CN108772102B - Efficient Heteropolymetallic Catalysts for Catalyzing Carbon Dioxide to Cyclocarbonate Efficiently - Google Patents
Efficient Heteropolymetallic Catalysts for Catalyzing Carbon Dioxide to Cyclocarbonate Efficiently Download PDFInfo
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- CN108772102B CN108772102B CN201810335694.2A CN201810335694A CN108772102B CN 108772102 B CN108772102 B CN 108772102B CN 201810335694 A CN201810335694 A CN 201810335694A CN 108772102 B CN108772102 B CN 108772102B
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- 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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- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
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Abstract
本发明提供了一种杂多金属配位聚合物材料高效催化二氧化碳合成环碳酸酯的方法，涉及一种化学合成催化剂及其制备方法。该催化剂是一种杂金属配位聚合物材料，具有良好的热稳定性，其结构为1D双链的平面结构，所有的催化活性位点都暴露在外边，具有较高的催化转化效率和选择性。该催化剂具有结构稳定、不易分解、反应过程无需有机溶剂，适用范围广、产品收率高、合成成本低等诸多优点。本发明可以解决以往催化二氧化碳与环氧化合物反应转化为环碳酸酯反应中合成温度和压力高、催化剂用量大、反应时间长、产品收率低、选择性差等诸多问题，可以用于二氧化碳温室气体的资源化利用。
The invention provides a method for efficiently catalyzing carbon dioxide to synthesize cyclic carbonate by a heteropolymetallic coordination polymer material, and relates to a chemical synthesis catalyst and a preparation method thereof. The catalyst is a heterometallic coordination polymer material with good thermal stability, its structure is a 1D double-chain planar structure, all catalytic active sites are exposed, and it has high catalytic conversion efficiency and selectivity sex. The catalyst has the advantages of stable structure, not easy to decompose, no organic solvent needed in the reaction process, wide application range, high product yield and low synthesis cost. The invention can solve many problems such as high synthesis temperature and pressure, large catalyst dosage, long reaction time, low product yield and poor selectivity in the previous reaction of catalyzing the reaction of carbon dioxide and epoxy compound into cyclic carbonate, and can be used for carbon dioxide greenhouse gas resource utilization.
Description
Technical Field
The invention relates to the field of chemistry, in particular to a high-efficiency catalyst for synthesizing cyclic carbonate from carbon dioxide by using heteropoly metal and a preparation method thereof.
Technical Field
In recent years, with the emphasis on carbon pollution and the development of carbon chemistry, CO has been developed2Carbon resources are also a main greenhouse gas and an important C1 resource as a final state of carbon resources. The characteristics of abundant reserves, no toxicity, inertia and the like are paid more and more attention by more and more chemical workers. Rational utilization of CO2Not only can weaken the environmental problem, but also has great significance for relieving the energy crisis. The chemical inertness of carbon dioxide has hindered its use in chemical reactions. In recent years, a large amount of attention has been paid to and a catalyst capable of activating carbon dioxide has been searched for, and carbon dioxide is used as a raw material to react with other simple organic substances to synthesize various organic compounds having chemical utility values. Cyclic carbonates are widely used as fine chemical intermediates, inert aproticPolar solvent, biomedical precursor and polycarbonate; polycarbonate is widely used in the fields of engineering plastics and the like. Carbonates (including cyclic carbonates and polycarbonates) are chemically fixed CO2One example of success. Therefore, it is necessary to reasonably design and develop a catalyst with high efficiency, environmental protection, mild conditions, simple preparation process, low cost and high selectivity. At present, many documents report carbon dioxide immobilized catalysts, mainly including inorganic metal catalysts, organic quaternary ammonium salts, phosphonium salt catalysts, organic catalysts, Metal Organic Framework (MOF), organic framework materials (COF), ionic liquid catalysts, and the like, but most of these catalysts have disadvantages, such as unstable catalysts, harsh catalytic conditions, low catalytic efficiency, high preparation cost, poor selectivity, and the like, and cannot meet the large-scale industrial requirements.
