CN114085189A - Preparation method and application of metal-diimidazole salt ionic liquid catalyst - Google Patents
Preparation method and application of metal-diimidazole salt ionic liquid catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 14
- 150000003839 salts Chemical class 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 230000003197 catalytic effect Effects 0.000 claims abstract description 21
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- 150000001339 alkali metal compounds Chemical class 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
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- 229920000515 polycarbonate Polymers 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
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- 230000005494 condensation Effects 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims 1
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- 239000000047 product Substances 0.000 abstract description 11
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- 239000007787 solid Substances 0.000 abstract description 5
- 239000012153 distilled water Substances 0.000 abstract description 4
- 239000012467 final product Substances 0.000 abstract description 4
- 239000012263 liquid product Substances 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000004939 coking Methods 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 229910052744 lithium Inorganic materials 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- AZUHIVLOSAPWDM-UHFFFAOYSA-N 2-(1h-imidazol-2-yl)-1h-imidazole Chemical compound C1=CNC(C=2NC=CN=2)=N1 AZUHIVLOSAPWDM-UHFFFAOYSA-N 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 229910052700 potassium Inorganic materials 0.000 description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 7
- 239000011591 potassium Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
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- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 4
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/307—General preparatory processes using carbonates and phenols
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种金属联咪唑盐离子液体催化剂的制备方法及应用，该催化剂是将含有两个咪唑环的联咪唑与碱金属化合物反应脱水结合，由碱金属化合物提供金属阳离子，联咪唑作为阴离子构成离子液体催化体系；制备方法为向反应釜中加入摩尔比1：1.5‑3的联咪唑与碱金属化合物，然后加入适量DMF作溶剂，100‑130℃氮气保护下冷凝回流磁力搅拌反应18‑24h，反应结束后液体产物90‑120℃真空旋蒸除去溶剂，然后加入适量蒸馏水洗涤并过滤，100‑130℃真空干燥24h，得最终产物黄色固体。本发明解决了传统催化剂影响产品PC的色差和色泽，还会在后续反应中发生枝化、焦化、降解等反应，并且在双酚A转化率上需要进一步提高等的问题。The invention relates to a preparation method and application of a metal biimidazolium salt ionic liquid catalyst. The catalyst comprises the following steps of reacting and dehydrating biimidazole containing two imidazole rings with an alkali metal compound, providing metal cations from the alkali metal compound, and using the biimidazole as an anion An ionic liquid catalytic system is formed; the preparation method is as follows: adding biimidazole and an alkali metal compound in a molar ratio of 1:1.5-3 to the reaction kettle, then adding an appropriate amount of DMF as a solvent, and condensing and refluxing under the protection of nitrogen at 100-130 ℃ with a magnetic stirring reaction for 18- 24h, after the reaction is completed, the liquid product is evaporated under vacuum at 90-120°C to remove the solvent, then an appropriate amount of distilled water is added to wash and filter, and vacuum-dried at 100-130°C for 24h to obtain the final product as a yellow solid. The invention solves the problems that the traditional catalyst affects the color difference and color of the product PC, and reactions such as branching, coking, and degradation occur in subsequent reactions, and the conversion rate of bisphenol A needs to be further improved.
Description
Technical Field
The invention relates to the technical field of catalysts, and particularly relates to a preparation method of a metal biimidazole salt basic ionic liquid catalyst and application of the catalyst in synthesizing Polycarbonate (PC) by catalyzing diphenyl carbonate (DPC) and bisphenol A (BPA).
Background
Polycarbonate (PC) is generally odorless, non-toxic, transparent, has good thermal properties and excellent mechanical properties, and is one of five major engineering plastics. According to different functional characteristics, the material is respectively suitable for different fields of mechanical equipment, optical materials, building materials, electronics and electricity and the like. Polycarbonates on the market are classified into several major types, such as aliphatic, alicyclic, and aromatic types, according to the raw materials, and bisphenol a Polycarbonate (PC) is currently most used. The bisphenol A polycarbonate is synthesized by using diphenyl carbonate (DPC) and bisphenol A as raw materials (the reaction formula is shown in figure 3), and the commonly used catalysts in the process are alkaline catalysts which can be divided into three types, namely alkaline metal salt catalysts, quaternary ammonium salt catalysts, quaternary phosphonium salt catalysts and heterocyclic N-containing catalysts. At present, in the PC market, a direct phosgene method or an indirect phosgene method is mostly adopted, an alkaline metal catalyst is used as a main catalyst, a large amount of solvents are used for industrial production, the alkaline metal catalyst has good catalytic performance and is cheap and easy to obtain, but the color difference and the color of the product PC are influenced, reactions such as branching, coking, degradation and the like can also occur in subsequent reactions, and the conversion rate of bisphenol A needs to be further improved.
