CN113582962A - Preparation method of cyclic carbonate - Google Patents
Preparation method of cyclic carbonate Download PDFInfo
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- CN113582962A CN113582962A CN202111033378.8A CN202111033378A CN113582962A CN 113582962 A CN113582962 A CN 113582962A CN 202111033378 A CN202111033378 A CN 202111033378A CN 113582962 A CN113582962 A CN 113582962A
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- 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
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- 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
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
The invention belongs to the technical field of materials, and particularly relates to a preparation method of cyclic carbonate, which takes a double-center porous polymer as a catalyst to catalyze CO2And converting into cyclic carbonate, wherein the double-center porous polymer is a double-center heterogeneous porous catalyst with metalloporphyrin and quaternary phosphonium sites. The invention solves the problem of complex recovery of the existing catalyst for synthesizing cyclic carbonate, and realizes the combination and the cooperation of two active centers on the molecular level by using a double-center porous polymer containing metalloporphyrin and quaternary phosphonium sites as the catalyst, thereby efficiently converting carbon dioxide into cyclic carbonate.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a preparation method of cyclic carbonate.
Background
With the large consumption of fossil energy, CO2Is considered to be a major factor in global warming and climate change. Despite CO2The method has adverse effect on the environment, but is also a rich, renewable, cheap and nontoxic C1 resource, and can be converted into various high-added-value industrial chemicals. Due to CO2Low reactivity and kinetic inertness, and there are still many difficulties and challenges to convert them into industrial chemicals. Therefore, a great deal of scientists are devoted to the development of catalytic systems with a significantly reduced activation barrier.
CO2The C atom in (B) is present in the highest oxidation state, so that CO is present2Has very high thermodynamic stability and kinetic inertia, and leads to harsh reaction conditions, so an efficient catalytic system is needed to enable the epoxy resin to react with an epoxy substrate efficiently under relatively mild conditions. Many homogeneous and heterogeneous catalytic systems have been developed to promote the reaction of epoxy substrates with CO2The cycloaddition reaction of (a) can be carried out under mild conditions. The invention patent 202011505400.X in China discloses a method for synthesizing cyclic carbonate based on a functionalized metalloporphyrin/quaternary phosphonium salt dual-catalytic system, wherein functionalized metalloporphyrin is used as a main catalyst, quaternary phosphonium salt is used as a cocatalyst, and epoxide and carbon dioxide are used as reaction substrates to carry out cycloaddition reaction to obtain the cyclic carbonate. In the process, the functionalized metalloporphyrin is used as a main catalyst, the quaternary phosphonium salt is used as a cocatalyst to form the synergistic catalysis, however, the catalytic system is formed by combining two catalysts, the product purification is difficult after the reaction is finished, and the catalyst residue is serious.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of cyclic carbonate, which solves the problem of complex recovery of the existing catalyst for cyclic carbonate synthesis, and realizes the combination and the cooperation of two active centers on the molecular level by using a double-center porous polymer containing metalloporphyrin and quaternary phosphonium sites as the catalyst, thereby efficiently converting carbon dioxide into cyclic carbonate.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a process for preparing cyclic carbonate from the dual-center porous polymer as catalyst to catalyze CO2And converting into cyclic carbonate, wherein the double-center porous polymer is a double-center heterogeneous porous catalyst with metalloporphyrin and quaternary phosphonium sites.
The catalysis is carried out in a solvent-free system.
The preparation method of the cyclic carbonate comprises the following steps: adding the catalyst into a Schlenk tube, adding an epoxy substrate, and grafting CO2Balloon reacting at 70-100 deg.c for 24-48 hr to obtain cyclic carbonate.
Furthermore, the catalyst is recovered after being filtered, separated, washed by ethyl acetate and dried in vacuum at 60 ℃, and can be applied to the next catalytic cycle.