In conclusion, the invention designs and synthesizes a high-efficiency catalyst containing heteropoly metals, which is suitable for the reaction of carbon dioxide and epoxy compounds to generate cyclic carbonate, thereby solving most problems and having potential industrial application value.
Disclosure of Invention
The invention aims to provide a method for synthesizing cyclic carbonate by catalyzing carbon dioxide with a heteropoly metal coordination polymer material with high efficiency aiming at the problem of the technical shortage of converting carbon dioxide and an epoxy compound into the cyclic carbonate at present, and the catalyst can solve the problems of low catalytic efficiency, poor stability, harsh conditions and the like of other catalysts. In order to effectively solve the problems of the existing catalyst, the invention adopts a brand new design idea, effectively combines transition metals and rare earth metals, utilizes multi-metal concerted catalysis to achieve the purpose of high-efficiency catalysis, and designs and synthesizes a series of novel catalysts for catalyzing the reaction of carbon dioxide and cyclic carbonate.
The purpose of the invention is realized by the following technical scheme:
the preparation raw materials of the organic ligand (L) required by the synthesis catalyst comprise: methyl 5-allyl-3-methoxysalicylate, hydrazine hydrate and aromatic aldehyde, wherein the organic ligand L has the following structure:
the structural formula of the ligand is shown as above, wherein R in the formula1、R2、R3、R4、R5Is any of the same or different substituents (H, hydroxyl, methyl, ethyl, alkoxy, tertiary butyl, carboxyl, aldehyde group, dimethylamino, diethylamino, halogen, quaternary ammonium salt and the like) on the benzene ring.
Further, the preparation of the organic ligand (L) required by the synthesis of the catalyst is carried out in two steps, wherein in the first step, 5-allyl-3-methoxy methyl salicylate and hydrazine hydrate react in a solvent to generate 5-allyl-3-methoxy salicylyl hydrazide; and secondly, reacting the 5-allyl-3-methoxysalicylhydrazine with aromatic aldehyde in a solvent, and after the reaction is finished, filtering, washing and drying the product to obtain a white solid. Wherein, the process is represented by a chemical reaction formula as follows:
further, the catalyst synthesis steps are as follows: adding a certain amount of organic ligand L into a reactor, adding a proper amount of solvent, adding triethylamine according to a certain proportion, stirring for 30 minutes, adding a certain amount of metal salt, stirring until the metal salt is completely dissolved, adding a certain amount of rare earth salt, stirring until the solution is clear, filtering, putting a proper amount of filtrate into a 10ml container, reacting for a period of time at a certain temperature to obtain a crystalline catalyst material, and filtering, washing and drying the crystalline catalyst material for later use. Wherein the catalyst has the following structure:
wherein Ln is Sc, Y, Ce, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb;
M＝Zn，Cd，Fe，Ti，Co，Ni，Cr，Zr，Cu，Mn，Al，Mg。
further, the catalytic reaction step is as follows: weighing a catalyst, a cocatalyst and an epoxy compound, putting the catalyst, the cocatalyst and the epoxy compound into a high-pressure reaction kettle, filling carbon dioxide with certain pressure, reacting for a period of time at a certain temperature, finishing the reaction, cooling the reaction kettle to room temperature, and taking a sample to pass through1H NMR was quantitatively analyzed.
Further, in the first step of synthesizing the 5-allyl-3-methoxysalicylhydrazine, the feeding molar ratio of the methyl 5-allyl-3-methoxysalicylate to hydrazine hydrate is 1: 1 to 1: 10; the solvent is any one of methanol, ethanol, acetonitrile and dioxane or a mixture of the solvents in any proportion, the reaction temperature is controlled to be 25-80 ℃, and the reaction time is 2-12 hours.
