WO2021057835A1 - 环氧烷烃加成反应催化剂及其应用 - Google Patents

环氧烷烃加成反应催化剂及其应用 Download PDF

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WO2021057835A1
WO2021057835A1 PCT/CN2020/117335 CN2020117335W WO2021057835A1 WO 2021057835 A1 WO2021057835 A1 WO 2021057835A1 CN 2020117335 W CN2020117335 W CN 2020117335W WO 2021057835 A1 WO2021057835 A1 WO 2021057835A1
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catalyst
cations
hours
reaction
hydrogen
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French (fr)
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俞峰萍
何文军
金铭
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中国石油化工股份有限公司
中国石油化工股份有限公司上海石油化工研究院
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Priority to JP2022518953A priority Critical patent/JP7490759B2/ja
Priority to US17/763,031 priority patent/US20220355285A1/en
Priority to BR112022005563A priority patent/BR112022005563A2/pt
Priority to KR1020227013721A priority patent/KR20220065065A/ko
Priority to EP20869127.9A priority patent/EP4035772A4/en
Publication of WO2021057835A1 publication Critical patent/WO2021057835A1/zh

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    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
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    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites

Definitions

  • the invention relates to an alkylene oxide addition reaction catalyst and its application, in particular to a nano composite ion exchange resin catalyst.
  • Alkylene carbonates such as ethylene carbonate and propylene carbonate are solvents and fine chemical intermediates with excellent performance and have a wide range of uses.
  • ethylene carbonate is widely used as a solvent in textiles, printing, polymer synthesis and electrochemistry. It can also be used as a raw material for cosmetics and medicines and as an intermediate for corresponding glycols. .
  • ethylene carbonate has been used in the production of lithium battery electrolyte and dimethyl carbonate, and the use of aliphatic polycarbonate and its various copolymers as degradable biological materials has made its industrial production more important.
  • the traditional production method of ethylene carbonate is the phosgene method.
  • Phosgene has high toxicity and serious pollution, and the process has shortcomings such as long flow, low yield and high cost.
  • the direct preparation of ethylene carbonate with carbon dioxide and ethylene oxide as raw materials under the action of corresponding catalysts is a new green and environmentally friendly approach.
  • the process can directly use carbon dioxide, a greenhouse gas, to alleviate the problem of carbon dioxide emissions.
  • catalyst systems that can be used for the addition reaction of carbon dioxide and epoxy compounds include quaternary ammonium salts, quaternary phosphonium salts, transition metal complexes, main group element complexes and alkali metal salts, ionic liquids, supercritical carbon dioxide, etc. Catalytic system.
  • the characteristics of the homogeneous catalytic system itself determine that the homogeneous process is difficult to separate products, the amount of catalyst is large and it is not easy to recycle, and the disadvantages such as environmental pollution.
  • heterogeneous catalysts facilitate the separation of subsequent products and catalysts, and the catalysts are easy to regenerate and can be reused many times.
  • the carrier of the heterogeneous catalytic system molecular sieve, silica gel, ion exchange resin, polyethylene glycol, poly(4-vinylpyridine), chitosan, etc. are commonly used.
  • Xiao et al. reported a supported zinc halide catalyst in Appl. Catal. A 279 (2005) 125-129, and the support was poly(4-vinylpyridine) or chitosan. In this system, homogeneous 1-butyl-3-methylimidazolium bromide must also be used as a co-catalyst, and the catalytic activity decreases significantly after being applied.
  • Van Kruvier et al. reported in CN 101511810A a zinc halide catalyst supported on a solid carrier. The carrier is a quaternary phosphonium type or quaternary ammonium type ion exchange resin. The activity of this catalytic system decreases rapidly after being applied.
  • heterogeneous catalytic system has many advantages, it still needs to be further improved in terms of abrasion resistance, swelling resistance and activity of the catalyst. It is very important to research and develop a catalytic system with high activity and easy separation.