The catalyst is prepared by copolymerizing vinyl functionalized porphyrin and a 4- (diphenylphosphino) styrene monomer, and then performing quaternary phosphonylation and metal coordination.
The preparation method of the catalyst comprises the following steps:
step 1, 4- (diphenylphosphino) styrene (Ph)2PSt) synthesis; preparing 4- (diphenylphosphino) styrene by taking 4-bromostyrene and diphenyl phosphine chloride as raw materials;
step 2, synthesizing tetra (4-vinylphenyl) porphyrin (VPP); preparing 4-vinylbenzaldehyde by using 4-bromostyrene and N, N-dimethylformamide as raw materials; and 4-vinylbenzaldehyde and pyrrole are used as raw materials to prepare tetra (4-vinylphenyl) porphyrin;
step 3, synthesis of porous polymer: preparing a porous organic polymer by taking 4- (diphenylphosphino) styrene, tetravinyl phenyl porphyrin and azobisisobutyronitrile as raw materials;
and 4, synthesizing a double-center porous polymer: carrying out quaternary phosphonylation on the porous polymer by adopting bromide to obtain a double-center porous polymer containing alkyl; then carrying out metal coordination reaction on the quaternary phosphonium treated porous organic polymer to obtain the double-center porous polymer containing the quaternary phosphonium sites and the metalloporphyrin.
The synthesis method of the step 1 comprises: adding magnesium powder into a three-neck round-bottom flask, vacuumizing, drying, adding N2Adding tetrahydrofuran under the atmosphere, dropwise adding 4-bromostyrene through a dropping funnel, continuing stirring at room temperature for two hours after dropwise adding, adding diphenyl phosphine chloride by the same operation, and reacting at room temperature overnight. After the reaction is stopped, quenching the solution by using saturated ammonium chloride aqueous solution, extracting by using ethyl acetate, combining organic layers, removing the organic solvent by rotary evaporation, and purifying by using column chromatography, wherein the eluent is petroleum ether: ethyl acetate 100: 1 (volume ratio), removing the solvent by rotary evaporation, and drying the obtained solid in vacuum to finally obtain a white solid product 4- (diphenylphosphino) styrene Ph2PSt. The 4-bromostyrene is purified by reduced pressure distillation before use.
The method for synthesizing 4-vinylbenzaldehyde in the step 2 comprises the following steps: adding magnesium powder into a three-neck round-bottom flask, vacuumizing, drying, adding N2Adding anhydrous tetrahydrofuran under the atmosphere, adding 4-bromostyrene by using a dropping funnel, stirring and reacting for two hours at room temperature, then adding N, N-dimethylformamide according to the same method, and reacting overnight at room temperature; after the reaction is stopped, quenching the solution by using saturated ammonium chloride aqueous solution, extracting by using ethyl acetate, combining organic layers, removing the solvent by rotary evaporation, and purifying a crude product by using column chromatography, wherein an eluent is petroleum ether: ethyl acetate ═ 20: 1 (volume ratio), and removing the solvent by rotary evaporation to obtain a light yellow transparent liquid 4-vinylbenzaldehyde.
The method for synthesizing tetra (4-vinylphenyl) porphyrin in the step 2 comprises the following steps: adding pure 4-vinylbenzaldehyde, pyrrole and propionic acid into a round-bottom flask, reacting at 140 ℃ for 1 hour, filtering, washing with ethyl acetate, and drying at 30 ℃ in vacuum to obtain purple solid tetravinyl phenyl porphyrin.
The method for synthesizing the porous polymer in the step 3 comprises the following steps: dissolving 4- (diphenylphosphino) styrene, tetravinylphenylporphyrin and Azobisisobutyronitrile (AIBN) in NMP, transferring the solution into a 50ml polytetrafluoroethylene reactor, reacting at 200 ℃ for 3 days, filtering and separating solid, extracting with dichloromethane in a Soxhlet extractor for 72 hours, and drying the obtained solid at 30 ℃ for 6 hours in vacuum to obtain the porous organic polymer PVPP-PPh2PSt-X，X＝1-6Wherein the number X represents VPP and Ph2Molar charge ratio of PSt.
