KR20170048739A - Method of preparation of five-membered cyclic carbonates by using the copper-aspartate-bipyridine metal organic frameworks as catalysts - Google Patents
Method of preparation of five-membered cyclic carbonates by using the copper-aspartate-bipyridine metal organic frameworks as catalysts Download PDFInfo
- Publication number
- KR20170048739A KR20170048739A KR1020150149198A KR20150149198A KR20170048739A KR 20170048739 A KR20170048739 A KR 20170048739A KR 1020150149198 A KR1020150149198 A KR 1020150149198A KR 20150149198 A KR20150149198 A KR 20150149198A KR 20170048739 A KR20170048739 A KR 20170048739A
- Authority
- KR
- South Korea
- Prior art keywords
- catalyst
- metal organic
- compound
- cuaspbpy
- carbon dioxide
- Prior art date
Links
Classifications
-
- 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
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
-
- 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
- C07D317/38—Ethylene carbonate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
Description
The present invention relates to a process for preparing copper-aspartate-bipyridine metal organic frameworks, which are copper-containing porous coordination compounds, and using these as catalysts to produce carbon dioxide and epoxy compounds under low temperature and pressure conditions, Can be easily synthesized. The present invention relates to a process for producing a 5-membered cyclic carbonate compound.
In general, the technique of using carbon dioxide as a raw material for organic synthesis has been studied for a long time. Especially, a technique of synthesizing a 5-membered ring carbonate compound by reacting an epoxy compound with carbon dioxide attracts much attention in terms of manufacturing monomers for functional polymer materials.
Conventionally, diol and phosgene are used in order to obtain a 5-membered ring carbonate compound in a high yield, but it is difficult to handle due to the toxicity of phosgene, which causes a lot of difficulties in the process. Therefore, a method for synthesizing a 5-membered ring carbonate compound at a high yield under a safe condition is desperately required.
On the other hand, Patent Literature 1 discloses a technique of synthesizing a 5-membered ring carbonate compound at a high yield by using amines such as alkylamine, dialkylamine, triethylamine, etc. as a catalyst to convert carbon dioxide and ethylene oxide or propylene oxide into ethylene carbonate Or propylene carbonate is disclosed. However, the conditions of the synthesis reaction are higher than the reaction pressure of 34 atm and the reaction temperature of 100 ~ 400 ° C.
In Non-Patent Document 1, Soga et al. Have reacted propylene oxide with carbon dioxide for 3 days at a temperature of 120 to 180 ° C under a pressure of 40 atm using ZnTe 2 , AlCl 3 , Ti (OBu) 4 , It is known that polypropylene carbonate of about 1800 to 3600 is synthesized.
In Non-Patent Document 2, Kihara et al. Have reported that polyglycidyl methacrylate reacts with gaseous carbon dioxide at 120 to 160 ° C to form poly [(2-oxo-1,3-dioxolan-4-yl) (Hereinafter referred to as " poly DOMA "). In addition, in Non-Patent Document 3, polyglycidyl methacrylate and carbon dioxide at normal pressure are mixed with alkali metal halides NaI and triphenylphosphine It is also known that poly DOMA is obtained by reacting at 100 ° C using a pin-blended catalyst as a catalyst.
In Non-Patent Document 4, Nishikubo et al. Used polystyrene prepared by co-copolymerizing styrene, divinylbenzene, and vinylbenzene chloride simultaneously with quaternary ammonium chloride or quaternary chloride salt as a catalyst, and using toluene as a solvent As a result of the reaction of carbon dioxide and phenylglycidyl ether at normal pressure and 80 ° C for 24 hours, it was known that the yield of phenoxymethylethylene carbonate was 30 to 95%. However, in this case, too, the structure of the catalyst was too dense, It is difficult for the reactant to approach the active site of the catalyst, so that the reaction yield is low and the reaction takes a long time.
On the other hand, in Non-Patent Document 5, the hydrogen bonding of the hydroxyl group of the catalyst is caused by the synergistic effect with the halogen anion and the ring opening of the epoxy compound in the addition reaction of carbon dioxide and the epoxy compound ring opening of the cells.