  • the first aspect of the present invention provides a catalyst for the addition reaction of alkylene oxide, the catalyst comprising a nanocomposite ion exchange resin with the structural formula P-Im + -M -, Where P is the nanocomposite resin matrix, Im + is a 5-6 member heterocyclic cation containing at least 1 nitrogen atom such as imidazole cation, pyrazole cation, pyrrolidine cation, piperidine cation, piperazine cation, pyrimidine cation, pyrazine Cations, pyridazine cations, triazine cations (for example, 5-6 membered heteroaromatic cations containing at least one nitrogen atom, such as imidazole cations, pyrazole cations, pyrimidine cations, pyrazine cations, pyridazine cations, triazine cations), M - is an anion
  • the second aspect of the present invention provides a method for the addition reaction of alkylene oxide and carbon dioxide.
  • the catalyst includes a nanocomposite ion exchange resin with the structural formula P-Im + -M - , wherein P is a nanocomposite resin matrix, and Im + is a 5-6 element containing at least one nitrogen atom Heterocyclic cations such as imidazole cations, pyrazole cations, pyrrolidine cations, piperidine cations, piperazine cations, pyrimidine cations, pyrazine cations, pyridazine cations, triazine cations (e.g.
  • Heteroaromatic cations such as imidazole cations, pyrazole cations, pyrimidine cations, pyrazine cations, pyridazine cations, triazine cations
  • M - is an anion.
  • the nanocomposite resin matrix includes a structural fragment shown in formula I and a -CH(POSS)-CH 2 -structural fragment,
  • R 1 -R 8 are the same or different, and are each independently selected from hydrogen and C 1 -C 6 alkyl, preferably selected from hydrogen, methyl, ethyl, propyl and butyl;
  • POSS is a cage silsesquioxane, and the general formula of the cage silsesquioxane is (-SiO 1.5 )m, and m is 6, 8, 10, or 12.
  • the catalyst includes the following structure:
  • R 1 -R 3 are the same or different, and are each independently selected from hydrogen and C 1 -C 6 alkyl;
  • R 4 -R 8 is selected from hydrogen, C 1 -C 6 alkyl and CH 2 Im + -M -, and wherein at least one of R 4 -R 8 as CH 2 Im + -M -, preferably, R 4 -R 8 is selected from hydrogen and CH 2 Im + -M -, and wherein at least one of R 4 -R 8 as CH 2 Im + -M -.
  • the catalyst includes -CH-(Ph-CH 2 -Im + -M - ) -CH 2 -structure fragment.
  • the M - is selected from one or more of halide ions and organic acid ions.
  • the M - is selected from one or more of fluoride ion, chloride ion, bromide ion, iodide ion, acetate, formate and hydrogen oxalate.
  • the mass content of POSS in the nanocomposite resin matrix P is 0.1-10%, for example, 0.1%, 0.2%, 0.5%, 1.0%, 1.2%, 1.5%, 2.0%, 2.5% , 3.0%, 3.5%, 4.0%, 4.3%, 4.5%, 5.0%, 5.5%, 6.0%, 7.0%, 8.0%, 9.1%, 9.5%, 10% and any value in between.
  • the mass content of POSS in the nanocomposite resin matrix P is 0.2-5%.
  • the mass content of POSS in the nanocomposite resin matrix P is 2-5%.
  • the structural formula P-Im + -M - represents the nanocomposite resin matrix P modified with Im + and M -.
  • the characteristic absorption peak at 1111 cm -1 is attributed to the stretching vibration absorption peak of the Si-O-Si skeleton in the silsesquioxane.
  • the preparation of the catalyst includes the following steps:
  • step S2 The nanocomposite resin matrix P obtained in step S1 is subjected to a chloromethylation reaction, an imidazole reaction and an ion exchange reaction.
  • the nanocomposite resin matrix P is a nanocomposite copolymer obtained by in-situ copolymerization of a styrene monomer, a crosslinking agent and a nanomaterial.