Disclosure of Invention
The purpose of the invention is as follows:
the invention provides a preparation method and application of a metal diimidazole salt basic ionic liquid catalyst, and aims to provide an ionic liquid catalyst system with a synergistic catalytic effect, which is composed of active component metal cations and diimidazole anions, so that the problems that the traditional catalyst influences the color difference and color of a product PC, can also cause reactions such as branching, coking, degradation and the like in subsequent reactions, and needs to be further improved in the conversion rate of bisphenol A and the like are solved.
The technical scheme is as follows:
a metal biimidazole saline-alkali ionic liquid catalyst is prepared through reaction and dewatering of biimidazole containing two imidazole rings with alkali metal compound, providing metal cation by alkali metal compound, and forming ionic liquid catalytic system by biimidazole as anion, and features that:
M＝Li、Na、K。
a preparation method of a metal biimidazole salt basic ionic liquid catalyst comprises the following steps of adding a catalyst with a molar ratio of 1: 1.5-3 of biimidazole and alkali metal compound, then adding a proper amount of N, N-Dimethylformamide (DMF) as a solvent, carrying out condensation reflux magnetic stirring reaction for 18-24h under the protection of nitrogen at the temperature of 100-.
The alkali metal compound is one of lithium hydroxide, sodium hydroxide or potassium hydroxide. Lithium hydroxide, sodium hydroxide, potassium hydroxide are used to provide lithium, sodium, potassium active sites.
An application of a metal biimidazole salt basic ionic liquid catalyst in catalyzing the reaction of diphenyl carbonate (DPC) and bisphenol A (BPA) for synthesizing Polycarbonate (PC).
Has the advantages that:
(1) compared with a single heterocyclic nitrogen-containing catalyst and a quaternary ammonium salt and quaternary phosphonium salt catalyst, the catalytic system has stronger coordination and nucleophilic abilities, and the biimidazole anions and the metal cations generate a synergistic effect, so that the reaction conversion rate can be improved, and the catalytic activity and the reaction selectivity can be enhanced.
(2) The catalyst system is based on the physical properties of the ionic liquid, is pasty or solid at normal temperature, is not easy to burn, explode or oxidize, and has better thermal stability and chemical stability.
(3) The conversion rate of the bisphenol A is improved to more than 90 percent from about 70 percent of the traditional conversion rate, and the molecular weight of the PC is controllable through process adjustment.
(4) The catalyst has a certain plasticizing and toughening effect in the process of synthesizing PC, and provides a new technology for synthesizing high-performance PC with controllable molecular weight.
Drawings
FIG. 1 is a schematic diagram of catalyst synthesis;
FIG. 2 is a diagram of a reaction apparatus;
FIG. 3 is a diagram showing the reaction mechanism of diphenyl carbonate and bisphenol A to synthesize Polycarbonate (PC);
FIG. 4 is a graph of IR spectroscopy analysis of the catalyst prepared;
fig. 5 is a thermogravimetric analysis chart of the prepared catalyst.
Detailed Description
The present invention will be described in further detail below with reference to examples.
As shown in figure 1, the catalyst of the invention is an ionic liquid catalytic system which is formed by reacting and dehydrating a biimidazole containing two imidazole rings with an alkali metal compound, providing metal cations by the alkali metal compound and using the biimidazole as an anion. The ionic liquid catalyst is designed and catalyzed by using the Biimidazole, the Biimidazole (2,2' -Biimidazole) contains an imidazole similar structure and is a white granular crystal at normal temperature, and an unshared electron pair of a nitrogen atom at the 1-position in an imidazole ring participates in cyclic conjugation, so that hydrogen on the nitrogen atom is easy to leave in a hydrogen ion form, and the ionic liquid catalyst has specific proton accepting and donating properties. In this reaction, the free imidazole ring was negative, and the metals lithium, sodium, and potassium were positive.
