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US-12616964-B2 - Spirocyclic compound containing catalyst for use in catalyzing reaction of epoxide compound and carbon dioxide

US12616964B2US 12616964 B2US12616964 B2US 12616964B2US-12616964-B2

Abstract

The present disclosure provides a use of a catalyst for catalyzing a reaction of an epoxide compound and carbon dioxide, the catalyst includes a spirocyclic compound including at least one compound of formula (1): where X is selected from nitrogen, or phosphorus; Y is selected from halogens; A and B are independently selected from materials having formulae (a) to (d). Compared with catalysts with a non-spirocyclic structure or Lewis acid metal catalysts, the catalyst including the spirocyclic compound having the structural shown in formula 1 has the advantages of better catalytic effect, more stable performance and longer service life when catalyzing the reaction of the epoxy compounds and carbon dioxide. The present catalyst has both high efficiency and safety, and thus has broad application prospects.

Inventors

  • Zhongtian Zheng
  • Tianqian HE
  • Yuanyuan Kang
  • Qiyou Huang

Assignees

  • SHENZHEN CAPCHEM TECHNOLOGY CO., LTD.

Dates

Publication Date
20260505
Application Date
20221028
Priority Date
20221021

Claims (15)

  1. 1 . A method for preparing a cyclic carbonate by using a catalyst for catalyzing a reaction of an epoxide compound and carbon dioxide, wherein the catalyst comprises a spirocyclic compound comprising at least one compound of formula (1): where X is selected from nitrogen, or phosphorus; Y is selected from halogens; A and B are both selected from the following formula (a) with a sign * representing a bonding position: R a1 -R a8 are independently selected from H, or a C1-C5 alkyl group; wherein the method comprises: dissolving the catalyst in a cyclic carbonate to obtain a mixed solution, and adding the epoxide compound to the mixed solution, and introducing carbon dioxide to adjust a pressure of a reaction system to allow the epoxide compound to react with carbon dioxide to generate the cyclic carbonate.
  2. 2 . The method of claim 1 , wherein Y is selected from Cl, Br, or I.
  3. 3 . The method of claim 1 , wherein the spirocyclic compound comprises 5-azoniaspiro[4.4]nonane halide.
  4. 4 . The method of claim 1 , wherein the spirocyclic compound comprises at least one selected from a group consisting of 5-azoniaspiro[4.4]nonane chloride; 5-azoniaspiro[4.4]nonane bromide; 5-azoniaspiro[4.4]nonane iodide; 2-butyl-5-phosphaspiro[4.4]nonane chloride; 2-butyl-5-phosphaspiro[4.4]nonane bromide; or 2-butyl-5-phosphaspiro[4.4]nonane iodide.
  5. 5 . The method of claim 1 , wherein the catalyst further comprises at least one of water or alcohol, water is present in the catalyst in a concentration of 2000 ppm or less, the alcohol is present in the catalyst in a concentration of 2000 ppm or less.
  6. 6 . The method of claim 5 , wherein the alcohol is selected from at least one of methanol, ethanol, propanol, isopropanol or n-butanol.
  7. 7 . The method of claim 1 , wherein the epoxide compound is selected from at least one of ethylene oxide or propylene oxide.
  8. 8 . The method of claim 1 , wherein a mass percent concentration of the spirocyclic compound in the mixed solution is in the range from 0.5 to 10%.
  9. 9 . The method of claim 1 , wherein a temperature of the reaction system is in a range from 100 to 200° C.
  10. 10 . The method of claim 8 , wherein the mass percent concentration of the spirocyclic compound in the mixed solution is in the range from 1 to 5%.
  11. 11 . The method of claim 1 , wherein the pressure of the reaction system is in a range from 0.5 to 10 MPa.
  12. 12 . The method of claim 11 , wherein the pressure of the reaction system is in a range from 1 to 5 MPa.
  13. 13 . The method of claim 1 , wherein a reaction time is in a range from 0.3h to 20h.
  14. 14 . The method of claim 13 , wherein the reaction time is in a range from 0.5h to 15h.
