Method and catalyst for synthesizing oxazolidinone compound based on carbon dioxide and hydramine

Abstract

The invention provides a method and a catalyst for synthesizing an oxazolidinone compound based on carbon dioxide and alcohol amine, the oxazolidinone compound prepared based on carbon dioxide and alcohol amine, and application of a cerium-based composite oxide in preparation of the oxazolidinone compound based on carbon dioxide and alcohol amine. The method comprises the following steps: taking carbon dioxide and alkylol amine as raw materials, and reacting the alkylol amine with the carbon dioxide under the action of a solid catalyst to generate the oxazolidinone compound, wherein the solid catalyst comprises a cerium-based composite oxide, and the reaction process comprises liquid-phase carboxylation and cyclization dehydration. According to the method provided by the invention, the catalyst can be easily separated from the product, and the reactant alcohol amine has a relatively high conversion rate.

Description

Technical Field

[0001] The present application relates to the technical field of catalytic conversion and utilization of carbon dioxide, and in particular to a method and catalyst for synthesizing oxazolidinone compounds based on carbon dioxide and alcohol amines, oxazolidinone compounds prepared based on carbon dioxide and alcohol amines, and the use of cerium-based composite oxides in the preparation of oxazolidinone compounds based on carbon dioxide and alcohol amines. Background Art

[0002] The abuse and misuse of antibiotics have led to the rapid development of antibiotic-resistant bacteria of various antibiotics and antibacterial drugs, which seriously threatens the life and health of patients with infectious diseases. Oxazolidinone antibacterial drugs (such as linezolid, redezolide, etc.) are a new type of chemical fully synthetic antibacterial drugs after sulfonamides and fluoroquinolones. They exert their antibacterial effects by inhibiting bacterial protein synthesis. Their core unit is oxazolidinone. The reaction of carbon dioxide with nitrogen-containing organic matter to prepare oxazolidinone antibacterial drugs can not only eliminate the greenhouse effect caused by carbon dioxide, but also be converted into high-value-added drugs. In theory, the carboxyl cyclization of amino alcohols and carbon dioxide is the simplest green and environmentally friendly way to convert carbon dioxide into oxazolidinone compounds. On the one hand, amino alcohols (derivatives of various amino acids) are ideal chemicals that are easy to obtain, inexpensive and generally safe; on the other hand, the cyclization of amino alcohols and carbon dioxide only produces water as a stoichiometric byproduct, which is an ideal green synthesis route. Electrophilic reagents such as trialkylphosphines, high-energy phosphorus compounds or strong bases such as DBU (1,8-diazacyclo[5.4.0]undec-7-ene), trialkylamines and guanidines, and homogeneous metal organic catalysts such as organic titanium complexes can promote the synthesis of oxazolidinone compounds from carbon dioxide and alcohol amines, but these methods use a large amount of condensing agents, which leads to a sharp increase in costs and forms a large amount of waste (such as alkylphosphine oxides, etc.), which is difficult to remove from the product. Therefore, it is urgent to develop a reaction system for the synthesis of oxazolidinone compounds that is easy to separate and highly selective. Summary of the invention

[0003] Based on this, the present application provides a method and catalyst for synthesizing oxazolidinone compounds based on carbon dioxide and alcohol amines, oxazolidinone compounds prepared based on carbon dioxide and alcohol amines, and the use of cerium-based composite oxides in the preparation of oxazolidinone compounds based on carbon dioxide and alcohol amines. The preparation method can easily separate and remove the catalyst from the system after the reaction.

[0004] The first aspect of the present application provides a method for synthesizing oxazolidinone compounds based on carbon dioxide and alcohol amine, comprising:

[0005] Carbon dioxide and alcohol amine are used as raw materials, and under the action of a solid catalyst, the alcohol amine and the carbon dioxide react to generate the oxazolidinone compound; wherein the solid catalyst comprises a cerium-based composite oxide, and the reaction process comprises liquid phase carboxylation and cyclodehydration.

[0006] In some embodiments of the present application, the cerium-based composite oxide includes one or more of a first cerium-based composite oxide, a second cerium-based composite oxide, and a third cerium-based composite oxide;

[0007] The first cerium-based composite oxide includes CeM1 x1 O y1 , wherein M1 includes a first metal cation different from Ce, and the values ​​of x1 and y1 make the CeM1 x1 O y1 The algebraic sum of the valences of is zero;

[0008] The second cerium-based composite oxide includes CeO 2 -M2 x2 O y2 , wherein M2 includes a second metal cation different from Ce, and the values ​​of x2 and y2 are such that M2 x2 O y2 The algebraic sum of the valences of is zero;

[0009] The third cerium-based composite oxide includes M3'-CeM3 x3 O y3 , wherein M3 includes a third metal cation different from Ce, M3' includes a fourth metal cation, and the values ​​of x3 and y3 make the CeM3 x3 O y3 The algebraic sum of the valences of is zero;

[0010] Optionally, the M1, the M2 and the M3 each independently include Zn 2+ ,La 3+ 、In 3+ 、Al 3+ and Zr 4+ At least one of;

[0011] Optionally, the M3' comprises Na + , Li + , Ba 2+ or Co x’+ At least one of .

[0012] In some embodiments of the present application, one or more of the following conditions are met:

[0013] (1) CeO 2 -M2 x2O y2 In it, the molar ratio of Ce to M2 is denoted as Ce / M2, then 0 < Ce / M2 ≤ 1000, optionally 0 < Ce / M2 ≤ 10, and further optionally 0.25 < Ce / M2 ≤ 4;

[0014] (2) The M3’-CeM3 as described above x3 O y3 In it, the molar ratio of M3’ to Ce is denoted as M3’ / Ce, then 0 < M3’ / Ce ≤ 1, optionally 0 < M3’ / Ce ≤ 0.5, and further optionally 0 < M3’ / Ce ≤ 0.1;

[0015] Optionally, the third cerium-based composite oxide is M3’-CeZr x3 O 2 , where the molar ratio of Ce to Zr is Ce / Zr, then 0 < Ce / Zr ≤ 1000, optionally 0 < Ce / Zr ≤ 10, and further optionally 0.25 < Ce / Zr ≤ 4.