Furthermore, in the second step of synthesizing the organic ligand L, the feeding molar ratio of the 5-allyl-3-methoxysalicylhydrazine to the aromatic aldehyde is 1: 1 to 1: 3; the solvent is any one of methanol, ethanol, acetonitrile and dioxane or a mixture of the solvents in any proportion, the reaction temperature is controlled to be 25-80 ℃, and the reaction time is 2-12 hours.
Further, the feeding molar ratio of the ligand L, the metal salt and the rare earth salt in the catalyst synthesis is 1: 1: 1 to 3: 2: 2; the solvent is any one of methanol, ethanol, acetonitrile and dioxane or a mixture of the solvents in any proportion, and the molar ratio of triethylamine to the ligand L is 1: 1 to 1: 6, controlling the reaction temperature to be 25-40 ℃ and the reaction time to be 12-72 h.
Further, in the catalyst reaction, the cocatalyst is one of PPN-Cl (triphenylphosphine) ammonium chloride, TBAB (tetrabutylammonium bromide), TBACl (tetrabutylammonium chloride), TBAI (tetrabutylammonium iodide) and TBAAc (tetrabutylammonium acetate); the molar ratio of the catalyst, the cocatalyst and the epoxy compound is 1: 10: 100 to 1: 100: 400, respectively; the pressure of the carbon dioxide is 0.1-1.5 MPa; the reaction temperature is 60-120 ℃.
The invention has the advantages and effects that:
1. the high-efficiency catalyst for the heteropoly metal coordination polymer, which is provided by the invention, is used as a catalyst for efficiently catalyzing carbon dioxide to synthesize cyclic carbonate, and has the characteristics of high catalytic efficiency, good selectivity, stable structure and the like.
2. The high-efficiency catalyst for the heteropoly metal coordination polymer provided by the invention has the advantages of no use of solvent, mild catalysis condition and wide application range, and has potential industrial utilization value.
3. The preparation method provided by the invention has the advantages of simplicity, mild conditions, easiness in control, energy conservation, environmental friendliness, high product purity, convenience in post-treatment and the like. The experimental results show that: the catalyst can realize the catalytic conversion of carbon dioxide and epoxy compounds under a mild condition, and the TOF is up to 30000h-1The conversion rate of the reaction is as high as 80-95%, and the method has potential industrial application value. The present invention relates to the field of catalytic chemistry.
Drawings
FIG. 1 is a schematic diagram of a catalytic reaction;
FIG. 2 is a schematic of coordination polymer catalyst synthesis;
FIG. 3 is a graph of the infrared spectra of an organic ligand and two different coordination polymers;
FIG. 4 is a graph of simulated XRD versus actual XRD test results for two different coordination polymers;
FIG. 5 is a thermogravimetric plot of two different coordination polymers;
FIG. 6 is a reaction product of propylene oxide and carbon dioxide1H NMR quantitative analysis chart;
FIG. 7 is a reaction product of epichlorohydrin and carbon dioxide1H NMR quantitative analysis chart
FIG. 8 is a reaction product of styrene oxide and carbon dioxide1H NMR quantitative analysis chart
Detailed Description
The following detailed description of the embodiments of the present invention, taken in conjunction with the accompanying drawings, enables those skilled in the art to better understand the advantages and features of the present invention, and thus, more clearly defines the scope of the invention. Please refer to fig. 1, 2, 3, 4, 5, 6, 7 and 8.
Example 1:
adding 2.22g of 5-allyl-3-methoxysalicylic acid methyl ester and 3.50g of hydrazine hydrate into a 25ml two-mouth bottle provided with a reflux condenser tube, a thermometer and a magneton, adding 10ml of methanol as a solvent, controlling the temperature at 60-65 ℃ for reaction for 12 hours, cooling to room temperature after the reaction is finished, separating out a white solid, and filtering, washing and drying the solid to obtain the white 5-allyl-3-methoxysalicylhydrazine solid.