The inventor of the present invention has developed a process for preparing a phase transfer catalyst and a 5-membered cyclic carbonate compound using the catalyst prepared by the process, and has already patented a technology as disclosed in Patent Document 2 In the case of the above patent, there is a disadvantage in that it is difficult to recover the catalyst during the synthesis of the 5-membered ring carbonate compound, and thus reuse is not easy.
The present inventor has also proposed a process for producing a 5-membered cyclic carbonate compound using an ionic liquid catalyst, which is a hybrid MCM-41 having an ionic liquid catalyst supported on a mobile composition of Matter No. 41 A method for producing a 5-membered ring carbonate compound using a catalyst and a method for producing a 5-membered ring carbonate compound using an ionic liquid catalyst supported on porous amorphous silica as in Patent Document 4 have been developed and patented. However, When MCM-41 or a porous amorphous silica carrier is used, the manufacturing process of the carrier is complicated and the production cost is high.
Since the conventional addition reaction of the epoxy compound with carbon dioxide as described above is mainly carried out using an expensive organometallic catalyst or a quaternary ammonium salt catalyst in a liquid state as a phase transfer catalyst, it is difficult to separate and recover the catalyst after the reaction, There is a problem in that it is costly, and even in the case of the catalyst prepared according to the method of Nishikubo, there is a problem that the diffusion resistance to the reactant is high and the stability is low and the yield is lowered.
The inventors of the present invention have found that the combination of metal and organic material can be close to infinite depending on the kind of metal, whether or not the metal is clusters, the kind of organic material, and the degree of coordination, and the metal organic skeleton (HIP) bipy metal organic skeleton catalyst in metal organic frameworks (hereinafter referred to as "MOF"), and has already filed a patent application for Patent Document 5 in order to synthesize a 5-membered ring carbonate compound.
In addition, the present inventor has already developed a technology for synthesizing a 5-membered ring carbonate compound using a zinc-glutamate metal organic skeletal catalyst, and has already filed a patent application in Patent Document 6.
For reference, MOF, which is a porous inorganic coordination compound applied to the present invention, was first named Metal-Organic Framework in 1995 and granted scholarly value to Omar M. Yaghi of UCLA and Michael O. Michael of Arizona State University O'Keeffe).
MOF can be used for various purposes such as: first, the pore size can be varied from several angstroms to 3 nm; second, since the MOF skeleton does not collapse even when a solvent or a template is removed like zeolite, Third, although organic matter is contained, the thermal stability reaches 300 ~ 400 ℃, which is a possibility of high temperature catalyst.
The inventors of the present invention have found that a zinc-containing metal organic skeleton chain [Zn (L-Glutamate) (H 2 O)], a copper-containing porous coordination compound having a structure and performance different from the 2H 2 O metal organic skeleton, Cu (L-Aspartate) (4,4' -bipyridine) 0.5] H 2 O ( hereinafter 'CuAspBpy'quot;) for producing a microwave synthesis of metal-organic framework catalyst body, and by using this catalyst in the synthesis of 5-membered ring carbonate compound The present invention has been completed.
In order to overcome the above-described problems, the present invention provides a CuAspBpy metal organic skeleton catalyst, which is a copper-containing porous coordination compound, and which is capable of easily producing a 5-membered ring carbonate compound at a high yield under mild reaction conditions. It is another object of the present invention to provide a method for producing a 5-membered ring carbonate compound using a sieve as a catalyst.
The present invention is characterized in that copper hydrate is selected as a metal source forming a skeleton in the CuAspBpy metal organic skeleton and aspartic acid is used as an organic substance and 4,4 -Bipyridine (4,4'-bipyridine) 4 by a microwave synthesis method. The present invention also provides a method for producing a 5-membered cyclic carbonate compound.
In order to solve the above problems, the present invention provides a method for producing a 5-membered cyclic carbonate compound, which comprises carbonylating carbon dioxide and an epoxy compound using a CuAspBpy metal organic skeletal catalyst.