[0016] In some embodiments of the present application, one or more of the following conditions are satisfied:

[0017] (1) The first cerium-based composite oxide is CeZr x1 O 2 , where the molar ratio of Ce to Zr is denoted as (Ce / Zr)’, then 0 < (Ce / Zr)’ ≤ 1000, optionally 0 < (Ce / Zr)’ ≤ 10, and further optionally 0.25 < (Ce / Zr)’ ≤ 4;

[0018] (2) The second cerium-based composite oxide includes one or more of CeO 2 -ZnO, CeO 2 -La 2 O 3 , CeO 2 -In 2 O 3 and CeO 2 -Al 2 O 3 .

[0019] In some embodiments of the present application, the alkanolamine includes one or more of substituted or unsubstituted ethanolamine and substituted or unsubstituted propanolamine;

[0020] Optionally, the alkanolamine includes one or more of ethanolamine, 3-amino-1,2-propanediol, and propanolamine.

[0021] In some embodiments of the present application, the reaction is carried out in a solution of the alkanolamine;

[0022] Optionally, the solvent in the solution includes one or more of acetonitrile, water, 1,4-dioxane and mesitylene, and further may be acetonitrile.

[0023] In some embodiments of the present application, one or more of the following conditions are met:

[0024] (1) The reaction temperature is 100°C to 300°C, optionally 100°C to 240°C, and further optionally 120°C to 220°C;

[0025] (2) The reaction time is 0.5h~100h, optionally 0.5h~60h, further optionally 0.5h~48h;

[0026] (3) During the reaction, the pressure of the carbon dioxide is 1 atm to 40 atm, optionally 1 atm to 20 atm, and further optionally 2 atm to 16 atm;

[0027] (4) The reaction is carried out under stirring conditions, and the stirring speed is 200 rpm to 1500 rpm.

[0028] In some embodiments of the present application, the ratio of the amount of the alcohol amine to the solid catalyst is (100-1500):(4-700), optionally (200-1300):(4-700), and further optionally (300-1300):(4-700);

[0029] Optionally, the amount of the alcoholamine is 100 mg to 1500 mg, optionally 200 to 1300 mg, further optionally 300 mg to 1300 mg;

[0030] Optionally, the amount of the solid catalyst used is 4 mg to 700 mg, and optionally 34 mg to 684 mg.

[0031] The second aspect of the present application provides an oxazolidinone compound prepared based on carbon dioxide and alcohol amine, which is prepared by the preparation method described in the first aspect of the present application.

[0032] The third aspect of the present application provides an application of a cerium-based composite oxide in the preparation of oxazolidinone compounds based on carbon dioxide and alcohol amines, wherein the cerium-based composite oxide is the cerium-based composite oxide used in the preparation method described in the first aspect of the present application.

[0033] The preparation method provided in the present application adopts a specific solid catalyst - a cerium-based composite oxide. The catalyst can exist in a solid form before and after the reaction. Therefore, compared with traditional homogeneous metal organic catalysts, it is easy to separate and remove from the product after the reaction. At the same time, the catalyst also has a high selectivity for the reaction of alcoholamines and carbon dioxide, thereby enabling the alcoholamines to have a higher conversion rate. DETAILED DESCRIPTION

[0034] In order to facilitate understanding of the present application, the present application will be described more comprehensively below. However, the present application can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present application more thorough and comprehensive.

[0035] For simplicity, this application only explicitly discloses some numerical ranges. However, any lower limit can be combined with any upper limit to form an unclearly recorded range; and any lower limit can be combined with other lower limits to form an unclearly recorded range, and any upper limit can be combined with any other upper limit to form an unclearly recorded range. In addition, although not clearly recorded, each point or single value between the range endpoints is included in the range. Thus, each point or single value can be combined with any other point or single value as its own lower limit or upper limit or with other lower limits or upper limits to form an unclearly recorded range.

[0036] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art to which this application belongs. The terms used herein in the specification of this application are for the purpose of describing specific embodiments only and are not intended to limit this application. It should be noted that, unless otherwise specified, the term "and / or" used herein includes any and all combinations of one or more related listed items, and "above" and "below" are inclusive of the number, and the meaning of "multiple" in "one or more" is more than two.

[0037] Herein, when it comes to a numerical interval (i.e., a numerical range), unless otherwise specified, the distribution of the optional numerical values ​​within the numerical interval is considered to be continuous and includes the two numerical endpoints (i.e., the minimum and maximum values) of the numerical interval, and each numerical value between the two numerical endpoints. Unless otherwise specified, when a numerical interval only refers to integers within the numerical interval, including the two endpoint integers of the numerical range, and each integer between the two endpoints, is equivalent to directly listing each integer. When multiple numerical ranges are provided to describe features or characteristics, these numerical ranges can be combined. In other words, unless otherwise specified, the numerical ranges disclosed herein should be understood to include any and all sub-ranges included therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, a percentage, a ratio, etc. "Numerical interval" allows broadly including numerical interval types such as percentage intervals, ratio intervals, and ratio intervals.

[0038] In this article, if there are multiple steps involved in the method flow, unless there is a clear different description in this article, there is no strict order restriction for the execution of these steps, and they can be executed in other orders than described. Moreover, any step can include multiple sub-steps or multiple stages, and these sub-steps or stages are not necessarily executed at the same time, but can be executed at different times, and their execution order is not necessarily sequential, but can be executed in turn, alternating or simultaneously with other steps or parts of sub-steps or stages of other steps.

[0039] The above application content of the present application is not intended to describe each disclosed embodiment or each implementation in the present application. The following description more specifically illustrates exemplary embodiments. In many places throughout the application, guidance is provided by a series of examples, which can be used in various combinations. In each example, enumeration is only used as a representative group and should not be interpreted as exhaustive.

[0040] At present, in the reaction of converting the carboxyl cyclization of amino alcohols and carbon dioxide into oxazolidinone compounds, commonly used catalysts are homogeneous metal organic catalysts such as trialkylphosphines, high-energy phosphorus compounds or strong bases such as DBU (1,8-diazacyclo[5.4.0]undec-7-ene), trialkylamines and guanidines, and organic titanium complexes. Although homogeneous metal organic catalysts can promote the synthesis of oxazolidinone compounds from carbon dioxide and alcohol amines, such catalysts and reactants are usually in liquid phase, and will mix with reactants and products in liquid phase during liquid phase reactions, and are prone to form a large number of by-products (such as alkylphosphine oxides, etc.), resulting in the catalyst itself and the by-products being difficult to remove from the product after the reaction. In view of this, the inventors proposed the following technical solution of this application.