Example 2:
adding 2.22g of 5-allyl-3-methoxysalicylhydrazine and 2.34g of 3, 5-di-tert-butylsalicylaldehyde into a 25ml two-mouth bottle provided with a reflux condenser tube, a thermometer and a magneton, adding 10ml of methanol as a solvent, controlling the temperature at 60-65 ℃ for reacting for 6h, cooling to room temperature after the reaction is finished, separating out a white solid, and filtering, washing and drying the solid to obtain the white organic ligand solid.
Example 3:
adding 0.01 mol% of catalyst, 0.75 mol% of cocatalyst TBAB and 10mmol of epoxy styrene as substrate into a 30ml high-pressure reaction kettle, charging 1MPa CO2Placing the reaction kettle in a constant-temperature heating jacket, heating to 120 ℃, reacting for 1h, cooling the reaction kettle to room temperature, discharging residual gas, sampling and utilizing1Quantitative analysis by H NMR showed 95% conversion and more than 99% selectivity.
Example 4:
adding 0.01 mol% of catalyst, 0.75 mol% of cocatalyst TBAB and 10mmol of propylene oxide as substrate into a 30ml high-pressure reaction kettle, charging 1MPa CO2Placing the reaction kettle in a constant-temperature heating jacket, heating to 120 ℃, reacting for 1h, cooling the reaction kettle to room temperature, discharging residual gas, sampling and utilizing1Quantitative analysis by H NMR showed that the conversion was 99% and the selectivity was greater than 99%.
Example 5:
adding 0.01 mol% of catalyst, 0.75 mol% of cocatalyst TBAB and 10mmol of substrate butylene oxide into a 30ml high-pressure reaction kettle, and charging 1MPa CO2Placing the reaction kettle in a constant-temperature heating jacket, heating to 120 ℃, and reacting for 1h, wherein the reaction is carried outThen cooling the reaction kettle to room temperature, discharging residual gas, sampling and utilizing1Quantitative analysis by H NMR showed 98% conversion and more than 99% selectivity.
Example 6:
adding 0.01 mol% of catalyst, 0.75 mol% of cocatalyst TBAB and 10mmol of epoxy hexane as substrate into a 30ml high-pressure reaction kettle, charging 1MPa CO2Placing the reaction kettle in a constant-temperature heating jacket, heating to 120 ℃, reacting for 1h, cooling the reaction kettle to room temperature, discharging residual gas, sampling and utilizing1Quantitative analysis by H NMR showed 94% conversion and more than 99% selectivity.
Example 7:
adding 0.01 mol% of catalyst, 0.75 mol% of cocatalyst TBAB and 10mmol of substrate epichlorohydrin into a 30ml high-pressure reaction kettle, charging 1MPa CO2Placing the reaction kettle in a constant-temperature heating jacket, heating to 120 ℃, reacting for 1h, cooling the reaction kettle to room temperature, discharging residual gas, sampling and utilizing1Quantitative analysis by H NMR showed that the conversion was 99% and the selectivity was greater than 99%.
Example 8:
adding 0.01 mol% of catalyst, 0.75 mol% of cocatalyst TBAB and 10mmol of epoxybromopropane as substrate into a 30ml high-pressure reaction kettle, charging 1MPa CO2Placing the reaction kettle in a constant-temperature heating jacket, heating to 120 ℃, reacting for 1h, cooling the reaction kettle to room temperature, discharging residual gas, sampling and utilizing1Quantitative analysis by H NMR showed 98% conversion and more than 99% selectivity.
Example 9:
adding 0.01 mol% of catalyst, 0.75 mol% of cocatalyst TBAB and 10mmol of substrate glycidol into a 30ml high-pressure reaction kettle, and charging 1MPa CO2Placing the reaction kettle in a constant-temperature heating jacket, heating to 120 ℃, reacting for 1h, cooling the reaction kettle to room temperature, discharging residual gas, sampling and utilizing1Quantitative analysis by H NMR showed that the conversion was 96% and the selectivity was greater than 99%.
