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CN-121975060-A - Ionic liquid functionalized metalloporphyrin porous copolymer, and preparation method and application thereof

CN121975060ACN 121975060 ACN121975060 ACN 121975060ACN-121975060-A

Abstract

The invention belongs to the technical field of high molecular compounds, and relates to an ionic liquid functionalized metalloporphyrin porous copolymer, a preparation method and application thereof. The ionic liquid functionalized metalloporphyrin porous copolymer catalyst provided by the invention has excellent chemical stability, rich mesoporous structure and higher specific surface area. The ionic liquid functionalized metalloporphyrin porous copolymer prepared by the invention is particularly suitable for catalyzing cycloaddition reaction of CO 2 and epoxide, and can convert the epoxide into cyclic carbonate at a milder reaction temperature and in a shorter reaction time by using a smaller amount of catalyst, thereby reducing cost, reducing reaction energy consumption and improving production efficiency.

Inventors

  • LUO RONGCHANG
  • CHEN ZONGJIE

Assignees

  • 广东工业大学

Dates

Publication Date
20260505
Application Date
20260403

Claims (10)

  1. 1. The ionic liquid functionalized metalloporphyrin porous copolymer is characterized in that the structure of the ionic liquid functionalized metalloporphyrin porous copolymer is shown in the following formula (I), formula (II), formula (III), formula (IV), formula (V) or formula (VI): 。
  2. 2. The ionic liquid functionalized metalloporphyrin porous copolymer according to claim 1, wherein the specific surface area of the ionic liquid functionalized metalloporphyrin porous copolymer is 200-600 m 2 ·g -1 , and the mesoporous area of the ionic liquid functionalized metalloporphyrin porous copolymer is 50-400 m 2 ·g -1 .
  3. 3. The method for preparing the ionic liquid functionalized metalloporphyrin porous copolymer according to claim 1 or 2, which comprises the following steps: S1, free radical polymerization, namely, carrying out free radical polymerization reaction on R 1 , R 2 and azodiisobutyronitrile in a solvent under the nitrogen atmosphere, wherein the temperature of the free radical polymerization reaction is 160-180 ℃, and the time of the free radical polymerization reaction is 72-80 hours, so as to obtain a metalloporphyrin-based porous copolymer; S2, performing ionic liquid functionalization, namely placing the metalloporphyrin-based porous copolymer obtained in the step S1 and F 1 in an organic solvent in a nitrogen atmosphere to perform a second polymerization reaction, wherein the temperature of the second polymerization reaction is 40-80 ℃, and the time of the second polymerization reaction is 18-26 hours, so as to obtain the ionic liquid functionalized metalloporphyrin porous copolymer shown in the formula (I), the formula (II) or the formula (V); wherein R 1 is 、 Or (b) ; R 2 is F 1 is 。
  4. 4. The method for preparing the ionic liquid functionalized metalloporphyrin porous copolymer according to claim 1 or 2, which comprises the following steps: s1, free radical polymerization, namely, carrying out free radical polymerization reaction on R 3 , R 4 and azodiisobutyronitrile in a solvent under the nitrogen atmosphere, wherein the temperature of the free radical polymerization reaction is 160-180 ℃, and the time of the free radical polymerization reaction is 72-80 hours, so as to obtain a metalloporphyrin-based porous copolymer; S2, performing ionic liquid functionalization, namely placing the metalloporphyrin-based porous copolymer obtained in the step S1 and F 2 in an organic solvent in a nitrogen atmosphere to perform a second polymerization reaction, wherein the temperature of the second polymerization reaction is 40-80 ℃, and the time of the second polymerization reaction is 18-26 hours, so as to obtain the ionic liquid functionalized metalloporphyrin porous copolymer shown in the formula (III), the formula (IV) or the formula (VI); Wherein R 3 is When R 4 is Or (b) F 2 is ; R 3 is R 4 is F 2 is 。
  5. 5. The method for preparing the ionic liquid functionalized metalloporphyrin porous copolymer according to claim 3 or 4, wherein, The said From the following components And diethyl aluminum chloride.
  6. 6. The use of the ionic liquid functionalized metalloporphyrin porous copolymer according to claim 1 or 2 in catalyzing the synthesis of cyclic carbonate by CO 2 , wherein the ionic liquid functionalized metalloporphyrin porous copolymer is used as a catalyst for catalyzing the synthesis of cyclic carbonate by CO 2 and epoxide.
  7. 7. A method for synthesizing cyclic carbonate by utilizing CO 2 and epoxide is characterized in that the ionic liquid functionalized metalloporphyrin porous copolymer and epoxide according to claim 1 or 2 are added into a closed container, CO 2 is introduced for exhausting and cycloaddition reaction is carried out, after the reaction is completed and cooled, the obtained filtrate is separated to obtain cyclic carbonate solution.
  8. 8. The method for synthesizing cyclic carbonate by utilizing CO 2 and epoxide according to claim 7, wherein the molar ratio of metal ions to epichlorohydrin in the ionic liquid functionalized metalloporphyrin porous copolymer is 0.0001-0.025, and after the CO 2 is introduced and air is exhausted, the introduction is continued until the pressure value is 0.1-3.0 MPa.
  9. 9. The method of synthesizing a cyclic carbonate using CO 2 and an epoxide according to claim 7, wherein the epoxide has the structural formula: Wherein R 5 、R 6 is selected from H, branched or straight chain alkyl with 1-4 carbon atoms, allyl, phenyl, halogen or alkyl substituted phenyl, chlorine or bromine substituted alkyl, R 7 -O-CH 2 -, R 7 is selected from phenyl, phenyl substituted with alkyl with 1-3 carbon atoms, allyl or branched or straight chain alkyl with 1-4 carbon atoms, or the epoxide is styrene oxide.
  10. 10. The method for synthesizing a cyclic carbonate using CO 2 and an epoxide according to claim 7, wherein the cycloaddition reaction is carried out at a temperature of 30 to 100 ℃ for a period of 3 to 72 hours with stirring.