[0041] In a first aspect, the present application provides a method for synthesizing oxazolidinone compounds based on carbon dioxide and alcohol amine, which may include the following step S1:

[0042] S1: using carbon dioxide and alcohol amine as raw materials, under the action of a solid catalyst, the alcohol amine and the carbon dioxide are reacted to generate the oxazolidinone compound; wherein the solid catalyst comprises a cerium-based composite oxide, and the reaction process comprises liquid phase carboxylation and cyclodehydration.

[0043] The above preparation method provided in the present application adopts a specific solid catalyst - cerium-based composite oxide, which can exist in solid form before and after the reaction. Therefore, compared with traditional homogeneous metal organic catalysts, it is easy to separate and remove from the product after the reaction. At the same time, the catalyst also has a high selectivity for the reaction of alcoholamine and carbon dioxide, so that the alcoholamine can have a higher conversion rate.

[0044] Thus, the present application converts alcohol amines into oxazolidinone compounds through the action of a specific solid catalyst, the catalyst is cheap and readily available, and the catalyst and the product are easy to separate. Based on this, the preparation method of oxazolidinone compounds based on alcohol amines provided in the present application has high research value and application prospects.

[0045] It should be noted that the “cerium-based composite oxide” mentioned in the present application refers to a composite oxide based on cerium element and formed together with one or more other metal elements.

[0046] In some embodiments, the cerium-based composite oxide includes one or more of a first cerium-based composite oxide, a second cerium-based composite oxide, and a third cerium-based composite oxide;

[0047] The first cerium-based composite oxide includes CeM1 x1 O y1 , wherein M1 includes a first metal cation different from Ce, and the values ​​of x1 and y1 make the CeM1 x1 O y1 The algebraic sum of the valences of is zero;

[0048] The second cerium-based composite oxide includes CeO 2 -M2 x2 O y2 , wherein M2 includes a second metal cation different from Ce, and the values ​​of x2 and y2 are such that M2 x2 O y2 The algebraic sum of the valences of is zero;

[0049] The third cerium-based composite oxide includes M3'-CeM3 x3 O y3, wherein, M3 includes a third metal cation different from Ce, M3' includes a fourth metal cation, and the values of x3 and y3 make the algebraic sum of the valences of the CeM3 x3 O y3 equal to zero.

[0050] It should be noted that "CeO 2 -M2 x2 O y2 " in this application refers to a cerium-based composite oxide formed by chemical bonding between CeO 2 and M2 x2 O y2 ; "M3'-CeM3 x3 O y3 " refers to a cerium-based composite oxide in which a third metal cation M3' is combined and loaded on CeM3 x3 O y3 .

[0051] In some embodiments, M1, M2, and M3 each independently include at least one of Zn 2+ , La 3+ , In 3+ , Al 3+ , and Zr 4+ .

[0052] In some embodiments, M3' includes at least one of Na + , Li + , Ba 2+ , or Co x’+ .

[0053] In some embodiments, in CeO 2 -M2 x2 O y2 , if the molar ratio of Ce to M2 is denoted as Ce / M2, then 0 < Ce / M2 ≤ 1000. For example, Ce / M2 can be 0.5, 1, 10, 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000 or within the range composed of any of the above values. Optionally, 0 < Ce / M2 ≤ 10, and further optionally, 0.25 < Ce / M2 ≤ 4. In this way, CeO 2 -M2 x2 O y2 can have high selectivity and catalytic performance, and the alkanolamine can have a high conversion rate.

[0054] In some embodiments, the M3'-CeM3 x3 O y3In it, the molar ratio of M3' to Ce is denoted as M3' / Ce, and 0 < M3' / Ce ≤ 1. For example, M3' / Ce can be 0.5%, 1%, 5%, 10%, 50%, 80%, 100% or within the range composed of any of the above values. Optionally, 0 < M3' / Ce ≤ 0.5, and further optionally, 0 < M3' / Ce ≤ 0.1. Thus, M3'-CeM3 x3 O y3 has high selectivity and catalytic performance, enabling the alkanolamine to have a high conversion rate.

[0055] In some embodiments, the third cerium-based composite oxide is M3'-CeZr x3 O 2 , where the molar ratio of Ce to Zr is denoted as Ce / Zr, and 0 < Ce / Zr ≤ 1000. For example, Ce / Zr can be 0.5, 1, 3, 10, 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000 or within the range composed of any of the above values. Optionally, 0 < Ce / Zr ≤ 10, and further optionally, 0.25 < Ce / Zr ≤ 4, and particularly optionally, 3. Thus, M3'-CeZr x3 O 2 has high selectivity and catalytic performance, enabling the alkanolamine to have a high conversion rate.

[0056] In some embodiments, the first cerium-based composite oxide is CeZr x1 O 2 , where the molar ratio of Ce to Zr is denoted as (Ce / Zr)', and 0 < (Ce / Zr)' ≤ 1000. For example, (Ce / Zr)' can be 0.5, 1, 10, 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000 or within the range composed of any of the above values. Optionally, 0 < (Ce / Zr)' ≤ 10, and further optionally, 0.25 < (Ce / Zr)' ≤ 4, and particularly optionally, 3. Thus, CeZr x1 O 2 has high selectivity and catalytic performance, enabling the alkanolamine to have a high conversion rate.

[0057] In some embodiments, the second cerium-based composite oxide includes CeO 2 -ZnO, CeO 2 -La 2 O 3 、CeO 2 -In 2 O 3 and CeO 2 -Al 2O 3 One or more of .

[0058] In some embodiments, the alcoholamine includes one or more of substituted or unsubstituted ethanolamine, substituted or unsubstituted propanolamine.

[0059] In some embodiments, the alcoholamine includes one or more of ethanolamine, 3-amino-1,2-propanediol, and propanolamine.

[0060] In some embodiments, the reaction is carried out in a solution of an alcoholamine.

[0061] In some embodiments, the solvent in the solution includes one or more of acetonitrile, water, 1,4-dioxane and mesitylene, and acetonitrile may be selected.

