Polyionic liquid with hydrogen bond donor as well as preparation method and application of polyionic liquid
By using polyionic liquid with hydrogen bond donor as catalyst, CO2 and epoxy compounds synthesize cyclic carbonate under mild conditions, solving the problems of high temperature and high pressure and complex separation in the prior art, achieving high efficiency, environmental protection and low cost catalytic effects.
Patent Information
- Application Number
- CN202510379800.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-28
- Publication Date
- 2025-07-01
AI Technical Summary
The prior art requires high temperature and high pressure conditions in the synthesis of cyclic carbonate with CO2 and epoxy compounds, and the separation of catalysts and products is complex, resulting in environmental pollution and high costs.
The polyionic liquid with hydrogen bond donor is used as a catalyst to achieve efficient synthesis of cyclic carbonates through reaction with carbon dioxide and epoxy compounds. The reaction conditions are mild and no cocatalysts and other solvents are required.
The high yield and high activity of the cyclic carbonate is achieved, the reaction conditions are mild, the stability is high, and the environment is free of pollution, reducing the cost of the catalyst.
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Figure CN120230251A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the fields of polyionic liquids and chemical catalysis, and particularly to a polyionic liquid with a hydrogen bond donor, a preparation method thereof, and an application thereof. Background Art
[0002] With the rapid development of modern industry, a large amount of fossil fuels such as coal, petroleum, and natural gas are consumed in many fields. However, the pollutants and CO2 emitted by the combustion of these fossil fuels also have a serious impact on society. On the other hand, CO2 is a non-toxic, inexpensive, and abundant carbon resource on the earth. CO2 can be catalytically converted into various chemicals as a raw material. The process of cycloaddition of CO2 and epoxides to synthesize cyclic carbonates has become one of the most promising and few industrializable ways to utilize CO2 due to the low price of raw materials and 100% atom utilization rate, which conforms to the development of "green chemistry" and "atom economy".
[0003] At present, quaternary ammonium salts are mostly used as catalysts in the industrial cycloaddition synthesis of cyclic carbonates. Although this process is relatively mature, it requires harsh conditions such as high temperature and high pressure during the process, and the reaction products and catalysts need to be separated through a series of complex processes.
[0004] Investigations have found that ionic liquid catalysts have attracted extensive attention due to their simple preparation, designable structure, low vapor pressure, low toxicity, high stability, unique solubility, easy separation, non-flammable and non-explosive properties, etc. However, with the continuous in-depth research and application of ionic liquids, conventional ionic liquids can no longer meet the requirements. Ionic liquid polymers (PILs) refer to polymers containing ionic liquids or structures containing ionic liquids. They contain both covalent bonds and ionic bonds and have the dual characteristics of ionic liquids and polymers. It has abundant and free halogen anions and excellent rigidity and polymer stability, which makes it have the advantages of catalytic activity, easy separation, and recyclability, better meeting the needs of society. Summary of the Invention
[0005] The object of the present invention is to provide a polyionic liquid with a hydrogen bond donor, which has the advantages of high yield, strong activity, no need for a co-catalyst and other solvents, mild reaction conditions, high stability, no pollution to the environment, and being green and environmentally friendly in the catalytic synthesis of cyclic carbonates from carbon dioxide and epoxides.
[0006] To achieve the above object, the technical solution adopted by the present invention is: a polyionic liquid with a hydrogen bond donor, and the structural formula of the polyionic liquid with a hydrogen bond donor is shown as (Ⅰ):
[0007]
[0008] Wherein, R = (CH2)n NH2, (CH2) n COOH, (CH2) n OH.
[0009] The preparation method of the above poly(ionic liquid) with a hydrogen bond donor is as follows:
[0010] 1) Dissolve 1-vinylimidazole and dibromomethane CH2Br2 in an organic solvent, stir and then react. After the reaction is completed, wash and dry to obtain the substance [C1DVIM]Br2.
[0011] 2) Mix 1-vinylimidazole and a hydrogen bond donor, carry out a heating reaction, and then remove the solvent through a rotary evaporator. After washing and drying, a yellow viscous liquid [YIN][HY] is obtained.