The quaternary phosphonium treatment in step 4 comprises: dispersing the porous organic polymer in anhydrous DMF, adding bromide and N2Reacting for 3d under protection, cooling to room temperature after the reaction is finished, washing with DMF for three times, and vacuum drying at 100 ℃ for 12 h. The bromide is one of ethyl bromide, 1-bromobutane, 1-bromohexane and 1-bromooctane.
The synthesis of the double-center porous polymer containing quaternary phosphonium sites and metalloporphyrin in the step 4 comprises dispersing the quaternary phosphonium treated porous organic polymer in anhydrous DMF, adding metal chloride, and adding N2Refluxing under atmosphere for 36h, cooling to room temperature, stirring with 3M hydrochloric acid in air, filtering, washing with large amount of water, and vacuum drying at 80 deg.C for 12h to obtain PMtVPP-PPh2PStR-X(Mt＝Zn,Ni,Fe,Cu)。
From the above description, it can be seen that the present invention has the following advantages:
1. the invention solves the problem of complex recovery of the existing catalyst for synthesizing cyclic carbonate, and realizes the combination and the cooperation of two active centers on the molecular level by using a double-center porous polymer containing metalloporphyrin and quaternary phosphonium sites as the catalyst, thereby efficiently converting carbon dioxide into cyclic carbonate.
2. The preparation method provided by the invention realizes the preparation of cyclic carbonate under the conditions of no cocatalyst, no solvent and milder conditions.
3. The POPs are constructed by free radical polymerization of vinyl functionalized monomers, an insoluble structure with high ligand concentration and excellent swelling performance is formed, convenience is provided for subsequent reaction, and meanwhile, double active sites are configured on the POPs framework to promote concerted catalysis of two active centers and efficiently catalyze cycloaddition of carbon dioxide and epoxide.
Drawings
FIG. 1 shows the PVPP-PPh polymer2Solid state of PSt-113A C NMR spectrum;
FIG. 2 is the polymer PVPP-PPh2Solid state of PSt-131P NMR spectrum.
Detailed Description
With reference to fig. 1, a specific embodiment of the present invention is described in detail, but the present invention is not limited in any way by the claims.
Example 1
1. Synthesis of a double-centered porous polymer:
step 1, 4- (diphenylphosphino) styrene (Ph)2PSt) synthesis;
preparing 4- (diphenylphosphino) styrene by taking 4-bromostyrene and diphenyl phosphine chloride as raw materials; the method comprises the following specific steps:
4-bromostyrene is purified by reduced pressure distillation before use; magnesium powder (1.5g, 62.5mmol) was charged into a 300ml three-necked round bottom flask, dried under vacuum, and charged with N2Tetrahydrofuran (50ml) was added under ambient conditions, 4-bromostyrene (6.6075g, 36.1mmol) was added dropwise through a dropping funnel, stirring was continued at room temperature for two hours after completion of the addition, diphenylphosphine chloride (6.6120g, 30.3mmol) was added thereto in the same manner, and the reaction was allowed to proceed at room temperature overnight. After the reaction was stopped, the solution was quenched with saturated aqueous ammonium chloride (200ml), extracted with ethyl acetate, the organic layers were combined, the organic solvent was removed by rotary evaporation and purified by column chromatography, the eluent was petroleum ether: ethyl acetate 100: 1 (volume ratio), removing the solvent by rotary evaporation, and drying the obtained solid in vacuum to finally obtain a white solid product 4- (diphenylphosphino) styrene Ph2PSt, yield 7.0g (80.86%)
Step 2, synthesizing tetra (4-vinylphenyl) porphyrin (VPP); preparing 4-vinylbenzaldehyde by using 4-bromostyrene and N, N-dimethylformamide as raw materials; the method comprises the following specific steps:
magnesium powder (4.8005g, 0.2mmol) was charged into a 500ml three-necked round bottom flask, dried under vacuum, and charged to N2Anhydrous tetrahydrofuran (90ml) was added under ambient conditions, 4-bromostyrene (18.3232g, 100mmol) was added via a dropping funnel, and after stirring at room temperature for two hours, N-dimethylformamide (7.3215g, 100mmol) was added in the same manner, and the mixture was reacted at room temperature overnight. After the reaction had stopped, the solution was quenched with saturated aqueous ammonium chloride (200ml), extracted with ethyl acetate, the organic layers were combined, the solvent was removed by rotary evaporation, and the crude product was purified by column chromatographyAnd the eluent is petroleum ether: ethyl acetate ═ 20: 1 (volume ratio), and removing the solvent by rotary evaporation to obtain light yellow transparent liquid 4-vinylbenzaldehyde (9.78g, 74.07%).