  15. 15 . The method of claim 1 , wherein an initial concentration of the epoxide compound in the mixed solution is in a range of 1 to 15 wt %.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS This application is a national phase of International Application No. PCT/CN2022/128216, filed Oct. 28, 2022, which claims priority to Chinese Patent Application No. 202211291150.3, filed Oct. 21, 2022, the entire disclosures of which are incorporated herein by reference. FIELD The present disclosure relates to the technical field of chemical synthesis, and specifically relates to use of a catalyst including a spirocyclic compound for catalyzing a reaction of an epoxide compound and carbon dioxide. BACKGROUND Carbon dioxide is a main greenhouse gas causing global warming, and it is also an inexhaustible, cheap, nontoxic and recyclable green carbon resource on the earth. Realizing the utilization of the carbon dioxide resource has a strategic significance for reducing carbon dioxide emissions, improving the environment, and reducing dependence on fossil fuels. The effective immobilization of carbon dioxide has become one of the most challenging topics in this century, and the synthesis of cyclic carbonate is one of the immobilization routes. In recent years, cyclic carbonate, as a high value-added chemical, has been widely used in fine chemical industry, lithium battery manufacturing, polycarbonate and polyurethane synthesis. However, the preparation of cyclic carbonate by cycloaddition of carbon dioxide and an epoxide compound is a green chemical method with nearly 100% atomic economy, which has been paid attention to by academia and industry. At present, the reported production of cyclic carbonates mostly uses binary catalysts composed of Lewis acid metals and Lewis bases. The Lewis metals include alkali metal halides, alkaline earth metal halides, transition metal salts, transition metal complexes, or tetradentate Schiff alkali metal complexes. The Lewis bases include organic bases, ammonium salts, imidazole salts, solid bases (such as metal oxides), crown ethers, or molecular sieves, etc. These catalyst systems have problems, such as low catalytic activity, poor stability, harsh reaction conditions, use of highly toxic organic solvents, and high catalyst cost. SUMMARY The present disclosure provides in embodiments a method for preparing a cyclic carbonate by using a catalyst for catalyzing a reaction of an epoxide compound and carbon dioxide in which the catalyst includes a spirocyclic compound including at least one compound of formula (1): where X is selected from nitrogen, or phosphorus; Y is selected from halogens; A and B are independently selected from the following formulae with a sign * representing a bonding position: Ra1-Ra8, Rb1-Rb10, Rc1-Rc12, and Rd1-Rd14 are independently selected from H, or a C1-C5 alkyl group. The method includes: dissolving the catalyst in a cyclic carbonate to obtain a mixed solution, and adding the epoxide compound to the mixed solution, and introducing carbon dioxide to adjust a pressure of a reaction system to allow the epoxide compound to react with carbon dioxide to generate the cyclic carbonate. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows detection results of a reverse reaction of a reaction of generating ethylene carbonate (EC) from an ethylene oxide and carbon dioxide catalyzed by 5-azoniaspiro[4.4]nonane bromide and tetra-n-butylammonium bromide. FIG. 2 shows detection results of a reverse reaction of a reaction of generating EC from an ethylene oxide and carbon dioxide catalyzed by 5-azoniaspiro[4.6]undecane bromide and lithium bromide. DETAILED DESCRIPTION Experimental methods in which specific conditions are not specified in the following embodiments of the present disclosure are usually in accordance with conventional conditions, or conditions recommended by manufacturers. Various common chemicals used in the embodiments are commercially available products. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the invention pertains. Terms used in the specification of the present disclosure are only for the purpose of describing specific embodiments, and are not intended to limit the present disclosure. Terms “including”, “having”, and any variations thereof of the present disclosure are intended to cover non-exclusive inclusions. For example, a process, a method, an apparatus, a product, or an equipment that includes a series of steps is not limited to the listed steps or modules, but alternatively also includes steps that are not listed, or alternatively includes other steps inherent to these processes, methods, products or equipment. Term “a plurality of” in the present disclosure refers to two or more. Term “and/or” describes an association relationship of associated objects, indicating that there may be three relationships. For example, A and/or B, may represent: A existing alone, A and B existing at the same time, and B existing alone. The character “/” generally indicates that the associated objects are items