Example 10:
adding 0.01 mol% of catalyst, 0.75 mol% of cocatalyst TBAB and 10mmol of substrate tert-butyl glycidyl ether into a 30ml high-pressure reaction kettle, and charging 1MPa CO2Placing the reaction kettle in a constant-temperature heating jacket, heating to 120 ℃, reacting for 1h, cooling the reaction kettle to room temperature, discharging residual gas, sampling and utilizing1Quantitative analysis by H NMR showed that the conversion was 90% and the selectivity was greater than 99%.
Example 11:
adding 0.01 mol% of catalyst, 0.75 mol% of cocatalyst TBAB and 10mmol of substrate vinyl glycidyl ether into a 30ml high-pressure reaction kettle, and charging 1MPa CO2Placing the reaction kettle in a constant-temperature heating jacket, heating to 120 ℃, reacting for 1h, cooling the reaction kettle to room temperature, discharging residual gas, sampling and utilizing1Quantitative analysis by H NMR showed 98% conversion and more than 99% selectivity.
Example 12:
adding 0.01 mol% of catalyst, 0.75 mol% of cocatalyst TBAB and 10mmol of substrate phenyl glycidyl ether into a 30ml high-pressure reaction kettle, and charging 1MPa CO2Placing the reaction kettle in a constant-temperature heating jacket, heating to 120 ℃, reacting for 1h, cooling the reaction kettle to room temperature, discharging residual gas, sampling and utilizing1Quantitative analysis by H NMR showed 95% conversion and more than 99% selectivity.
Example 13:
adding 0.01 mol% of catalyst, 0.75 mol% of cocatalyst TBAB and 10mmol of isopropyl glycidyl ether as substrate into a 30ml high-pressure reaction kettle, and charging 1MPa CO2Placing the reaction kettle in a constant-temperature heating jacket, heating to 120 ℃, reacting for 1h, cooling the reaction kettle to room temperature, discharging residual gas, sampling and utilizing1Quantitative analysis by H NMR showed 93% conversion and more than 99% selectivity.
Example 14:
adding 0.01 mol% of catalyst, 0.75 mol% of cocatalyst TBAB and 10mmol of substrate glycidyl methacrylate into a 30ml high-pressure reaction kettle, and charging 1MPa CO2Placing a reaction kettle inHeating to 120 deg.C in a constant temperature heating jacket, reacting for 1h, cooling the reaction kettle to room temperature, discharging residual gas, sampling, and utilizing1Quantitative analysis by H NMR showed that the conversion was 99% and the selectivity was greater than 99%.
The above examples merely represent several embodiments of the present invention, which are described in more detail and detail, but are not to be construed as limiting the scope of the patent. It should be noted that, for a person skilled in the art, many variations and modifications can be made without departing from the spirit of the invention, which falls within the scope of the invention. Therefore, the protection granted to this patent shall be subject to the appended claims.
Claims (8)
1. A high-efficiency catalyst of heteropolymetal for catalyzing carbon dioxide to synthesize cyclic carbonate is characterized in that the organic ligand L used for synthesizing the catalyst is prepared from the following raw materials: 5-allyl-3-methoxy methyl salicylate, hydrazine hydrate and aromatic aldehyde, wherein the organic ligand L has the structure:
in the formula R1、R2、R3、R4、R5The substituent groups are the same or different on the benzene ring and are any group of H, hydroxyl, methyl, ethyl, alkoxy, tert-butyl, carboxyl, aldehyde group, dimethylamino, diethylamino, halogen and quaternary ammonium salt;
wherein, the high-efficiency catalyst for catalyzing carbon dioxide to synthesize cyclic carbonate with heteropolymetal has the following structure:
wherein Ln = one of Sc, Y, Ce, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb;
m = one of Zn, Cd, Fe, Ti, Co, Ni, Cr, Zr, Cu, Mn, Al and Mg.
2. The high efficiency heteropoly metal catalyst for catalyzing carbon dioxide to synthesize cyclic carbonate with high efficiency according to claim 1, which is characterized in that the preparation of the organic ligand L used in the synthesis catalyst is carried out in two steps, wherein in the first step, 5-allyl-3-methoxy methyl salicylate and hydrazine hydrate are reacted in a solvent to generate 5-allyl-3-methoxy salicylhydrazine;
and secondly, reacting the 5-allyl-3-methoxysalicylhydrazine with aromatic aldehyde in a solvent, and after the reaction is finished, filtering, washing and drying the product to obtain a white solid.