Preparing tetra (4-vinyl phenyl) porphyrin by taking 4-vinyl benzaldehyde and pyrrole as raw materials; the method comprises the following specific steps:
a500 mL round bottom flask was charged with pure 4-vinylbenzaldehyde (4.3380g, 32.9mmol), freshly distilled pyrrole (2.2011g, 32.9mmol) and propionic acid (250mL), reacted at 140 ℃ for 1 hour, filtered and washed with ethyl acetate and dried under vacuum at 30 ℃ to give a purple solid tetravinylphenylporphyrin VPP (2.0g, 23.92%).
Step 3, synthesis of porous polymer: preparing a porous organic polymer by taking 4- (diphenylphosphino) styrene, tetravinyl phenyl porphyrin and azobisisobutyronitrile as raw materials; the method comprises the following specific steps:
dissolving 4- (diphenylphosphino) styrene (0.7892g, 2.8mmol), tetravinylphenylporphyrin (1.9847g, 2.8mmol) and Azobisisobutyronitrile (AIBN) (0.1348g, 0.821mmol) in (NMP) (15ml), transferring the solution into a 50ml polytetrafluoroethylene reactor, reacting at 200 ℃ for 3 days, filtering to separate the solid, extracting with dichloromethane in a Soxhlet extractor for 72 hours, and vacuum drying the solid at 30 ℃ for 6 hours to obtain the porous organic polymer PVPP-PPh2PSt-1(2.76g，99.52％)；
And 4, synthesizing a double-center porous polymer: carrying out quaternary phosphonylation on the porous polymer by adopting bromide to obtain a double-center porous polymer containing alkyl; then carrying out metal coordination reaction on the quaternary phosphonium treated porous organic polymer to obtain a double-center porous polymer containing quaternary phosphonium sites and metalloporphyrin; mixing porous organic polymer PVPP-PPh2PSt-1(0.2503g) was dispersed in anhydrous DMF (8ml), and bromoethane (0.3359g, 3.3mmol) and N were added2And reacting for 3d in an oil pan at 60 ℃ under protection. After the reaction is finished, the reaction product is cooled to room temperature, washed three times by DMF, and dried for 12 hours in vacuum at 100 ℃. Obtaining the product PVPP-PPh of ethyl quaternary phosphonium2PStE-1；
The quaternary phosphonium salt product PVPP-PPh2PStE-1 was dispersed in anhydrous DMF and cobalt chloride hexahydrate (0.7852g, 3.3mmol) was added in N2Refluxing for 36h under ambient conditions, cooling to room temperature, and stirring with 3M hydrochloric acid (60ml) in air to remove Co2+Oxidation to Co3+. Filtering, washing with a large amount of water, and vacuum drying at 80 deg.C for 12 hr to obtain Co3+Coordinated porous polymer catalyst PCoVPP-PPh2PStE-1。
The preparation is carried out according to the method sequentially: PCoVPP-PPh2PStB-1、PCoVPP-PPh2PStH-1、PCoVPP-PPh2PStO-1、PCoVPP-PPh2PStO-1、PCoVPP-PPh2PStO-1、PCoVPP-PPh2PStO-1、PCoVPP-PPh2PStE-6；
The 8 double-centered porous polymers described above were then used as catalysts in the synthesis of cyclic carbonates:
adding a catalyst (50-55 mg) into a 25ml Schlenk tube filled with magnetons, adding an epoxy substrate (20mmol), and connecting with CO2(1atm) reacting the mixture with a balloon at 70-100 ℃ for 24-48 h. After the reaction has stopped, by1H NMR was used to determine the conversion and selectivity of the substrate. The catalyst is applied to the next catalytic cycle after being filtered, separated, washed by ethyl acetate and dried in vacuum at 60 ℃.