The catalyst of the invention has the following structure:
M＝Li、Na、K。
the catalyst is stable in property, easy to store, green and pollution-free based on ionic liquid, and the biimidazole anion has higher selectivity for ester exchange reaction, can generate synergistic effect with metal cations, enhances catalytic activity and improves reaction conversion rate. The invention utilizes an infrared spectrometer (FT-IR), a thermal weight loss analyzer (TG) and the like to represent the structure and the thermal stability of the catalyst, DPC and BPA are used as raw materials, and the prepared metal imidazole basic ionic liquid is used as the catalyst to investigate the catalytic performance of the catalyst.
Example 1:
adding 0.1mol of biimidazole and 0.2mol of lithium hydroxide into a three-neck flask, then adding 50mL of DMMF serving as a solvent, carrying out condensation reflux magnetic stirring reaction for 16h under the protection of nitrogen at 100 ℃, removing the solvent by vacuum rotary evaporation at 120 ℃ of a liquid product after the reaction is finished, then adding 60mL of distilled water for washing and filtering, and carrying out vacuum drying at 120 ℃ for 24h to obtain a final product, namely yellow solid biimidazole lithium. The infrared spectrum analysis is shown in FIG. 4, and the thermogravimetric analysis is shown in FIG. 5.
The curve A3 corresponding to the biimidazole lithium in FIG. 4 has a characteristic peak of N-H bond of 2600cm-1To 2800cm-1In the range A3 is 2780cm in comparison to biimidazole A1-1The peak pattern becomes small because the N — H bond energy decreases after the biimidazole is linked to lithium metal. Wave number of 1500cm-1Near the imidazole ring, the C-N characteristic peak is 1600cm-1The peak is a characteristic peak of C ═ C double bond, and the bending vibration peak of the imidazole ring is 750cm-1From this, it was found that the sample was lithium biimidazole as a target product.
The T2 curve corresponding to the biimidazole lithium in FIG. 5 rapidly decreases at about 100 ℃ due to water loss, while the temperature of the sample actually starting thermal decomposition is 290 ℃, and the catalytic temperature of the sample reaches up to 260 ℃, so that the thermal stability of the catalyst meets the requirement of catalytic reaction. When the temperature reaches 500 ℃, the thermal decomposition is basically finished, and the corresponding residual quantity is more than 20%. Therefore, the thermal stability of the biimidazole lithium meets the temperature requirement of catalytic reaction, and thermal decomposition does not occur in the catalytic process.
Example 2:
adding 0.1mol of biimidazole and 0.2mol of sodium hydroxide into a three-neck flask, then adding 50mL of DMMF serving as a solvent, carrying out condensation reflux magnetic stirring reaction for 24 hours at the temperature of 110 ℃ under the protection of nitrogen, removing the solvent by vacuum rotary evaporation at the temperature of 120 ℃ of a liquid product after the reaction is finished, then adding 60mL of distilled water for washing and filtering, and carrying out vacuum drying at the temperature of 120 ℃ for 24 hours to obtain a final product, namely light yellow solid biimidazole sodium. The infrared spectrum analysis is shown in FIG. 4, and the thermogravimetric analysis is shown in FIG. 5.
In FIG. 4, the curve A2 for bisimidazole sodium corresponds to A2 at 2750cm in comparison with bisimidazole A1-1The peak shape becomes smaller, also because the N-H bond energy is reduced after the biimidazole is connected with the metallic sodium. Other analyses are as above, and figure 4 illustrates the sample, sodium biimidazole, as the desired product.
The T3 curve corresponding to the bisimidazole sodium in FIG. 5 is caused by water loss within 100 ℃, the temperature of the sample actually starting thermal decomposition is 290 ℃, and the catalytic temperature of the sample reaches 260 ℃ at most, so that the thermal stability of the catalyst bisimidazole sodium meets the requirement of catalytic reaction.