According to the present invention, a CuAspBpy metal organic skeleton having a regular and stable copper-containing porous coordination structure is prepared by a "microwave synthesis method" and a 5-membered ring carbonate compound is synthesized using the catalyst, It has an excellent reactivity and stability, and is capable of synthesizing a 5-membered ring carbonate compound with a high yield under relatively mild conditions.
In order to achieve the above-described effect, a 5-membered ring carbonate compound (hereinafter referred to as a " CuAspBpy metal organic framework catalyst "), which is a copper-containing porous coordination compound prepared by a microwave synthesis method according to the present invention, The preparation method of the catalyst is as follows.
In the present invention, a 5-membered ring carbonate compound is produced by addition reaction of carbon dioxide and an epoxy compound using a CuAspBpy metal organic framework catalyst, which is a coordination compound.
Particularly, the present invention is characterized in that only a carbon dioxide and an epoxy compound are used to carry out a reaction for producing a five-membered ring carbonate compound, and no additional solvent is used.
In the present invention, carbon dioxide and an epoxy compound are subjected to an addition reaction, and the CuAspBpy metal organic skeleton, which is a catalyst to be added at this time, is added at a molar ratio of epoxy compound to metal organic skeleton of 100 to 0.5 to 5. If the amount of the added catalyst is less than 0.5, the carbon dioxide and the epoxy compound do not sufficiently react with each other, and the unreacted epoxy compound may remain in the reactant. When the amount of the catalyst exceeds 5, The mixing of the catalyst is poor and the catalytic activity may decrease.
Tetrabutylammonium bromide (hereinafter referred to as TBAB) is added as a cocatalyst in a molar ratio of CuAspBpy metal organic skeleton to TBAB at a ratio of 1: 1 to 3: 1. When the amount of the TBAB, which is a co-catalyst to be added, is less than 1, the carbon dioxide and the epoxy compound do not sufficiently react and the unreacted epoxy compound may remain in the reactant. When the amount of TBAB as the co- The mixture of the reactant and the catalyst is poor and the catalytic activity may decrease.
The reaction conditions for the synthesis of the epoxy compound are preferably a reaction at a reaction temperature of 100 to 150 ° C and a pressure of carbon dioxide of 0.8 to 1.6 MPa for 4 to 20 hours. If the reaction conditions are less than the above- , There is a possibility that the yield of the product is decreased. If it exceeds the range defined above, the product may be decomposed or the yield may decrease.
In the present invention, the amount of carbon dioxide used in the synthesis of the 5-membered ring carbonate compound is in the same molar ratio as the molar ratio of the epoxy compound. In the present invention, the number of moles of carbon dioxide is not particularly limited since the carbon dioxide charged in the reactor is pressurized and filled in the reactor. The number of moles of carbon dioxide charged in the reactor is determined by considering the number of moles of carbon dioxide As shown in FIG.
The epoxy compound is an epoxide derivative selected from the group consisting of propylene oxide, allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, glycidyl methacrylate and vinylcyclohexene oxide desirable.
Therefore, it is characterized in that a high yield can be obtained when a 5-membered cyclic carbonate compound is synthesized using the coordination compound CuAspBpy metal organic skeletal catalyst prepared according to the present invention.
On the other hand, as a catalyst used in the present invention, a CuAspBpy metal organic skeleton as a coordination compound is a compound to be added for the catalyst preparation reaction. As a result, copper hydrate of metal source, aspartic acid, And the molar ratio of 4,4'-bipyridine was 1: 1.5 ~ 4.0: 0.5 ~ 2.0, and the mixture was mixed with 20 ~ 50 mL of distilled water. The product prepared by the microwave synthesis method was filtered by using a microwave having a frequency of 2.45 GHz for 10 to 20 minutes by electric power, sufficiently washed with distilled water and methanol, and then subjected to a vacuum pressure of 10 to 20 mmHg at a temperature of 120 to 140 ° C., Followed by vacuum drying for 14 hours.
If the mixing amount of aspartic acid and 4,4'-bipyridine and the amount of distilled water used for the copper nitrate copper hydrate is out of the range defined above, the yield of CuAspBpy metal organic skeleton decreases There is a concern.