[0012] 3) Stir [C1DVIM]Br2, [YIN][HY], AIBN, water and polyethylene glycol - 200 at room temperature to carry out a polymerization reaction. Wash and dry to obtain a poly(ionic liquid) with a hydrogen bond donor.
[0013] In the above preparation method, in step 1), the reaction is carried out at 100 °C for 24 hours.
[0014] In the above preparation method, in step 2), the hydrogen bond donor is 2-bromoethanol or 2-bromopropionic acid or 2-bromoethylamine hydrobromide, and the molar ratio of 1-vinylimidazole to the hydrogen bond donor is 1:1.1.
[0015] In the above preparation method, in step 2), the heating reaction is carried out at 75 °C for 48 hours.
[0016] In the above preparation method, in step 3), the polymerization reaction is carried out at 100 °C for 24 hours.
[0017] The application of the above poly(ionic liquid) with a hydrogen bond donor in the synthesis of cyclic carbonates from epoxides.
[0018] The above application method is as follows: Mix the catalyst, carbon dioxide and epoxide, and react at a pressure of 0.1 - 0.5 MPa and a temperature of 110 - 130 °C for 12 - 14 hours; the catalyst is the poly(ionic liquid) with a hydrogen bond donor described in claim 1.
[0019] In the above application, the addition amount of the catalyst is 3% - 8% of the mass of the epoxide.
[0020] In the above application, the epoxide is epichlorohydrin, propylene oxide, butylene oxide, 1,2-epoxyethylbenzene or epibromohydrin.
[0021] The beneficial effects of the present invention are as follows: The polyionic liquid with a hydrogen bond donor is used as a catalyst in the cycloaddition reaction of epoxides and carbon dioxide to synthesize cyclic carbonates. Compared with traditional catalysts, the catalytic process of the present invention is simple, the reaction system does not require solvents and cocatalysts, the reaction conditions are mild, while ensuring the catalytic effect, the cost of the catalyst is greatly reduced, and the yield of cyclic carbonates is very high. Description of the Drawings
[0022] Figure 1 It is the 1H NMR spectrum of propylene carbonate obtained in Example 4.
[0023] Figure 2 It is the 1H NMR spectrum of styrene oxide obtained in Example 4.
[0024] Figure 3 It is the 1H NMR spectrum of propylene chlorocarbonate obtained in Example 4.
[0025] Figure 4 It is the 1H NMR spectrum of butylene carbonate obtained in Example 4.
[0026] Figure 5 It is the 1H NMR spectrum of propylene bromocarbonate obtained in Example 4. Detailed Embodiments
[0027] Example 1 Preparation of Polyionic Liquid with Hydrogen Bond Donor
[0028] (I) Preparation of Functionalized Polyionic Liquid PDMBr-HY
[0029] Dissolve 5.00 g of 1-vinylimidazole and 4.62 g of dibromomethane \(CH_2Br_2\) in 10 mL of tetrahydrofuran. Stir the mixture at room temperature and react in an oil bath at 100 °C for 24 hours. After the reaction, cool it to room temperature. Wash the obtained product with an organic solvent multiple times, and vacuum dry the washed product for a period of time to obtain a pale yellow powdery product 3,3-methylenedi(vinylimidazolium) dibromide \([C_1DVIM]Br_2\). Accurately weigh 0.1 mol of 1-vinylimidazole and dissolve it in 50 mL of acetonitrile. Then add 0.11 mol of 2-bromoethanol to the mixture and react at 75 °C for 48 hours. After the reaction, rotary evaporate to remove the organic solvent to obtain a yellow viscous liquid \([YIN][HY]\). Wash it with an organic solvent 5 times, and then place the ionic liquid in a vacuum drying oven for drying. Finally, accurately weigh 0.30 g of the pale yellow powdery product \([C_1DVIM]Br_2\), 0.20 g of the yellow viscous liquid \([YIN][HY]\), and 0.03 g of AIBN and put them into a mixed solution of 1.75 g of water and 6 g of polyethylene glycol-200. Stir at room temperature until the mixed solution is clear. Subsequently, place it in a reactor and react at 100 °C for 24 hours to initiate the polymerization reaction. After the reaction, obtain a cured composite material, wash it with deionized water 5 times, and then vacuum dry it for 48 hours to obtain the final catalyst PDMBr-HY, and the structural formula is as follows.