Example 3:
adding 0.1mol of biimidazole and 0.2mol of potassium hydroxide into a three-neck flask, then adding 50mL of DMMF serving as a solvent, carrying out condensation reflux magnetic stirring reaction for 22 hours at 120 ℃ under the protection of nitrogen, removing the solvent by vacuum rotary evaporation at 120 ℃ of a liquid product after the reaction is finished, then adding 60mL of distilled water for washing and filtering, and carrying out vacuum drying at 120 ℃ for 24 hours to obtain a final product, namely yellow solid biimidazole potassium. The infrared spectrum analysis is shown in FIG. 4, and the thermogravimetric analysis is shown in FIG. 5.
Curve A4 for potassium bisimidazole in FIG. 4, A4 at 2700cm, in comparison with bisimidazole A1-1The peak shape becomes smaller, also because the N-H bond energy is reduced after the biimidazole is connected with the metal potassium. Other analyses are as above, and figure 4 illustrates the sample potassium biimidazole as the target product.
The T4 curve corresponding to the potassium biimidazole in FIG. 5 is due to the fact that the temperature of the sample actually starts to be thermally decomposed is 285 ℃, and the catalytic temperature of the sample reaches 260 ℃ at most, so that the thermal stability of the catalyst potassium biimidazole meets the requirement of catalytic reaction.
Example 4
The procedure for the lithium bisimidazole catalyzed synthesis of polycarbonate was the same as in example 1, with the molar ratio of bisimidazole to lithium hydroxide being changed to 1: 1.5, the results are shown in Table 2.
Example 5
The procedure for the lithium bisimidazole catalyzed synthesis of polycarbonate was the same as in example 1, with the molar ratio of bisimidazole to lithium hydroxide being changed to 1: 2.5, the experimental results are shown in table 2.
Example 6
The procedure for the lithium bisimidazole catalyzed synthesis of polycarbonate was the same as in example 1, with the molar ratio of bisimidazole to lithium hydroxide being changed to 1: 3, the experimental results are shown in table 2.
A specific implementation method of a reaction for synthesizing Polycarbonate (PC) by catalyzing diphenyl carbonate (DPC) and bisphenol A (BPA) with a metal biimidazole saline-alkali ionic liquid catalyst is as follows:
weighing 1-1.2: pouring the DPC and the BPA of 1 into a three-neck flask, introducing nitrogen to detect the tightness, blowing and exhausting air in the flask, starting mechanical stirring, opening a heating sleeve, setting the heating temperature to be 150 ℃ until the materials are completely melted, adding a catalyst after the temperature of the kettle liquid reaches 140 ℃, wherein the using amount of the catalyst is 0.25 percent of the mass of the reaction product, closing the nitrogen after detecting the good tightness again, opening a vacuum pump, vacuumizing to 15-5KPa, continuously heating to the temperature of 150 and 180 ℃ for carrying out the first-step ester exchange reaction, gradually heating to 220 ℃ after continuously reacting for 30-60min, and collecting the phenol generated in the process through a condensing device. After the gas phase temperature decreased to 50 ℃ and became stable, the second polycondensation was started. Gradually raising the temperature to 220-280 ℃ at the speed of 5 ℃ per minute, adjusting the pressure to 10-1KPa, continuously reacting for 20-60min under the condition, stopping the reaction, and casting the corresponding mould to prepare the corresponding PC sample strip or sample, wherein the reaction device is shown as the figure 2.
After the distillate is detected by a gas chromatograph, the percentage content of each component in the product is determined by an area normalization method, the conversion rate, the selectivity and the yield of reactants and target products are calculated, the products are measured by an Ubbelohde viscometer, and the viscosity-average molecular weight is estimated by a one-point method so as to measure and evaluate the catalytic performance.
The catalysts prepared in examples 1-3 and conventional catalysts sodium hydroxide, heterocyclic nitrogen-containing catalyst (pyridine), quaternary ammonium salt (tetrabutylammonium hydroxide) and quaternary phosphonium salt (tetrabutylammonium hydroxide) were used to catalyze the synthesis of Polycarbonate (PC) from diphenyl carbonate (DPC) and bisphenol a (bpa), respectively. The results of the catalytic evaluation are shown in Table 1.