  • the nanomaterial is selected from the group consisting of vinyl silsesquioxane, hydrogen-containing polysilsesquioxane, alkoxy-containing polysilsesquioxane, and epoxy-containing polysilsesquioxane. At least one of semisiloxanes.
  • the styrenic monomer is selected from one or more of the styrenic monomers represented by formula II;
  • R 1 -R 8 are the same or different, and are each independently selected from hydrogen and C 1 -C 6 alkyl, preferably selected from hydrogen, methyl, ethyl, propyl and butyl.
  • the styrenic monomer is selected from at least one of styrene, ⁇ -methylstyrene or 4-butylstyrene, preferably styrene.
  • the cage silsesquioxane is selected from the group consisting of vinyl silsesquioxane, hydrogen-containing polysilsesquioxane, alkoxy-containing polysilsesquioxane, and One or more of epoxy polysilsesquioxanes.
  • the vinyl-containing silsesquioxane is selected from octavinyl silsesquioxane
  • the crosslinking agent is selected from one or more of ethylene glycol dimethacrylate, dipropenylbenzene, divinylphenylmethane, or divinylbenzene.
  • the initiator is selected from at least one of benzoyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile, lauroyl peroxide or cumene hydroperoxide .
  • step S1 based on the total weight of the raw materials, the mass of the styrene monomer is 85-95%.
  • step S1 based on the total weight of the raw materials, the mass of the crosslinking agent is 1-6%.
  • the mass of the cage silsesquioxane is 0.1-10%, for example, 0.1%, 0.2%, 0.5%, 1.0%, 1.2%. %, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.3%, 4.5%, 5.0%, 5.5%, 6.0%, 7.0%, 8.0%, 9.1%, 9.5%, 10% and Any value between them.
  • step S1 based on the total weight of the raw materials, the mass of the cage silsesquioxane is 0.2-5%.
  • step S1 based on the total weight of the raw materials, the mass of the cage silsesquioxane is 2-5%.
  • step S1 based on the total weight of the raw materials, the mass of the initiator is 0.1-5%.
  • the amount of styrene monomer is 85-95 parts
  • the amount of crosslinking agent is 2-5 parts
  • the amount of nanomaterials is 0.1-10 parts
  • the amount of initiator The dosage is 0.1-5 parts.
  • the preparation method of the catalyst includes the following steps:
  • the chloromethylating reagent is selected from at least one of chloromethyl ether, chloromethyl ethyl ether or 1,4-dichloromethoxybutane;
  • the salt solution is selected from at least one of fluoride ion, chloride ion, bromide ion, iodide ion, acetate, formate, and hydrogen oxalate salt solution.
  • the method for the addition reaction of alkylene oxide and carbon dioxide includes reacting alkylene oxide and carbon dioxide in the presence of the above-mentioned catalyst.
  • the alkylene oxide has the following general formula:
  • R 9 -R 12 are the same or different, each independently selected from hydrogen and C 1 -C 6 alkyl and C 6 -C 10 aryl, preferably selected from hydrogen, methyl, ethyl, propyl, butyl and Phenyl.
  • the alkylene oxide is selected from ethylene oxide, propylene oxide or styrene oxide.
  • the mass ratio of the catalyst to the alkylene oxide is (0.001-1):1, preferably (0.1-0.3):1.
  • the temperature of the reaction is 60-180°C, such as 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 1800°C and any value in between.
  • the temperature of the reaction is 100-160°C.
  • the pressure of the reaction is 0.1-10.0 MPa, for example, 0.1 MPa, 0.5 MPa, 1 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, 6 MPa, 7 MPa, 8 MPa, 9 MPa, 10 MPa and any amount in between. Any value.
  • the pressure of the reaction is 2-5 MPa.
  • the reaction time is 1-8 hours, preferably 3-6 hours.
  • the nano composite ion exchange resin catalyst of the present invention is used in the addition reaction of alkylene oxide and carbon dioxide.
  • the catalyst has high abrasion resistance, high swelling resistance and high activity. After the reaction, the product is easy to separate, and the catalyst can be used continuously for many times.
