Search

KR-102954702-B1 - Double Metal Cyanide Catalyst, Preparing Method Thereof And Preparing Method For Poly Propylene Carbonates

KR102954702B1KR 102954702 B1KR102954702 B1KR 102954702B1KR-102954702-B1

Abstract

A bimetallic cyanide catalyst and a method for manufacturing it are introduced. The bimetallic cyanide catalyst comprises a first metal; a second metal cyanide; an organic complexing agent composed of a hydroxy carbonyl compound; and a co-complexing agent of the glycol class. Polypropylene glycol is used as the co-complexing agent. The weight ratio of the organic complexing agent to the co-complexing agent is 1:1 to 120:1, and the weight ratio of the first metal to the organic complexing agent is 1:3 to 1:1. Using this catalyst, poly(propylene carbonate) with a large molecular weight can be manufactured in high yield.

Inventors

  • 백준현
  • 황지원
  • 김하린
  • 정수민
  • 권기범
  • 한재성

Assignees

  • 숙명여자대학교산학협력단

Dates

Publication Date
20260513
Application Date
20230228

Claims (9)

  1. First metal; Secondary metal cyanide; An organic complexing agent composed of a hydroxy carbonyl compound; and It includes a glycol co-conjugation agent, The above organic complexing agent is one or more selected from the group of hydroxy ketones consisting of 1-hydroxy-2-butanone, 3-hydroxy-2-butanone, 3-hydroxy-3-methyl-2-butanone, and 4-hydroxy-4-methyl-2-pentanone. The above-mentioned co-forming agent is a polypropylene glycol with a number average molecular weight (Mn) of 400 to 1,000 g/mol, a bimetallic cyanide catalyst for the manufacture of polycarbonate.
  2. delete
  3. delete
  4. delete
  5. delete
  6. A bimetallic cyanide catalyst for manufacturing polycarbonate according to claim 1, wherein the weight ratio of the organic complexing agent to the co-complexing agent is 1:1 to 120:1.
  7. A bimetallic cyanide catalyst for manufacturing polycarbonate according to claim 1, wherein the weight ratio of the first metal to the organic complexing agent is 1:3 to 1:1.
  8. A step of obtaining a first mixed solution by combining and reacting a first aqueous solution of a metal salt and a second aqueous solution of a metal cyanide, wherein the aqueous solution of the metal salt contains an organic complexing agent; and The method includes the step of obtaining a second mixed solution by mixing and reacting a third aqueous solution containing the organic complexing agent and the co-complexing agent with the first mixed solution. The above organic complexing agent is one or more selected from the group of hydroxy ketones consisting of 1-hydroxy-2-butanone, 3-hydroxy-2-butanone, 3-hydroxy-3-methyl-2-butanone, and 4-hydroxy-4-methyl-2-pentanone. A method for preparing a bimetallic cyanide catalyst for polycarbonate production, wherein the above-mentioned co-forming agent is polypropylene glycol with a number average molecular weight (Mn) of 400 to 1,000 g/mol.
  9. delete

Description

Double Metal Cyanide Catalyst, Preparing Method Thereof And Preparing Method For Poly(Propylene Carbonates) The present invention relates to a bimetallic cyanide catalyst, a method for manufacturing the same, and a method for manufacturing poly(propylene carbonate) using the catalyst. The present invention is the result of a research service supported by SKPIC Global Co., Ltd. The research project title is "Development of Catalyst and Process Technology for Polypropylene Carbonate Polymerization," and the implementing agency is the Industry-Academic Cooperation Foundation of Sookmyung Women's University (Research period: March 15, 2022 – March 14, 2023). Carbon dioxide conversion technology is defined as a technology that captures carbon dioxide emitted from industries and converts it into recyclable (resource recovery) or immobilized energy. Innovative technological development is required to utilize carbon dioxide on a large scale, and active research on this topic is being conducted worldwide. Although CO2 is used as a raw material in various chemical processes, CO2 consumption is relatively low in product groups other than urea and mineral carbonation. To achieve CO2 reduction targets, it is necessary to develop new chemical conversion technologies for CO2 and new processes that use CO2 as a raw material. The chemical conversion of CO2 can be broadly classified into three parts. The first is a pathway to replace carbon monoxide using a highly reactive chemical raw material for the activation of CO2 , the second is a pathway to insert CO2 into a molecular structure, which is related to the present invention, and the third is a pathway to utilize it as a raw material in chemical synthesis by biological metabolism. CO₂ has a generation Gibbs energy of 394.6 kJ/mol, making it very stable and weakly reactive, but it can be chemically converted by catalytic reactions. A useful example is the double metal cyanide (DMC) catalyst used in the ring-opening polymerization of epoxides. As one example, it is known that Co-Zn-based DMC catalysts can incorporate about 43% CO₂ in the process of manufacturing polycarbonate polyols. DMC catalysts are prepared by reacting an aqueous solution of a metal salt with an aqueous solution of a metal cyanide to form a precipitate, and typically a complexing agent (CA) is used in conjunction. Bimetallic cyanide compounds prepared in the absence of a complexing agent have a crystalline structure according to X-ray diffraction analysis and are inert to epoxide polymerization reactions. Reference may be made to Korean Patent No. 429297. It is said that a Co-Zn-based DMC catalyst is prepared as an example using a mixture of zinc chloride ( ZnCl₂ ) and potassium hexacyanocobaltate { K₃ [Co(CN) ₆ ]}, and its chemical formula can be expressed as Zn₃ [Co(CN) ₆ ] ₂ · xZnCl₂ · yH₂O . Reference may be made to 'A Study on the Preparation of Polyether Polyols Using Bimetallic Cyanide Catalysts' in the October 2017 issue of the Journal of the Korean Society of Environmental Technology. Examples of complexing agents used in the preparation of DMC catalysts include alcohols, aldehydes, ketones, ethers, esters, amides, ureas, nitriles, sulfates, or mixtures thereof, among which ethers or water-soluble aliphatic alcohols are preferred. In the case of tert-butyl alcohol (t-BuOH) used as a complexing agent, the catalyst synthesis process is complex and time-consuming, and environmental pollution caused by excessive use is a problem. Poly(alkylene carbonate) is an amorphous, transparent material with low thermal stability, offering the advantage of decomposing completely at relatively low temperatures without leaving carbon residues. Due to these properties, it can be utilized as a biodegradable packaging material, coating material, or plasticizer. As research on the commercialization of poly(alkylene carbonates) continues, zinc glutarate (ZnGA) catalysts and salen catalysts have been developed. However, these catalysts have low productivity, making commercialization difficult. When DMC catalysts are used for the copolymerization of propylene oxide and CO2 , there is a problem that productivity is significantly low and the molecular weight of the poly(propylene carbonate) produced is small. The background technologies described above are intended solely to enhance understanding of the background of the present invention, and should not be construed as an acknowledgment that the described background technologies are already publicly known or constitute general knowledge in this technical field. Furthermore, it should be understood that the background technology described above is intended to enhance understanding of the present invention or the elements constituting the present invention. It should not be misunderstood that, based on the described background technology, it would be easy for a person skilled in the art to discover any combination thereof or any motivation leading to the present invention