[0062] In some embodiments, the reaction may include the following steps S10:

[0063] S10: Add amine, solvent and solid catalyst into the reactor and seal it. 2 Replacement to remove the residual air in the reactor; after the replacement is completed, high-purity CO is introduced into the reactor at room temperature 2 , and then the temperature is raised to the specified reaction temperature to react.

[0064] In some embodiments, the reactor may be an autoclave reactor.

[0065] In some embodiments, high purity CO 2 The number of replacements can be 5 to 8 times.

[0066] In some embodiments, the reaction is carried out under stirring, and the stirring speed is 200 rpm to 1500 rpm. For example, the speed can be 400 rpm, 600 rpm, 800 rpm, 1000 rpm, 1200 rpm, 1500 rpm or within the range of any of the above values. Optionally, the speed is 1000 rpm.

[0067] In some embodiments, the ratio of the amount of the alcohol amine to the solid catalyst is (100-1500): (4-700). For example, the ratio can be 100:700, 305:684, 610:342, 1500:700, 750:171, 915:34, 100:4, 1220:17, 1500:4 or within the range of any of the above values. It can be (200-1300): (34-684), and further can be (300-1300): (34-684). In this way, it is beneficial to promote the catalytic performance of the solid catalyst and enable the alcohol amine to have a higher conversion rate.

[0068] In some embodiments, the amount of the alcoholamine is 100 mg to 1500 mg. For example, the amount of the alcoholamine can be 100 mg, 305 mg, 610 mg, 750 mg, 915 mg, 1220 mg, 1500 mg, or within the range of any of the above values. It can be 200 to 1300 mg, and further can be 300 mg to 1300 mg.

[0069] In some embodiments, the amount of the solid catalyst is 4 mg to 700 mg. For example, the amount of the solid catalyst can be 4 mg, 8 mg, 17 mg, 34 mg, 171 mg, 342 mg, 684 mg, 700 mg, or within the range of any of the above values. It can be selected to be 34 mg to 684 mg. In this way, it is beneficial to promote the catalytic performance of the solid catalyst and enable the alcohol amine to have a higher conversion rate.

[0070] In some embodiments, the reaction temperature is 100°C to 300°C. For example, the temperature may be 120°C, 140°C, 160°C, 180°C, 200°C, 220°C, or any range thereof. It may be 100°C to 240°C, and further 120°C to 220°C. This is conducive to a higher conversion rate of the alcohol amine.

[0071] It should be noted that the reaction temperature refers to the real-time temperature of the reactor.

[0072] In some embodiments, the reaction time is 0.5h to 100h. For example, the reaction time can be 0.5h, 1h, 2h, 4h, 8h, 12h, 24h, 48h or within the range of any of the above values. It can be 0.5h to 60h, and further 0.5h to 48h. In this way, it is beneficial to make the alcohol amine have a higher conversion rate.

[0073] In some embodiments, during the reaction, the pressure of the carbon dioxide is 1 atm to 40 atm. For example, the pressure of the carbon dioxide may be 1 atm, 2 atm, 4 atm, 6 atm, 8 atm, 10 atm, 12 atm, 14 atm, 16 atm, or any range thereof. It may be 1 atm to 20 atm, further 2 atm to 16 atm, and particularly 8 atm. This is beneficial for achieving a higher conversion rate of the alcohol amine.

[0074] It should be noted that the cerium-based composite oxide described in the present application may be a commercial product or a commercially available product, or may be prepared by a traditional method or a well-known method.

[0075] In some embodiments, the preparation method of the cerium-based composite oxide includes a coprecipitation method, an impregnation method, etc. Optionally, the cerium-based composite oxide is prepared by a coprecipitation method.

[0076] In some embodiments, the step of preparing the first cerium-based composite oxide and / or the second cerium-based composite oxide by coprecipitation may include:

[0077] S20: after uniformly mixing the cerium salt solution and the non-cerium metal salt solution, continuously stirring and dropping an alkaline reagent until the solution becomes alkaline and a precipitate is completely precipitated; after a first calcination treatment of the precipitate, a first cerium-based composite oxide and / or a second cerium-based composite oxide is obtained.

[0078] In some embodiments, before the precipitate is subjected to the first calcination treatment, the precipitate may be subjected to one or more steps of static aging, filtering, washing, drying, etc.

[0079] In some embodiments, the alkaline agent includes one or more of ammonia, NaOH, or KOH.

[0080] In some embodiments, the cerium source in the cerium salt solution includes one or more of cerium nitrate, cerium ammonium nitrate, and cerium chloride, and may be cerium ammonium nitrate.

[0081] In some embodiments, the non-cerium metal source in the non-cerium metal salt solution includes one or more of a nitrate, an oxynitrate, and a chloride of the non-cerium metal. In other embodiments, the non-cerium metal includes at least one of Zn, La, In, Al, and Zr, which may be Zr. For example, when the non-cerium metal is zirconium, the zirconium source includes zirconium oxynitrate and / or zirconium chloride, which may be zirconium oxynitrate.

[0082] It can be understood that in the above preparation step S20, by adjusting the ratio of the added cerium source and the non-cerium metal source and the pH of the solution during preparation, the first cerium-based composite oxide and / or the second cerium-based composite oxide with different (Ce / non-cerium metal) molar ratios can be obtained.

[0083] In some embodiments, in the above preparation step S20, the mixed solution of the cerium salt solution and the non-cerium metal salt solution may be heated to promote the precipitation of the precipitate. Optionally, the heating temperature is 0-100° C., and the continuous stirring time is 1 h-12 h.

[0084] In some embodiments, the temperature of the first calcination treatment of the precipitate is 300°C to 1000°C. For example, the temperature of the first calcination treatment can be 300°C, 400°C, 600°C, 700°C, 750°C, 800°C, 850°C, 900°C, 1000°C, or within the range of any of the above values. It can be selected from 400°C to 900°C, and further selected from 400°C to 850°C. In this way, the prepared cerium-based composite oxide has higher selectivity and catalytic performance.