[0030] R = (CH2) n OH
[0031] (II) Preparation of functionalized poly(ionic liquid) PDMBr-CA
[0032] The method is the same as (I). Replace 2-bromoethanol with 3-bromopropionic acid to obtain a pure catalyst PDMBr-CA, and the structural formula is as follows.
[0033] R = ((CH2) n COOH
[0034] (III) Preparation of functionalized poly(ionic liquid) PDMBr-AM
[0035] The method is the same as (I). Replace 2-bromoethanol with 2-bromoethylamine hydrobromide to obtain a pure catalyst PDMBr-AM, and the structural formula is as follows.
[0036] R = (CH2) n NH2
[0037] Example 2: Ring-Opening Polymerization of Epoxides Catalyzed by Poly(ionic Liquid) with Hydrogen Bond Donors
[0038] (I) Effect of Temperature on Reaction Yield
[0039] In a 50 mL high-pressure reactor, the catalyst PDMBr-AM and epichlorohydrin were added, mixed, and 0.3 MPa of CO2 was introduced. The reaction was carried out for 14 hours at the temperature shown in Table 1. The amount of the catalyst added was 0.14 g, and the amount of epichlorohydrin added was 2.7756 g. After the reaction, the yield of the cyclic carbonate was calculated, and the results are shown in Table 1.
[0040] Table 1
[0041] Temperature °C 90 100 110 120 130 Yield % 76.6 86.7 92.7 97.3 98.8
[0042] (II) Influence of CO2 pressure on the reaction yield
[0043] The method was the same as (I), the temperature was 120 °C, and the pressure was changed as shown in Table 2. The results are shown in Table 2.
[0044] Table 2
[0045] Pressure MPa 0.1 0.2 0.3 0.4 0.5 Yield % 87.0 94.4 97.3 98 98.2
[0046] (III) Influence of reaction time on the reaction yield
[0047] The method was the same as (I), the temperature was 120 °C, and the reaction time was changed as shown in Table 3. The results are shown in Table 3.
[0048] Table 3
[0049] Time h 6 8 10 12 14 Yield % 52.8 74.6 85.8 93.2 97.3
[0050] (IV) Influence of catalyst dosage on the reaction yield
[0051] The method was the same as (I), the temperature was 120 °C, and the amount of the catalyst added was changed as shown in Table 4. The results are shown in Table 4.
[0052] Table 4
[0053] Catalyst dosage % 0.08 0.1 0.12 0.14 0.15 Yield % 86.2 91.0 95.7 97.3 97.6
[0054] In summary, for the cycloaddition reaction of epoxides catalyzed by poly(ionic liquid) with a hydrogen bond donor, it is preferred that in a 50 mL high-pressure reactor, the catalyst and epoxide are added, mixed, 0.3 MPa of CO2 is introduced, and the reaction is carried out at 120 °C for 14 hours. The amount of the catalyst added is 0.14 g, and the amount of epichlorohydrin added is 2.7756 g. The 1H NMR results ( Figure 3 ) are consistent with the reference (DOI: 10.1039 / d1cy01765a), proving that the pure target product propylene chlorocarbonate is obtained.
[0055] Example 3 Cycloaddition reaction of epoxides catalyzed by poly(ionic liquid) with a hydrogen bond donor
[0056] In a 50 mL high-pressure reactor, a catalyst (as shown in Table 5) and epichlorohydrin were added, mixed, and 0.3 MPa of CO2 was introduced. The reaction was carried out at 120 °C for 14 hours. The amount of catalyst added was 0.14 g, and the amount of epichlorohydrin was 2.7756 g. After the reaction, the yield of cyclic carbonate was calculated, and the results are shown in Table 5.