3. The high efficiency catalyst for synthesizing cyclic carbonate from carbon dioxide with heteropoly metal as claimed in claim 1, wherein the synthesis steps of the catalyst are: adding a certain amount of organic ligand L into a reactor, adding a proper amount of solvent, adding triethylamine according to a certain proportion, stirring for 30 minutes, adding a certain amount of metal salt, stirring until the metal salt is completely dissolved, adding a certain amount of rare earth salt, stirring until the solution is clear, filtering, putting a proper amount of filtrate into a 10ml container, reacting for a period of time at a certain temperature to obtain a crystalline catalyst material, and filtering, washing and drying crystals for later use.
4. The high efficiency heteropoly metal catalyst for high efficiency catalysis of carbon dioxide to cyclic carbonate according to claim 1, which is characterized in that the step of carbon dioxide to cyclic carbonate is: weighing a catalyst, a cocatalyst and an epoxy compound, placing the catalyst, the cocatalyst and the epoxy compound in a high-pressure reaction kettle, charging 1 MPa-2MPa of carbon dioxide, reacting for a period of time at a certain temperature, finishing the reaction, cooling the reaction kettle to room temperature, and taking a sample to pass through1H NMR was quantitatively analyzed.
5. The heteropoly metal high-efficiency catalyst for efficiently catalyzing carbon dioxide to synthesize cyclic carbonate according to claim 2, which is characterized in that in the first step of synthesizing 5-allyl-3-methoxysalicylhydrazine, the feeding molar ratio of methyl 5-allyl-3-methoxysalicylate to hydrazine hydrate is 1: 1 to 1: 10; the solvent is any one of methanol, ethanol, acetonitrile and dioxane or a mixture of the solvents in any proportion, the reaction temperature is controlled to be 25-80 ℃, and the reaction time is 2-12 hours.
6. The high efficiency heteropoly metal catalyst for catalyzing carbon dioxide to synthesize cyclic carbonate in high efficiency according to claim 2, wherein in the second step of synthesizing organic ligand L, the feeding molar ratio of 5-allyl-3-methoxysalicylhydrazine to aromatic aldehyde is 1: 1 to 1: 3; the solvent is any one of methanol, ethanol, acetonitrile and dioxane or a mixture of the solvents in any proportion, the reaction temperature is controlled to be 25-80 ℃, and the reaction time is 2-12 hours.
7. The high efficiency heteropoly metal catalyst for high efficiency catalysis of carbon dioxide to cyclic carbonate according to claim 3, wherein the molar ratio of ligand L, metal salt and rare earth salt fed in the catalyst synthesis is 1: 1: 1 to 3: 2: 2; the solvent is any one of methanol, ethanol, acetonitrile and DMF or a mixture of the methanol, the ethanol, the acetonitrile and the DMF in any proportion, and the molar ratio of triethylamine to the ligand L is 1: 1 to 1: 6, controlling the reaction temperature to be 25-40 ℃ and the reaction time to be 12-72 h.
8. The high efficiency catalyst for catalyzing carbon dioxide to synthesize cyclic carbonate with heteropoly metals as claimed in claim 4, wherein the catalyst promoter in the catalyst reaction is one of PPN-Cl (bis (triphenylphosphine) ammonium chloride), TBAB (tetrabutylammonium bromide), TBACl (tetrabutylammonium chloride), TBAI (tetrabutylammonium iodide) and TBAAc (tetrabutylammonium acetate); the molar ratio of the catalyst, the cocatalyst and the epoxy compound is 1: 10: 100 to 1: 100: 400, respectively; the pressure of the carbon dioxide is 0.1-1.5 MPa; the reaction temperature is 60-120 ℃.
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