[0085] In some embodiments, based on step S20, the third cerium-based composite oxide M3'-CeZr x3 O 2 The following steps can be used for preparation:

[0086] S30: impregnating the first cerium-based composite oxide and / or the second cerium-based composite oxide with a third metal cation M3', so that the third metal cation M3' is combined and loaded on the first cerium-based composite oxide and / or the second cerium-based composite oxide, and then drying, performing a second calcination treatment, etc. to obtain M3'-CeZr x3 O 2 .

[0087] In some embodiments, the temperature of the second calcination treatment is 300°C to 1000°C. For example, the temperature of the second calcination treatment may be 300°C, 400°C, 600°C, 700°C, 750°C, 800°C, 850°C, 900°C, 1000°C, or any range thereof. It may be 400°C to 900°C, and further 400°C to 850°C. In this way, the prepared cerium-based composite oxide may have higher selectivity and catalytic performance.

[0088] It can be understood that in the above step S30, by adjusting the molar concentration (molar percentage) of the third metal ion M3', the third cerium-based composite oxide M3'-CeZr with different M3' / Ce molar ratios can be obtained. x3 O 2 .

[0089] In a second aspect, the present application provides an oxazolidinone compound prepared based on carbon dioxide and alcohol amine, which is prepared by the preparation method described in the first aspect of the present application.

[0090] In a third aspect, the present application provides an application of a cerium-based composite oxide in the preparation of oxazolidinone compounds based on carbon dioxide and alcohol amines, wherein the cerium-based composite oxide is the cerium-based composite oxide used in the preparation method described in the first aspect of the present application.

[0091] The following are specific examples, which more specifically describe the contents disclosed in this application, and these examples are only for illustrative purposes, because it is obvious to those skilled in the art that various modifications and variations are made within the scope of the disclosure of this application. Unless otherwise stated, all parts, percentages, and ratios reported in the following examples are based on weight, and all reagents used in the examples are commercially available or synthesized according to conventional methods and can be used directly without further processing, and the instruments used in the examples are commercially available.

[0092] Example 1

[0093] Preparation of Cerium-based Composite Oxides

[0094] After 0.2 mol / L cerium ammonium nitrate solution and 0.2 mol / L zirconium oxynitrate solution were mixed evenly with a Ce / Zr molar ratio of 3:1, 1 mol / L ammonia water was added dropwise until the solution pH = 10. After vigorous stirring at room temperature for 1 h, a hydroxide precipitate was obtained. After multiple washings, it was dried at 110 °C for 12 h. Finally, it was placed in a muffle furnace and calcined at 700 °C for 3 h to obtain a cerium-based composite oxide, which was recorded as CeZrO 2 (3:1)-700, wherein 3:1 represents the Ce / Zr molar ratio of 3:1, and 700 represents the calcination temperature.

[0095] Preparation of oxazolidinone

[0096] The reaction of carbon dioxide and alcohol amine to prepare oxazolidinone compounds is carried out in a liquid phase batch reactor. The specific operation process is as follows: 34 mg of CeZrO prepared above 2 (3:1)-700, 610 mg ethanolamine and 16.4 g acetonitrile were added to a polytetrafluoroethylene liner and sealed; 8 atm of high-purity CO 2 Replace 5 times to remove the residual air in the kettle; after the replacement is completed, 8 atm high-purity CO is introduced into the reactor at room temperature 2 Then the temperature was raised to 140 °C and stirred at 1000 rpm for 2 h. The reaction products were detected by gas chromatography, and the results are shown in Table 1.

[0097] Embodiment 2~5

[0098] The preparation method of the cerium-based composite oxide and the preparation process of oxazolidinone in Examples 2 to 5 are basically the same as those in Example 1, except that the Ce / Zr molar ratios in the solutions in Examples 2 to 5 are 1:3, 1:1, 2:1 and 4:1, respectively, and the Ce / Zr molar ratios in the prepared cerium-based composite oxides measured by XRF (X-ray fluorescence spectroscopy) are 1:3, 1.06:1, 2.17:1 and 3.96:1. The reaction product was detected by gas chromatography, and the results are shown in Table 1.

[0099] Table 1 Effect of composition on the catalytic performance of the reaction of carbon dioxide and ethanolamine to prepare 2-oxazolidinone

[0100]

[0101] It can be seen that by controlling the Ce / Zr molar ratio in the cerium-based composite oxide within a more appropriate range, ethanolamine can have a higher conversion rate and 2-oxazolidinone can have a higher selectivity, that is, the cerium-based composite oxide has a higher catalytic performance; and the catalytic performance is better when the Ce / Zr molar ratio is (1~4):1.

[0102] Embodiment 6-12

[0103] The preparation methods of the cerium-based composite oxides and the preparation process of oxazolidinone in Examples 6 to 12 are substantially the same as those in Example 1, except that the calcination temperatures for preparing the cerium-based composite oxides in Examples 6 to 12 are 400°C, 500°C, 600°C, 750°C, 800°C, 850°C and 900°C, respectively. The reaction products were detected by gas chromatography, and the results are shown in Table 2.

[0104] Table 2 Effect of calcination temperature on the performance of cerium-based composite oxide CeZrO 2 (3:1) Effect of catalytic performance

[0105]

[0106] It can be seen that by controlling the calcination temperature in the preparation of cerium-based composite oxides within a more appropriate range, ethanolamine can have a higher conversion rate and 2-oxazolidinone can have a higher selectivity, that is, the cerium-based composite oxide has a higher catalytic performance; and the catalytic performance is better when the calcination temperature is 500°C~900°C.

[0107] Embodiments 13 to 19

[0108] The preparation methods of the cerium-based composite oxides and the preparation processes of oxazolidinone in Examples 13 to 19 are substantially the same as those in Example 9, except that: the cerium-based composite oxides CeZrO 2The reaction time of (3:1)-750 catalyzing carbon dioxide and ethanolamine to prepare 2-oxazolidinone was 0.5 h, 1 h, 4 h, 8 h, 12 h, 24 h, and 48 h, respectively. The reaction products were detected by gas chromatography, and the results are shown in Table 3.

[0109] Table 3 Effect of reaction time on the cerium-based composite oxide CeZrO 2 Effect of (3:1)-750 on catalytic performance

[0110]

[0111] It can be seen that by 2 The reaction time of (3:1)-750 catalyzing carbon dioxide and ethanolamine to prepare 2-oxazolidinone is controlled within a suitable range, which can enable ethanolamine to have a higher conversion rate and 2-oxazolidinone to have a higher selectivity, that is, the cerium-based composite oxide has a higher catalytic performance; and the catalytic performance is better when the reaction time is 2h~48h.