[0057] Table 5
[0058] Catalyst PDMBr-HY PDMBr-AM PDMBr-CA Yield % 97.9 97.3 97.0
[0059] Example 4: Poly(ionic liquid) with a hydrogen bond donor catalyzed the cycloaddition reaction of different epoxides
[0060] In a 50 mL high-pressure reactor, the catalyst PDMBr-AM and an epoxide (Table 6) were added, mixed, and 0.3 MPa of CO2 was introduced. The reaction was carried out at 120 °C for 14 hours. The amount of catalyst added was 0.08 g - 0.22 g, and the amount of epoxide added was 3% - 8% of the mass of the catalyst. After the reaction, the yield of cyclic carbonate was calculated, and the results are shown in Table 6.
[0061] Detected by 1H NMR, the results are shown in Table 6 and Figure 1 - 5 as follows. Figure 1 : 1 H NMR (400 MHz, CDCl3): δ 4.91 (m, 1H), 4.58 (q, 1H), 4.05 (q, 1H), 1.50 (d, 3H); Figure 2 : 1 H NMR (400 MHz, CDCl3): δ 7.44 (m, 5H), 5.70 (t, 1H), 4.83 (t, 1H), 4.37 (q, 1H); Figure 3 : 1 H NMR (400 MHz, CDCl3): δ 5.00 (m, 1H), 4.55 (m, 1H), 4.40 (q, 1H), 3.76 (m, 2H); Figure 4 : 1 H NMR (400 MHz, CDCl3) δ 4.60 (dd, 1H), 4.47 (t, 1H), 4.14 - 4.08 (m, 1H), 1.84 - 1.76 (m, 1H), 1.04 (dd, 3H); Figure 5 : 1 H NMR (400 MHz, CDCl3): δ 4.97 (m, 1H), 4.61 (t, 1H), 4.44 (dd, 1H), 3.66 - 3.54 (m, 2H).
[0062] Table 6
[0063]
Claims
1. A polyionic liquid with a hydrogen bond donor, characterized in that: The structural formula of the polyionic liquid with hydrogen bond donor is shown in (I): Where R = (CH2) n NH2, (CH2) n COOH, (CH2) n OH.
2. The method for preparing a polyionic liquid with a hydrogen bond donor according to claim 1, characterized in that: The preparation method of the polyionic liquid with hydrogen bond donor is as follows: 1) Dissolve 1-vinylimidazole and dibromomethane CH2Br2 in an organic solvent, stir and react, and after the reaction is completed, wash and dry to obtain a substance [C1DVIM]Br2, 2) 1-vinylimidazole and a hydrogen bond donor are mixed, heated for reaction, and then the solvent is removed by a rotary evaporator, and a yellow viscous liquid [YIN] [HY] is obtained after washing and drying. 3) [C1DVIM]Br2, [YIN][HY], AIBN, water and polyethylene glycol-200 are stirred at room temperature to carry out polymerization reaction, washed and dried to obtain a polyionic liquid with a hydrogen bond donor.
3. The preparation method according to claim 2, characterized in that: In step 1), the reaction is carried out at 100° C. for 24 hours.
4. The preparation method according to claim 2, characterized in that: In step 2), the hydrogen bond donor is 2-bromoethanol or 2-bromopropionic acid or 2-bromoethylamine hydrobromide, and the molar ratio of 1-vinylimidazole to the hydrogen bond donor is 1:1.
1.
5. The preparation method according to claim 2, characterized in that: In step 2), the heating reaction is carried out at 75° C. for 48 hours.
6. The preparation method according to claim 2, characterized in that: In step 3), the polymerization reaction is carried out at 100° C. for 24 hours.
7. Use of the polyionic liquid with hydrogen bond donor according to claim 1 in catalyzing the synthesis of cyclic carbonates from epoxy compounds.
8. The use according to claim 7, characterized in that: The method is as follows: a catalyst, carbon dioxide and an epoxy compound are mixed, and the mixture is reacted for 12 to 14 hours at a pressure of 0.1 to 0.5 MPa and 110 to 130° C.; the catalyst is the polyionic liquid with a hydrogen bond donor as claimed in claim 1.
9. The use according to claim 8, characterized in that: The added amount of the catalyst is 3%-8% of the mass of the epoxy compound.
10. The use according to claim 8 or 9, characterized in that: The epoxy compound is epichlorohydrin, propylene oxide, butylene oxide, 1,2-epoxyethylbenzene or epibromohydrin.