In the case of CuAspBpy produced by the microwave synthesis method, the yield of the CuAspBpy metal organic skeleton may be reduced when the reaction conditions are less than the above-described conditions. When the reaction conditions are limited, May be reduced.
After the reaction, the synthesized product is filtered by a conventional method such as filter filtration, washed thoroughly with distilled water and methanol, and vacuum-dried at 120 to 140 ° C under a pressure of 10 to 20 mmHg.
At this time, when the vacuum drying condition is less than the conditions defined above, there is a fear that the produced metal organic skeleton may not be sufficiently dried. If the conditions are limited, the product may be lost by rapid drying .
The catalyst prepared by the above method is a coordination compound having a high degree of structure and high crystallinity, and the CuAspBpy metal organic skeleton has acidity and basicity at the same time, and is characterized by excellent reactivity and stability.
Hereinafter, the present invention will be described in detail with reference to examples. However, the scope of the present invention is not limited to these examples.
(Example 1)
Using 0.2 mmol of the coordination compound CuAspBpy metal organic framework catalyst and 0.2 mmol of cocatalyst TBAB, the reaction was carried out at a relatively low temperature of 100 ° C and a low pressure of 1.6 MPa, a pressure of 1.6 MPa, without using a solvent. 40 mmol of propylene oxide (PO) was added for 20 hours to synthesize propylene carbonate (PC) as a 5-membered ring carbonate compound.
The coordination compound CuAspBpy metal organic skeletal catalyst prepared in the present Example 1 was first prepared by mixing 2 mmol of copper nitrate and 2 mmol of aspartic acid as an organic source were added to 25 mL of distilled water together with 1.5 mmol of NaHCO 3 and 2 mmol of 4,4'-bipyridine dissolved in 25 mL of methanol '-Bipyridine. The solution was placed in a 100 mL microwave reactor and synthesized by irradiating microwaves with a frequency of 2.45 GHz at a power of 100 W for 20 minutes. The solution was then slowly cooled to room temperature, filtered, washed thoroughly with distilled water and methanol, , And dried in a vacuum of 10 mmHg for 14 hours to finally prepare a light blue solid, CuAspBpy-1.
(Example 2)
Using 0.2 mmol of the coordination compound CuAspBpy-2 metal organic skeleton catalyst and 0.6 mmol of co-catalyst TBAB, the reaction was carried out at a relatively low temperature of 150 ° C and a low pressure of 0.8 MPa, a carbon dioxide pressure of 0.8 MPa, 4 mmol of propylene oxide (PO) as a compound was added for 4 hours to synthesize propylene carbonate (PC) as a 5-membered ring carbonate compound.
The coordination compound CuAspBpy-2 metal organic framework catalyst prepared in Example 2 was prepared by preparing a catalyst by the same method as in the preparation of CuAspBpy-1 of Example 1, raising the microwave power to 200 W, heating the mixture at a frequency of 2.45 GHz And then slowly cooled to room temperature. After filtration, it was thoroughly washed with distilled water and methanol, and then dried at 140 ° C under a vacuum of 20 mmHg for 12 hours. Finally, a light blue solid CuAspBpy- 2.
(Comparative Example 1)
The reaction for synthesizing propylene carbonate (PC) as a 5-membered ring carbonate compound was carried out by the same method as in Example 1 above.
However, the CuAspBpy-3 metal organic framework catalyst of the coordination compound was prepared by the same method as the preparation of CuAspBpy-1 of Example 1, and the microwave power was reduced to 50 W to prepare CuAspBpy-3 by microwave synthesis.
[Table 1] shows the yield of PC according to the change of the CuAspBpy metal organic framework catalyst.
As can be seen from the above Table 1, according to the same conditions as in the case of Example 1 and Comparative Example 1, even in the production of the five-membered ring carbonate compound, the formation of the coordination compound CuAspBpy metal organic skeleton catalyst It was confirmed that the yield of PC as the toric carbonate compound was different.
That is, CuAspBpy catalyst prepared by selecting copper nitrate as a metal source and aspartic acid as an organic substance and 4,4'-bipyridine as a secondary structure forming organic material in the preparation of the coordination compound CuAspBpy metal organic framework catalyst Showed that the PC yield was slightly lower at 72% when the power of the microwave synthesis reactor was 50 W, but was very high at 94% at 100 W and 95% at 200 W.