[0112] Embodiment 20-23

[0113] The preparation method of the cerium-based composite oxide and the preparation process of oxazolidinone in Examples 20 to 23 are substantially the same as those in Example 9, except that: the cerium-based composite oxide CeZrO in Examples 20 to 23 is 2 The reaction temperatures for preparing 2-oxazolidinone by catalyzing carbon dioxide and ethanolamine with (3:1)-750 were 120 ℃, 160 ℃, 180 ℃ and 200 ℃, respectively. The reaction products were detected by gas chromatography, and the results are shown in Table 4.

[0114] Table 4 Effect of reaction temperature on CeZrO 2 Effect of (3:1)-750 on catalytic performance

[0115]

[0116] It can be seen that by 2 The reaction temperature of (3:1)-750 catalyzing carbon dioxide and ethanolamine to prepare 2-oxazolidinone is controlled within a more appropriate range, which can enable ethanolamine to have a higher conversion rate and 2-oxazolidinone to have a higher selectivity, that is, the cerium-based composite oxide has a higher catalytic performance; and the catalytic performance is better when the reaction temperature is 140°C~200°C.

[0117] Embodiment 24

[0118] The preparation method of the cerium-based composite oxide and the preparation process of oxazolidinone in Example 24 are basically the same as those in Example 21, except that: the cerium-based composite oxide CeZrO in Example 24 2The amount of (3:1)-750 added was 17 mg. The reaction product was detected by gas chromatography, and the results are shown in Table 5.

[0119] Embodiment 25

[0120] The preparation method of the cerium-based composite oxide and the preparation process of oxazolidinone in Example 25 are basically the same as those in Example 22, except that: the cerium-based composite oxide CeZrO in Example 25 2 The amount of (3:1)-750 added was 8 mg. The reaction product was detected by gas chromatography, and the results are shown in Table 5.

[0121] Embodiment 26

[0122] The preparation method of the cerium-based composite oxide and the preparation process of oxazolidinone in Example 26 are basically the same as those in Example 23, except that: the cerium-based composite oxide CeZrO in Example 25 2 The amount of (3:1)-750 added was 4 mg. The reaction product was detected by gas chromatography, and the results are shown in Table 5.

[0123] Table 5 CeZrO 2 (3:1)-750 Catalytic Performance

[0124]

[0125] It can be seen that by controlling the ratio of ethanolamine to catalyst within a more appropriate range, ethanolamine can have a higher conversion rate and 2-oxazolidinone can have a higher selectivity, that is, the cerium-based composite oxide has a higher catalytic performance.

[0126] Embodiments 27 to 31

[0127] The preparation methods of the cerium-based composite oxides and the preparation process of oxazolidinone in Examples 27 to 31 are substantially the same as those in Example 9, except that: the cerium-based composite oxides CeZrO 2 (3:1)-750 catalyzes the CO reaction of carbon dioxide and ethanolamine to produce 2-oxazolidinone 2 The reaction pressures were 2 atm, 4 atm, 6 atm, 10 atm and 12 atm respectively. The reaction products were detected by gas chromatography, and the results are shown in Table 6.

[0128] Table 6 Effect of carbon dioxide pressure on CeZrO 2 Effect of (3:1)-750 on catalytic performance

[0129]

[0130] It can be seen that by 2(3:1)-750 catalyzes the CO reaction of carbon dioxide and ethanolamine to produce 2-oxazolidinone 2 When the reaction pressure is controlled within a suitable range, ethanolamine can have a higher conversion rate and 2-oxazolidinone can have a higher selectivity, that is, the cerium-based composite oxide has a higher catalytic performance; and the catalytic performance is better when the reaction pressure is 4 atm ~12 atm.

[0131] Embodiment 32-35

[0132] The preparation method of the cerium-based composite oxide and the preparation process of oxazolidinone in Examples 32 to 35 are substantially the same as those in Example 14, except that: the cerium-based composite oxide CeZrO in Examples 32 to 35 is 2 The addition amount of ethanolamine in the preparation of 2-oxazolidinone by (3:1)-750 catalyzing carbon dioxide and ethanolamine was 305 mg, 458 mg, 915 mg and 1220 mg respectively. The reaction products were detected by gas chromatography, and the results are shown in Table 7.

[0133] Table 7 Effect of ethanolamine addition on CeZrO 2 Effect of (3:1)-750 on catalytic performance

[0134]

[0135] It can be seen that by controlling the dosage ratio of ethanolamine to catalyst within a more appropriate range, ethanolamine can have a higher conversion rate and 2-oxazolidinone can have a higher selectivity, that is, the cerium-based composite oxide has a higher catalytic performance; and the catalytic performance is better when the dosage ratio is (305~915):34.

[0136] Embodiment 36

[0137] The preparation method of the cerium-based composite oxide and the preparation process of oxazolidinone in Example 36 are basically the same as those in Example 17, except that: the cerium-based composite oxide CeZrO in Example 36 2 In the preparation of 2-oxazolidinone by (3:1)-750 catalyzing carbon dioxide and ethanolamine, the amount of ethanolamine added was 305 mg and the amount of cerium-based composite oxide added was 684 mg. The reaction product was detected by gas chromatography, and the results are shown in Table 8.

[0138] Embodiment 37

[0139] The preparation method of the catalyst and the preparation process of the oxazolidinone in Example 37 are basically the same as those in Example 36, except that: the cerium-based composite oxide CeZrO in Example 37 2 (3:1)-750 catalyzes the reaction of carbon dioxide with ethanolamine to produce CO2 in 2-oxazolidinone 2The reaction pressure was 16 atm. The reaction products were detected by gas chromatography, and the results are shown in Table 8.

[0140] Embodiment 38

[0141] The preparation method of the cerium-based composite oxide and the preparation process of oxazolidinone in Example 38 are basically the same as those in Example 36, except that: the cerium-based composite oxide CeZrO in Example 38 2 In the preparation of 2-oxazolidinone by (3:1)-750 catalyzing carbon dioxide and ethanolamine, the amount of ethanolamine added was 915 mg and the amount of cerium-based composite oxide added was 342 mg. The reaction product was detected by gas chromatography, and the results are shown in Table 8.