Table 1 comparison of catalytic performance of examples 1-3 with conventional catalysts
As can be seen from the data in table 1, the catalytic effect of the present invention is significant, and the reaction conversion rate and the product selectivity are both greatly improved compared with the conventional catalyst, wherein the best catalytic effect is the biimidazole lithium of example 1, the conversion rate is as high as 97.31%, and the selectivity is as high as 95.47%. In addition, the molecular weight distribution of the synthesized PC product is narrow, and the molecular weight can be controlled. The notch impact strength test shows that the notch impact strength of the PC synthesized by the invention is higher than that of the traditional catalyst, which shows that the invention not only has good catalytic action, but also has certain plasticizing and toughening action.
TABLE 2 evaluation of catalytic Effect of examples 1 and 4 to 6
As can be seen from Table 2, the reactivity gradually increased with the increasing amount of the lithium-containing compound, and the conversion rate and the notched impact strength reached the maximum values when the molar ratio of biimidazole to lithium hydroxide was 1:2 (example 1).
Compared with the traditional alkaline catalyst, the method has the advantages of mild and easily-controlled reaction process and further improved reaction conversion rate and selectivity. The catalyst not only plays a role in catalysis in the catalysis process, but also has certain plasticizing and toughening effects in the process of synthesizing PC, and the synthesized PC has good impact resistance and perfect comprehensive performance.
Claims (4)
1. A metal biimidazole salt basic ionic liquid catalyst is characterized in that: the catalyst is prepared by reacting and dehydrating biimidazole containing two imidazole rings with an alkali metal compound, providing metal cations by the alkali metal compound, and forming an ionic liquid catalytic system by using biimidazole as an anion, and has the following structure:
2. a method for preparing the metal biimidazole salt basic ionic liquid catalyst of claim 1, which is characterized in that: adding a mixture of the components in a molar ratio of 1: 1.5-3 of biimidazole and alkali metal compound, then adding a proper amount of N, N-dimethylformamide as a solvent, carrying out condensation reflux magnetic stirring reaction for 18-24h under the protection of nitrogen at the temperature of 100-.
3. The preparation method of the metal diimidazole salt basic ionic liquid catalyst according to claim 2, which is characterized in that: the alkali metal compound is one of lithium hydroxide, sodium hydroxide or potassium hydroxide.
4. The use of the metal-biimidazole salt basic ionic liquid catalyst of claim 1 in catalyzing the reaction of diphenyl carbonate and bisphenol a to synthesize polycarbonate.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115041227A (en) * | 2022-07-22 | 2022-09-13 | 抚顺东科新能源科技有限公司 | Metal carboxylic group ionic liquid catalyst and preparation method and application thereof |
| CN116239613A (en) * | 2023-03-15 | 2023-06-09 | 沈阳工业大学 | Catalyst, preparation method thereof and application of catalyst in catalytic synthesis of degradable polycarbonate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107670690A (en) * | 2017-09-08 | 2018-02-09 | 常州大学 | A kind of iron-based cyano-containing anion imidazole ion liquid catalyst and its preparation method and application |
-
2021
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Non-Patent Citations (3)
| Title |
|---|
| PETER KIRCHER,等: "Four-Coordinate Group-14 Elements in the Formal Oxidation State of Zero – Syntheses, Structures, and Dynamics of [{(CO)5Cr}2Sn(L2)] and Related Species" * |
| 梁金花;任晓乾;王锦堂;姜岷;李振江;: "双核碱性离子液体催化棉籽油酯交换制备生物柴油" * |
| 马程明;许杰;薛冰;李永昕;: "碱性离子液体催化碳酸乙烯酯甲醇酯交换合成碳酸二甲酯" * |
Cited By (3)
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|---|---|---|---|---|
| CN115041227A (en) * | 2022-07-22 | 2022-09-13 | 抚顺东科新能源科技有限公司 | Metal carboxylic group ionic liquid catalyst and preparation method and application thereof |
| CN115041227B (en) * | 2022-07-22 | 2024-03-29 | 抚顺东科新能源科技有限公司 | A metal carboxylic acid-based ionic liquid catalyst and its preparation method and application |
| CN116239613A (en) * | 2023-03-15 | 2023-06-09 | 沈阳工业大学 | Catalyst, preparation method thereof and application of catalyst in catalytic synthesis of degradable polycarbonate |
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