(Examples 3 to 6)
The reaction was carried out under the same conditions as in Example 1, but the yield of PC was measured by changing only the reaction temperature, and the results are shown in Table 2 below.
As can be seen from the above Table 2, the PC yield was 93% or more at a reaction temperature of 120 to 150 ° C and the maximum value at 140 ° C. This is because if the temperature is too high, a side reaction in which PC is converted to an oligomer proceeds.
(Examples 7 to 9 and Comparative Example 2)
The reaction was carried out under the same conditions as in Example 1, but the yield of PC was measured by changing only the reaction time, and the results are shown in Table 3 below. [Table 3] shows the yield of PC according to the change of reaction time.
As shown in Table 3, the reaction time steadily increases from 4 hours to 12 hours. However, the equilibrium reaction was reached when the yield was almost constant over 12 hours.
(Examples 10 to 13)
The reaction was carried out under the same conditions as in Example 1 except that only the carbon dioxide pressure was changed to perform the reaction, and the yield of PC was measured. The results are shown in Table 4 below. [Table 4] shows the yield of PC according to the carbon dioxide pressure.
As can be seen from Table 4, the PC yield increased as the carbon dioxide pressure increased to 1.4 MPa. However, it decreased slightly at 1.6 MPa. It is believed that this is due to the dilution effect that the contact between the PO and the catalyst is not smooth at high pressure.
(Examples 14-17)
The reaction was carried out under the same conditions as in Example 1 except that the type of the epoxide used was changed to prepare a 5-membered ring carbonate compound and its yield was shown in Table 5 below.
As shown in Table 5, it can be seen that the catalyst of the present invention is effective in the addition reaction of various types of epoxide with carbon dioxide.
(Comparative Examples 3 and 4)
PC was synthesized using a catalyst obtained by carrying out the reaction under the same conditions as in Example 1 except that a tetrabutylammonium bromide ionic liquid was supported on silica or alumina instead of CuAspBpy metal organic skeletal catalyst, Are shown in Table 6 below.
As can be seen from the above Table 6, when a catalyst obtained by supporting a tetrabutylammonium bromide ionic liquid on a silica or alumina carrier is used, the yield of PC is much higher than that of the CuAspBpy metal organic skeleton catalyst of the present invention fell.
Therefore, as shown in the above examples, the coordination compound CuAspBpy metal organic framework catalyst prepared according to the present invention has excellent reactivity and stability, and it has been confirmed that carbonate can be synthesized with high yield under relatively mild reaction conditions.
The present invention described above is not necessarily limited to the above configuration, and various substitutions, modifications, and changes may be made without departing from the technical spirit of the present invention.
Claims (6)
Wherein the carbonylation reaction is carried out at a temperature of 100 to 150 ° C and a carbon dioxide pressure of 0.8 to 1.6 MPa for 4 to 20 hours.
Wherein the amount of the CuAspBpy metal organic framework catalyst is in the range of 100 to 0.5 molar ratio of the epoxy compound to the metal organic skeleton catalyst.
Wherein the epoxy compound is an epoxide derivative selected from the group consisting of allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, propylene oxide, and vinylcyclohexene oxide. Gt;
The CuAspBpy metal organic framework catalyst may be prepared by selecting copper nitrate hydrate as a metal source forming a skeleton, using aspartic acid as an organic material, and using 4,4'-bipyridine as a secondary structure- (4,4'-bipyridine) is used as a starting material to prepare a 5-membered cyclic carbonate compound.
