DEG C in temperature, after stirring 3h, is placed in cold in frozen water
But, after slowly discharging remaining carbon dioxide, catalyst is filtered to isolate, taking appropriate filtrate carries out gas chromatographic analysis, gained
The yield of cyclic carbonate is 98%.
Embodiment 14
In to the stainless steel autoclave of 10mL, 7.5 × 10 are sequentially added-3(M is the catalyst of mmol in logical formula (I)
Al, R1And R2All it is H), 6mmol expoxy propane and 0.12mmol co-catalysts (lead to R in formula (II)3It is Ph, Y is Cl), it is passed through two
Carbonoxide makes its initial pressure for 1.0MPa, under the conditions of being 40 DEG C in temperature, after stirring 1h, is placed in frozen water and cools down, and slowly releases
After putting remaining carbon dioxide, catalyst is filtered to isolate, taking appropriate filtrate carries out gas chromatographic analysis, gained cyclic carbonate
Yield be 99%.
Embodiment 15
In to the stainless steel autoclave of 10mL, 7.5 × 10 are sequentially added-3(M is the catalyst of mmol in logical formula (I)
Al, R1And R2All it is H), the expoxy propane and 0.12mmol co-catalysts of 3mmol (lead to R in formula (II)3It is normal-butyl, Y is Br),
It is passed through industrial waste gas (15%CO2) make its initial pressure for 3.0MPa, under the conditions of being 100 DEG C in temperature, after stirring 6h, put rapidly
Room temperature is cooled in cold water, continuation is cooled down in being subsequently placed at frozen water, after slowly discharging remaining gas, filters to isolate catalysis
Agent, taking appropriate filtrate carries out gas chromatographic analysis, and the yield of gained cyclic carbonate is 90%.
Claims (6)
1. a kind of method of heterogeneous catalysis synthesizing annular carbonate, it is characterised in that with carbon dioxide and epoxides as raw material,
With super crosslink metallic porphyrin porous material as catalyst, with quaternary salt as co-catalyst, gas concentration lwevel be 15~
100%, pressure is 0.1MPa~3.0MPa, and temperature obtains cyclic carbonate under conditions of 25~100 DEG C, to react 1~6h.
2. method according to claim 1, it is characterised in that the super crosslink metallic porphyrin porous material uses Fu Ke alkane
Glycosylation reaction, with metalloporphyrin as monomer, with formal as crosslinking agent, with anhydrous FeCl3Catalyst preparation is obtained, its
Structure such as logical formula (I)：
In formula, metallic atom M is Al, Zn, Co, Cu, Fe, Mn and Cr one of which, and X is halogen, R1And R2Be respectively selected from H,
Me, Br and OCH3。
3. method according to claim 1, it is characterised in that described super crosslink metallic porphyrin porous material catalyst
Structure is selected from logical formula (I)；
The co-catalyst selected from the one kind in logical formula (II)：
R in formula3Selected from Me, Et,nBu and Ph, Y are halogen.
4. method according to claim 1, it is characterised in that described epoxides is selected from logical formula (III)：
5. method according to claim 1, it is characterised in that described catalyst amount for epoxides 0.05~
2.50mol‰。
6. method according to claim 1, it is characterised in that described co-catalyst consumption for epoxides 0.5~
2.0mol%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107721970A (en) * | 2017-12-06 | 2018-02-23 | 河南工程学院 | A kind of method that nickel-base catalyst prepares cyclic carbonate |
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| CN107954973A (en) * | 2017-12-06 | 2018-04-24 | 河南工程学院 | A kind of method that zinc based catalyst prepares cyclic carbonate |
| CN107973772A (en) * | 2017-12-06 | 2018-05-01 | 河南工程学院 | A kind of method that ferrum-based catalyst chemical recycling of carbon dioxide prepares 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 |
| CN107987050A (en) * | 2017-12-06 | 2018-05-04 | 河南工程学院 | A kind of method that magnesium-base catalyst prepares cyclic carbonate |
| CN108047457A (en) * | 2017-12-29 | 2018-05-18 | 南开大学 | It is a kind of to be catalyzed preparation method and applications of the carbon dioxide for the metal organic frame of epoxy carbonate |
| CN112521362A (en) * | 2020-12-18 | 2021-03-19 | 浙江理工大学 | Method for synthesizing cyclic carbonate based on functionalized metalloporphyrin/quaternary phosphonium salt dual-catalytic system |