Description

Ionic liquid functionalized metalloporphyrin porous copolymer, and preparation method and application thereof Technical Field The invention relates to the technical field of high molecular compounds, in particular to an ionic liquid functionalized metalloporphyrin porous copolymer, a preparation method and application thereof. Background CO 2 is the main greenhouse gas in the atmosphere, and carbon capture and utilization technology uses chemical conversion pathways to convert CO 2 into a commercially valuable product, wherein cyclic carbonates are prepared by cycloaddition reaction of CO 2 with epoxides, which is a very promising conversion pathway due to atomic economy. The synthesized cyclic carbonate product has wide application, has important application value in green chemistry, and can improve the performance and stability of the battery in the lithium battery electrolyte. Catalysts having dual active sites of lewis acid and base exhibit excellent catalytic performance in promoting the cycloaddition reaction of CO 2 with epoxide. The catalyst system realizes efficient and high-selectivity cycloaddition reaction through the synergistic effect of acid and alkali active sites without depending on solvents or cocatalysts. Chinese patent CN115894871B discloses a metalloporphyrin-based porous ionic polymer, however, the polymer is mainly made of microporous materials, and when CO 2 and epoxide are catalyzed to synthesize cyclic carbonate, a large amount of catalyst, higher reaction temperature and longer reaction time are required to achieve complete conversion of epoxide into cyclic carbonate. However, a large amount of catalyst increases the cost, a higher reaction temperature increases the reaction energy consumption, and a longer reaction time decreases the production efficiency. Disclosure of Invention The invention aims to overcome the defects and shortcomings of large dosage, high reaction temperature and long catalysis time of the existing catalyst for catalyzing CO 2 and epoxide to synthesize cyclic carbonate, and provides the ionic liquid functionalized metalloporphyrin porous copolymer, when the CO 2 and epoxide are catalyzed to synthesize the cyclic carbonate, the epoxide can be converted into the cyclic carbonate at a milder reaction temperature and a shorter reaction time by using a smaller catalyst, so that the cost is reduced, the reaction energy consumption is reduced, and the production efficiency is improved. The above object of the present invention is achieved by the following technical solutions: an ionic liquid functionalized metalloporphyrin porous copolymer, the structure of which is shown in the following formula (I), formula (II), formula (III), formula (IV), formula (V) or formula (VI): 。 In the catalyst, the nitrogen-rich structure of the porphyrin ring and the ionic liquid can selectively enrich CO 2, and meanwhile, halogen ions in the catalyst can be used as an attack nucleophile in the cycloaddition reaction of epoxide, so that the reaction process can be accelerated, and the reaction efficiency can be improved. The catalyst has a high specific surface area and a rich mesoporous structure, the contact area with reactants is increased when the catalytic reaction is carried out, the catalytic efficiency is improved, in addition, the larger specific surface area is beneficial to increasing the containing amount of carbon dioxide, and meanwhile, the larger mesoporous area is beneficial to substrate transfer and cycloaddition reaction of carbon dioxide, so that the high yield of the cyclic carbonate can be realized by using fewer catalysts. Preferably, the specific surface area of the ionic liquid functionalized metalloporphyrin porous copolymer is 200-600 m 2·g-1, and the mesoporous area of the ionic liquid functionalized metalloporphyrin porous copolymer is 50-400 m 2·g-1. The invention also provides a preparation method of the ionic liquid functionalized metalloporphyrin porous copolymer, which comprises the following steps: S1, free radical polymerization, namely, carrying out free radical polymerization reaction on R 1, R 2 and azodiisobutyronitrile in a solvent under the nitrogen atmosphere, wherein the temperature of the free radical polymerization reaction is 160-180 ℃, and the time of the free radical polymerization reaction is 72-80 hours, so as to obtain a metalloporphyrin-based porous copolymer; S2, performing ionic liquid functionalization, namely placing the metalloporphyrin-based porous copolymer obtained in the step S1 and F 1 in an organic solvent in a nitrogen atmosphere to perform a second polymerization reaction, wherein the temperature of the second polymerization reaction is 40-80 ℃, and the time of the second polymerization reaction is 18-26 hours, so as to obtain the ionic liquid functionalized metalloporphyrin porous copolymer shown in the formula (I), the formula (II) or the formula (V); wherein R 1 is 、Or (b); R 2 is(4-Chloromethylstyrene) F 1 is(N-meth