1-8 pairs of epichlorohydrin and CO by using double-center porous polymer catalyst2The effect of the cycloaddition reaction, as shown in the following table, shows that when the alkyl group of the quaternary phosphonium is octyl, the porous organic polymer PCoVPP-PPh is obtained2The PStO-1 catalyst has higher catalytic activity, and the conversion rate of carbon dioxide and epoxy chloropropane can reach 95.25 percent after the catalytic reaction for 48 hours at 100 ℃.
| Entry | Catalyst | Tem.(℃) | Conv.(％) | Sel.(％) |
| 1 | PCoVPP-PPh2PStE-1 | 80 | 71.91 | >99 |
| 2 | PCoVPP-PPh2PStB-1 | 80 | 76.42 | >99 |
| 3 | PCoVPP-PPh2PStH-1 | 80 | 83.05 | >99 |
| 4 | PCoVPP-PPh2PStO-1 | 80 | 86.47 | >99 |
| 5 | PCoVPP-PPh2PStO-1 | 70 | 78.02 | >99 |
| 6 | PCoVPP-PPh2PStO-1 | 90 | 88.29 | >99 |
| 7 | PCoVPP-PPh2PStO-1 | 100 | 95.25 | >99 |
| 8 | PCoVPP-PPh2PStE-6 | 80 | 62.26 | >99 |
Based on the experimental results in the table, PCoVPP-PPh with higher catalytic activity2PStO-1 is taken as an example, and the usability of the catalyst on other epoxides is studied, so that various epoxides are catalyzed under the catalysis condition of 100 ℃. As shown in the following table, for epoxides other than epichlorohydrin, good catalytic effects were achieved by reducing the amount of the substrate and increasing the reaction time.
Randomly extracting catalyst for performance detection by using PCoVPP-PPh2PStB-1 as an example, PVPP-PPh2Of PStB-113C NMR and31p NMR analysis, as shown in FIG. 1, which shows the porous organic polymer PVPP-PPh2Solid state of PStB-113C NMR spectrum. Peaks at 110-150 ppm are attributed to the carbons on the porphyrin macrocycle and the carbons on the benzene ring. The significant peak at 30-50ppm is due to the carbon of the polymerized vinyl group. FIG. 2 also shows PVPP-PPh2PStB-1 of31A P NMR spectrum of the sample to be analyzed,13c NMR spectra and31p NMR spectra show that porous organic polymers containing porphyrins and functionalizable phosphines are successfully prepared. The polymer is reacted with a metal salt to form a metal coordination structure, e.g., PVPP-PPh2Formation of PCoVPP-PPh by coordination on the basis of PStB-12PStB-1. The structure has not only the active center of metalloporphyrin but also the active center of quaternary phosphonium site.
In summary, the invention has the following advantages:
1. the invention solves the problem of complex recovery of the existing catalyst for synthesizing cyclic carbonate, and realizes the combination and the cooperation of two active centers on the molecular level by using a double-center porous polymer containing metalloporphyrin and quaternary phosphonium sites as the catalyst, thereby efficiently converting carbon dioxide into cyclic carbonate.