[0142] Table 8 CeZrO 2 (3:1)-750 Catalytic Performance

[0143]

[0144] Embodiments 39 to 41

[0145] The preparation method of the cerium-based composite oxide and the preparation process of oxazolidinone in Examples 39 to 41 are substantially the same as those in Example 37, except that: the cerium-based composite oxide CeZrO in Examples 39 to 41 is 2 The reaction time of (3:1)-750 in the preparation of 2-oxazolidinone from carbon dioxide and ethanolamine was 1 h, 2 h and 4 h respectively. The reaction products were detected by gas chromatography, and the results are shown in Table 9.

[0146] Table 9 Effect of reaction time on CeZrO 2 Effect of (3:1)-750 on catalytic performance

[0147]

[0148] Embodiment 42-43

[0149] The preparation method of the cerium-based composite oxide and the preparation process of oxazolidinone in Examples 42-43 are substantially the same as those in Example 9, except that: the cerium-based composite oxide CeZrO in Examples 42-43 is 2 The solvents in the preparation of 2-oxazolidinone by (3:1)-750 catalyzing carbon dioxide and ethanolamine were 1,4-dioxane and mesitylene. The reaction products were detected by gas chromatography, and the results are shown in Table 10.

[0150] Table 10 Effect of solvents on CeZrO 2 Effect of (3:1)-750 on catalytic performance

[0151]

[0152] It can be seen that the selection of a suitable solvent can enable ethanolamine to have a higher conversion rate and 2-oxazolidinone to have a higher selectivity, that is, the cerium-based composite oxide has a higher catalytic performance.

[0153] Embodiment 44

[0154] The preparation method of the cerium-based composite oxide and the preparation process of oxazolidinone in Example 44 are basically the same as those in Example 9, except that: the cerium-based composite oxide CeZrO in Example 44 2 (3:1)-750 catalyzes carbon dioxide and ethanolamine to prepare 2-oxazolidinone, and 610 mg of ethanolamine is converted into 750 mg of propanolamine. The reaction product is detected by gas chromatography, and the results are shown in Table 11.

[0155] Embodiment 45

[0156] The preparation method of the cerium-based composite oxide and the preparation process of oxazolidinone in Example 45 are basically the same as those in Example 9, except that: the cerium-based composite oxide CeZrO in Example 45 2 (3:1)-750 catalyzes carbon dioxide and ethanolamine to prepare 2-oxazolidinone, and 610 mg of ethanolamine is converted into 910 mg of 3-amino-1,2-propanediol. The reaction product is detected by gas chromatography, and the results are shown in Table 11.

[0157] Table 11 Effect of ethanolamine addition on CeZrO 2 Effect of (3:1)-750 on catalytic performance

[0158]

[0159] Embodiment 46

[0160] Preparation of Cerium-based Composite Oxides

[0161] After 0.2 mol / L cerium nitrate ammonia solution and 0.2 mol / L zirconium oxide nitrate solution were mixed evenly with a Ce / Zr molar ratio of 3:1, 1 mol / L ammonia water was added dropwise until the solution pH = 10. After vigorous stirring at room temperature for 1 h, a hydroxide precipitate was obtained. After multiple washings, it was dried at 110 °C for 12 h. Finally, it was placed in a muffle furnace and calcined at 600 °C for 3 h. The cerium-based composite oxide obtained was recorded as CeZrO 2 (3:1)-600.

[0162] In CeZrO 2 The (3:1)-600 catalyst was impregnated with 1 mol% sodium hydroxide (Na / Ce molar ratio = 0.01) and dried at 110 °C for 12 h. Finally, it was calcined at 600 °C in a muffle furnace for 3 h. The obtained cerium-based composite oxide was recorded as 1% Na-CeZrO2 (3:1)-600.

[0163] The preparation process of oxazolidinone in Example 46 is basically the same as that in Example 9. The reaction product was detected by gas chromatography, and the results are shown in Table 12.

[0164] Embodiment 47-48

[0165] The preparation method of the cerium-based composite oxide and the preparation process of oxazolidinone in Examples 47-48 are basically the same as those in Example 46, except that the molar percentage of sodium hydroxide is adjusted in Examples 47-48 so that the Na / Ce ratio of the prepared cerium-based composite oxide is 0.05 and 0.10, respectively. The reaction product is detected by gas chromatography, and the results are shown in Table 12.

[0166] Embodiments 49 to 51

[0167] The preparation method of the cerium-based composite oxide and the preparation process of oxazolidinone in Examples 49 to 51 are basically the same as those in Example 46, except that lithium hydroxide, barium chloride, and cobalt nitrate are used in place of sodium hydroxide in Examples 49 to 51, and their molar percentages are adjusted so that the prepared cerium-based composite oxides are 1% Li-CeZrO 2 (3:1)-600, 0.5%Ba-CeZrO 2 (3:1)-750 and 0.5%Co-CeZrO 2 (3:1)-750. The reaction product was detected by gas chromatography, and the results are shown in Table 12.

[0168] Table 12 Effect of additives on CeZrO 2 Effect of (3:1)-750 on catalytic performance

[0169]

[0170] It can be seen that by controlling the molar ratio of Na / Ce within a more appropriate range, ethanolamine can have a higher conversion rate and 2-oxazolidinone can have a higher selectivity, that is, the cerium-based composite oxide has a higher catalytic performance; and the catalytic performance is better when the molar ratio of Na / Ce is (0.01~0.05):1.

[0171] Embodiment 52

[0172] Preparation of Cerium-based Composite Oxides

[0173] After 0.2 mol / L zinc nitrate solution and 0.2 mol / L zirconium oxide nitrate solution were mixed evenly with a Ce / Zn molar ratio of 3:1, 1 mol / L ammonia water was added dropwise until the solution pH = 10. After vigorous stirring at room temperature for 1 h, a hydroxide precipitate was obtained. After multiple washings, it was dried at 110 °C for 12 h. Finally, it was placed in a muffle furnace and calcined at 600 °C for 3 h to obtain a cerium-based composite oxide, which was recorded as CeO 2 -ZnO(3:1)-600, wherein 3:1 represents the Ce / Zn molar ratio of 3:1, and 600 represents the calcination temperature.