Wherein the microwave synthesis is performed by irradiating a microwave for 10 to 20 minutes at a power of 100 to 200 W in a microwave reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150149198A KR20170048739A (en) | 2015-10-27 | 2015-10-27 | Method of preparation of five-membered cyclic carbonates by using the copper-aspartate-bipyridine metal organic frameworks as catalysts |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150149198A KR20170048739A (en) | 2015-10-27 | 2015-10-27 | Method of preparation of five-membered cyclic carbonates by using the copper-aspartate-bipyridine metal organic frameworks as catalysts |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20170048739A true KR20170048739A (en) | 2017-05-10 |
Family
ID=58743678
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020150149198A KR20170048739A (en) | 2015-10-27 | 2015-10-27 | Method of preparation of five-membered cyclic carbonates by using the copper-aspartate-bipyridine metal organic frameworks as catalysts |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR20170048739A (en) |
-
2015
- 2015-10-27 KR KR1020150149198A patent/KR20170048739A/en not_active Application Discontinuation
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jose et al. | Functionalized zeolitic imidazolate framework F-ZIF-90 as efficient catalyst for the cycloaddition of carbon dioxide to allyl glycidyl ether | |
| CN112341394B (en) | Method for preparing cyclic carbonate ester by catalysis of hydrogen bond donor functionalized polymeric ionic liquid | |
| KR100999360B1 (en) | Preparation of immobilized ionic liquid catalyst on porous amorphous silica and its use for the synthesis of five-membered cyclic carbonates | |
| CN111138591B (en) | N-heterocyclic carbene/CO2Adduct functionalized organic porous polymer, preparation method and application | |
| KR102235012B1 (en) | Heterogeneous Organic Catalyst Based on Imidazoline and Method of Preparing Cyclic Carbonate Using the Same | |
| KR101536351B1 (en) | Method of preparation of five-membered cyclic carbonates by using the zinc containing metal organic frameworks as catalysts | |
| Ravi et al. | Organic sulphonate salts tethered to mesoporous silicas as catalysts for CO 2 fixation into cyclic carbonates | |
| KR100911494B1 (en) | Preparation of immobilized ionic liquid catalyst on mesoporous hybrid MCM-41 and its use for the synthesis of five member cyclic carbonates | |
| CN111185212A (en) | Bifunctional catalyst for photocatalytic synthesis of dihydroxyacetone and hydrogen, and preparation method and application thereof | |
| JP2017141432A (en) | Composition comprising phosphazenium compound, lewis acid and active hydrogen-containing compound | |
| KR101825671B1 (en) | Method of preparation of five-membered cyclic carbonates by using the copper-aspartate-bisimidazole metal organic frameworks as catalysts | |
| CN114276322A (en) | Method for preparing cyclic carbonate by photo-initiated polymerization of ionic liquid material | |
| KR101368349B1 (en) | Method of preparation of glycerol carbonate by using the metal organic frameworks as catalysts | |
| KR101635756B1 (en) | Method of preparation of five-membered cyclic carbonates by using the zinc-glutamate metal organic frameworks as catalysts | |
| KR101855297B1 (en) | Novel zinc metal organic frameworks compound and method of preparation of five-membered cyclic carbonates by using the same as catalyst | |
| Munoz-Hernandez et al. | Six-coordinate aluminium cations: characterization, catalysis, and theory | |
| KR101545257B1 (en) | Method of preparation of glycerol carbonate by using the zirconium containing metal organic frameworks as catalysts | |
| CN111185239B (en) | CO (carbon monoxide)2Preparation method and application of epoxidation fixed catalyst | |
| KR101430259B1 (en) | Method for preparation of five-membered cyclic carbonate by using immobilized ionic liquid on a biopolymer cellulose as catalyst | |
| KR20170048739A (en) | Method of preparation of five-membered cyclic carbonates by using the copper-aspartate-bipyridine metal organic frameworks as catalysts | |
| KR102627604B1 (en) | Novel zinc metal organic frameworks compound and method of preparation of five-membered cyclic carbonates by using the same as catalyst | |
| CN114433228A (en) | Method for synthesizing cyclic carbonate ester by catalyzing core-shell type polymeric ionic liquid | |
| KR101494833B1 (en) | Manufacturing method of polyalkylenecarbonate | |
| KR20160013721A (en) | Method for preparation of five-membered cyclic carbonate from carbon dioxide and epoxide by using alkanolamine as catalyst | |
| KR102485203B1 (en) | Ionic metal-organic frameworks catalysts and fabrication method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| E902 | Notification of reason for refusal | ||
| E601 | Decision to refuse application |