2. The preparation method provided by the invention realizes the preparation of cyclic carbonate under the conditions of no cocatalyst, no solvent and milder conditions.
3. The POPs are constructed by free radical polymerization of vinyl functionalized monomers, an insoluble structure with high ligand concentration and excellent swelling performance is formed, convenience is provided for subsequent reaction, and meanwhile, double active sites are configured on the POPs framework to promote concerted catalysis of two active centers and efficiently catalyze cycloaddition of carbon dioxide and epoxide.
It should be understood that the detailed description of the invention is merely illustrative of the invention and is not intended to limit the invention to the specific embodiments described. It will be appreciated by those skilled in the art that the present invention may be modified or substituted equally as well to achieve the same technical result; as long as the use requirements are met, the method is within the protection scope of the invention.
Claims (6)
1. A method for preparing cyclic carbonate is characterized in that: catalyzing CO by using double-center porous polymer as catalyst2And converting into cyclic carbonate, wherein the double-center porous polymer is a double-center heterogeneous porous catalyst with metalloporphyrin and quaternary phosphonium sites.
2. The method for producing a cyclic carbonate according to claim 1, characterized in that: the catalysis is carried out in a solvent-free system.
3. The method for producing a cyclic carbonate according to claim 2, characterized in that: the preparation method of the cyclic carbonate comprises the following steps: adding the catalyst into a Schlenk tube, adding an epoxy substrate, and grafting CO2Balloon reacting at 70-100 deg.c for 24-48 hr to obtain cyclic carbonate.
4. The method for producing a cyclic carbonate according to claim 3, characterized in that: the catalyst is recovered after filtration separation, ethyl acetate washing and vacuum drying at 60 ℃, and can be applied to the next catalytic cycle.
5. The method for producing a cyclic carbonate according to claim 1, characterized in that: the catalyst is prepared by copolymerizing vinyl functionalized porphyrin and a 4- (diphenylphosphino) styrene monomer, and then performing quaternary phosphonylation and metal coordination.
6. The method for producing a cyclic carbonate according to claim 5, wherein: the preparation method of the catalyst comprises the following steps:
step 1, 4- (diphenylphosphino) styrene (Ph)2PSt) synthesis; preparing 4- (diphenylphosphino) styrene by taking 4-bromostyrene and diphenyl phosphine chloride as raw materials;
step 2, synthesizing tetra (4-vinylphenyl) porphyrin (VPP); preparing 4-vinylbenzaldehyde by using 4-bromostyrene and N, N-dimethylformamide as raw materials; and 4-vinylbenzaldehyde and pyrrole are used as raw materials to prepare tetra (4-vinylphenyl) porphyrin;
step 3, synthesis of porous polymer: preparing a porous organic polymer by taking 4- (diphenylphosphino) styrene, tetravinyl phenyl porphyrin and azobisisobutyronitrile as raw materials;
and 4, synthesizing a double-center porous polymer: carrying out quaternary phosphonylation on the porous polymer by adopting bromide to obtain a double-center porous polymer containing alkyl; then carrying out metal coordination reaction on the quaternary phosphonium treated porous organic polymer to obtain the double-center porous polymer containing the quaternary phosphonium sites and the metalloporphyrin.
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| CN114014833A (en) * | 2021-12-09 | 2022-02-08 | 浙江理工大学 | Method for preparing cyclic carbonate from low-concentration carbon dioxide and catalyst used in method |
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| CN114014833A (en) * | 2021-12-09 | 2022-02-08 | 浙江理工大学 | Method for preparing cyclic carbonate from low-concentration carbon dioxide and catalyst used in method |
| CN114014833B (en) * | 2021-12-09 | 2023-09-15 | 浙江理工大学 | Method for preparing cyclic carbonate from low-concentration carbon dioxide and catalyst used by method |
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