[0174] The preparation process of oxazolidinone in Example 52 is basically the same as that in Example 1, except that: 2 -ZnO (3:1)-600 was used as the catalyst. The reaction product was detected by gas chromatography, and the results are shown in Table 13.

[0175] Embodiment 53~55

[0176] The preparation process of oxazolidinone in Examples 53 to 55 is basically the same as that in Example 52, except that: 2 -La 2 O 3 (3:1)-600, CeO 2 -In 2 O 3 (3:1)-600, CeO 2 -Al 2 O 3 (3:1)-600 was used as the catalyst. The reaction product was detected by gas chromatography, and the results are shown in Table 13.

[0177] Table 13 CeO 2 -M x O y Catalytic performance of the reaction of carbon dioxide with ethanolamine to prepare 2-oxazolidinone

[0178]

[0179] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0180] The above-mentioned embodiments only express several implementation methods of the present application, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for a person of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present application, and these all belong to the protection scope of the present application. Therefore, the protection scope of the patent of the present application shall be subject to the attached claims.

Claims

1. A method for synthesizing oxazolidinone compounds based on carbon dioxide and alcohol amines, characterized in that: include: Carbon dioxide and alcohol amine are used as raw materials, and under the action of a solid catalyst, the alcohol amine and the carbon dioxide react to generate the oxazolidinone compound; wherein the solid catalyst comprises a cerium-based composite oxide, and the reaction process comprises liquid phase carboxylation and cyclodehydration.

2. The method according to claim 1, characterized in that The cerium-based composite oxide includes one or more of a first cerium-based composite oxide, a second cerium-based composite oxide, and a third cerium-based composite oxide; The first cerium-based composite oxide includes CeM1 x1 O y1 , wherein M1 includes a first metal cation different from Ce, and the values ​​of x1 and y1 make the CeM1 x1 O y1 The algebraic sum of the valences of is zero; The second cerium-based composite oxide includes CeO2-M2 x2 O y2 , wherein M2 includes a second metal cation different from Ce, and the values ​​of x2 and y2 are such that M2 x2 O y2 The algebraic sum of the valences of is zero; The third cerium-based composite oxide includes M3'-CeM3 x3 O y3 , wherein M3 includes a third metal cation different from Ce, M3' includes a fourth metal cation, and the values ​​of x3 and y3 make the CeM3 x3 O y3 The algebraic sum of the valences of is zero; Optionally, the M1, the M2 and the M3 each independently include Zn 2+ ,La 3+ 、In 3+ 、Al 3+ and Zr 4+ At least one of; Optionally, the M3' comprises Na + , Li + , Ba 2+ or Co x’+ At least one of .

3. The method according to claim 2, characterized in that One or more of the following conditions are met: (1) In the CeO2-M2 x2 O y2 wherein, the molar ratio of Ce to M2 is denoted as Ce / M2, then 0 < Ce / M2 ≤ 1000, optionally 0 < Ce / M2 ≤ 10, and further optionally 0.25 < Ce / M2 ≤ 4; (2)The M3'-CeM3 x3 O y3 In this case, the molar ratio of M3' to Ce is denoted as M3' / Ce, and 0 < M3' / Ce ≤ 1, optionally 0 < M3' / Ce ≤ 0.5, and further optionally 0 < M3' / Ce ≤ 0.1; Optionally, the third cerium-based composite oxide is M3'-CeZr x3 O2, where the molar ratio of Ce to Zr is Ce / Zr, then 0 < Ce / Zr ≤ 1000, optionally 0 < Ce / Zr ≤ 10, and further optionally 0.25 < Ce / Zr ≤ 4.

4. The method according to claim 2, characterized in that: One or more of the following conditions are met: (1) The first cerium-based composite oxide is CeZr x1 O2, wherein the molar ratio of Ce to Zr is denoted as (Ce / Zr)', then 0<(Ce / Zr)'≤1000, which may be 0<(Ce / Zr)'≤10, and further may be 0.25<(Ce / Zr)'≤4; (2) The second cerium-based composite oxide includes one or more of CeO2-ZnO, CeO2-La2O3, CeO2-In2O3 and CeO2-Al2O3.

5. The method according to any one of claims 1 to 4, characterized in that: The alcoholamine includes one or more of substituted or unsubstituted ethanolamine and substituted or unsubstituted propanolamine; Optionally, the alcoholamine includes one or more of ethanolamine, 3-amino-1,2-propanediol and propanolamine.

6. The method according to any one of claims 1 to 4, characterized in that: The reaction is carried out in a solution of the alcoholamine; Optionally, the solvent in the solution includes one or more of acetonitrile, water, 1,4-dioxane and mesitylene, and further may be acetonitrile.

7. The method according to any one of claims 1 to 4, characterized in that: One or more of the following conditions are met: (1) The reaction temperature is 100°C to 300°C, optionally 100°C to 240°C, and further optionally 120°C to 220°C; (2) The reaction time is 0.5h~100h, optionally 0.5h~60h, further optionally 0.5h~48h; (3) During the reaction, the pressure of the carbon dioxide is 1 atm to 40 atm, optionally 1 atm to 20 atm, and further optionally 2 atm to 16 atm; (4) The reaction is carried out under stirring conditions, and the stirring speed is 200 rpm to 1500 rpm.

8. The method according to any one of claims 1 to 4, characterized in that: The ratio of the amount of the alcohol amine to the solid catalyst is (100-1500):(4-700), which may be (200-1300):(4-700), and may further be (300-1300):(4-700); Optionally, the amount of the alcoholamine is 100 mg to 1500 mg, optionally 200 to 1300 mg, further optionally 300 mg to 1300 mg; Optionally, the amount of the solid catalyst used is 4 mg to 700 mg, and optionally 34 mg to 684 mg.

9. An oxazolidinone compound prepared based on carbon dioxide and alcohol amine, characterized in that: Prepared by the method according to any one of claims 1 to 8.

10. An application of a cerium-based composite oxide in the preparation of oxazolidinone compounds based on carbon dioxide and alcohol amine, characterized in that: The cerium-based composite oxide is the cerium-based composite oxide used in the method according to any one of claims 1 to 8.

Images