| CN113307789A (en) * | 2021-04-12 | 2021-08-27 | 中国科学院过程工程研究所 | Method for synthesizing cyclic carbonate by catalyzing urea and dihydric alcohol through metalloporphyrin ion framework |
| CN114669332A (en) * | 2022-04-24 | 2022-06-28 | 齐齐哈尔大学 | Preparation method of ionic type ultrahigh cross-linked porous organic polymer supported cobalt catalyst |
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Cited By (24)
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| CN107721971A (en) * | 2017-12-06 | 2018-02-23 | 河南工程学院 | A kind of method that magnesium-base catalyst chemical recycling of carbon dioxide prepares cyclic carbonate |
| CN107721970A (en) * | 2017-12-06 | 2018-02-23 | 河南工程学院 | A kind of method that nickel-base catalyst prepares cyclic carbonate |
| CN107805239A (en) * | 2017-12-06 | 2018-03-16 | 河南工程学院 | A kind of method that chromium-based catalysts chemical recycling of carbon dioxide prepares cyclic carbonate |
| CN107827860A (en) * | 2017-12-06 | 2018-03-23 | 河南工程学院 | A kind of method that zinc based catalyst chemical recycling of carbon dioxide prepares cyclic carbonate |
| CN107827859A (en) * | 2017-12-06 | 2018-03-23 | 河南工程学院 | A kind of method that aluminium-based catalyst chemical recycling of carbon dioxide prepares cyclic carbonate |
| CN107827858A (en) * | 2017-12-06 | 2018-03-23 | 河南工程学院 | A kind of method that aluminium-based catalyst prepares cyclic carbonate |
| CN107827857A (en) * | 2017-12-06 | 2018-03-23 | 河南工程学院 | A kind of method that chromium-based catalysts prepare cyclic carbonate |
| CN107827863A (en) * | 2017-12-06 | 2018-03-23 | 河南工程学院 | A kind of method that copper-based catalysts chemical recycling of carbon dioxide prepares cyclic carbonate |
| CN107827856A (en) * | 2017-12-06 | 2018-03-23 | 河南工程学院 | A kind of method that catalytic component based on vanadium prepares cyclic carbonate |
| CN107827861A (en) * | 2017-12-06 | 2018-03-23 | 河南工程学院 | A kind of method that ferrum-based catalyst prepares cyclic carbonate |
| CN107827862A (en) * | 2017-12-06 | 2018-03-23 | 河南工程学院 | A kind of method that nickel-base catalyst chemical recycling of carbon dioxide prepares cyclic carbonate |
| CN107903239A (en) * | 2017-12-06 | 2018-04-13 | 河南工程学院 | A kind of method that catalytic component based on vanadium chemical recycling of carbon dioxide prepares cyclic carbonate |
| CN107903238A (en) * | 2017-12-06 | 2018-04-13 | 河南工程学院 | A kind of method that copper-based catalysts prepare cyclic carbonate |
| CN107954972A (en) * | 2017-12-06 | 2018-04-24 | 河南工程学院 | A kind of method that manganese-based catalyst prepares cyclic carbonate |
| CN107954974A (en) * | 2017-12-06 | 2018-04-24 | 河南工程学院 | A kind of method that manganese-based catalyst chemical recycling of carbon dioxide prepares cyclic carbonate |
| CN107954973A (en) * | 2017-12-06 | 2018-04-24 | 河南工程学院 | A kind of method that zinc based catalyst prepares cyclic carbonate |
| CN107973772A (en) * | 2017-12-06 | 2018-05-01 | 河南工程学院 | A kind of method that ferrum-based catalyst chemical recycling of carbon dioxide prepares 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 |
| CN107987050A (en) * | 2017-12-06 | 2018-05-04 | 河南工程学院 | A kind of method that magnesium-base catalyst prepares cyclic carbonate |
| CN108047457A (en) * | 2017-12-29 | 2018-05-18 | 南开大学 | It is a kind of to be catalyzed preparation method and applications of the carbon dioxide for the metal organic frame of epoxy carbonate |
| CN108047457B (en) * | 2017-12-29 | 2020-10-30 | 南开大学 | Preparation method and application of metal organic framework for catalyzing carbon dioxide to be epoxy carbonate |
| CN112521362A (en) * | 2020-12-18 | 2021-03-19 | 浙江理工大学 | Method for synthesizing cyclic carbonate based on functionalized metalloporphyrin/quaternary phosphonium salt dual-catalytic system |
| CN113307789A (en) * | 2021-04-12 | 2021-08-27 | 中国科学院过程工程研究所 | Method for synthesizing cyclic carbonate by catalyzing urea and dihydric alcohol through metalloporphyrin ion framework |
| CN114669332A (en) * | 2022-04-24 | 2022-06-28 | 齐齐哈尔大学 | Preparation method of ionic type ultrahigh cross-linked porous organic polymer supported cobalt catalyst |
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