  • Figure 1 The infrared spectrum of the ion exchange resin in Example 1.
  • Styrene analytically pure, purchased by Sinopharm, used after removing the polymerization inhibitor
  • Divinylbenzene analytically pure, purchased by Sinopharm, used for removing polymerization inhibitor
  • Benzoyl peroxide analytically pure, purchased from Sinopharm, and used after recrystallization;
  • Polyvinyl alcohol ⁇ gelatin analytically pure, purchased from Sinopharm, and used directly;
  • Chloromethyl ether ⁇ chloromethyl ethyl ether ⁇ 1,4-dichloromethoxybutane analytically pure, purchased from Sinopharm, and used directly;
  • Acetonitrile analytically pure, purchased from Sinopharm, and used directly;
  • the upper liquid was poured out, washed with hot water at 85°C, then washed with cold water, then filtered, dried in an oven at 80°C, sieved, and collected composite microspheres with a particle size in the range of 0.35 ⁇ 0.60 mm A1.
  • Chloromethylation of composite microspheres In a 500ml three-necked flask, add 40 grams of composite microspheres A1 and 250ml of chloromethyl ether, let stand at room temperature for 3 hours, start stirring, add 10 grams of zinc chloride as a catalyst, and heat to 60°C After reacting for 10 hours, cooling to room temperature after chloromethylation is completed, the chlorination mother liquor is filtered out, washed repeatedly with methanol, and dried at 100° C. for 8 hours to obtain composite chlorine balls A1.
  • Imidazolation Add 30 grams of composite chlorine ball A1 (chlorine content 3.4mmol Cl/g), 1-methylimidazole (102.0mmol) and 200ml acetonitrile into a 500ml three-necked flask, react at 60°C for 24 hours, and cool to room temperature , Filtered, washed with ethyl acetate, 0.1 mol/L HCl, deionized water, methanol, and then vacuum-baked at 60°C for 12 hours to obtain composite imidazole microspheres A1.
  • Ion exchange In a 1000ml three-necked flask, add 30g of composite imidazole microspheres A1, 500ml of 0.1mol/L NaBr deionized aqueous solution, stir at room temperature for 24 hours; then wash with deionized water until washed The pH of the solution is 7, and the ion exchange resin catalyst is obtained after vacuum drying, denoted as Cat-A1, and the structural formula is as follows:
  • a 500 ml three-necked flask was charged with a monomer mixture solution containing initiator (60.0 g styrene, 1.0 g divinylbenzene, 1.6 g octavinyl silsesquioxane and 1.0 g benzoyl peroxide).
  • initiator 60.0 g styrene, 1.0 g divinylbenzene, 1.6 g octavinyl silsesquioxane and 1.0 g benzoyl peroxide.
  • start the stirrer add a mixed solution of 200ml deionized water and 4g polyvinyl alcohol, heat up to 85°C, react for 3 hours, then heat up to 90°C, react for 9 hours, and finally heat up To 100°C, react for 10 hours.
  • the upper liquid was poured out, washed with hot water at 85°C, then washed with cold water, then filtered, dried in an oven at 80°C, sieved, and collected composite microspheres with a particle size in the range of 0.35 ⁇ 0.60 mm B1.
  • Chloromethylation of composite microspheres In a 500 ml three-necked flask, add 50 grams of composite microspheres B1 and 200 ml of chloromethyl ether, let stand at room temperature for 6 hours, add 30 grams of zinc chloride as a catalyst, and start stirring. The temperature was raised to 50°C to react for 30 hours, and after the chloromethylation was completed, it was cooled to room temperature, the chlorination mother liquor was filtered out, washed repeatedly with methanol, and dried at 100°C for 8 hours to obtain composite chlorine balls B1.
  • Imidazolation Add 50 grams of composite chlorine ball B1 (chlorine content of 4.6mmol Cl/g), 1-methylimidazole (230.0mmol) and 300ml acetonitrile into a 500ml three-necked flask, react at 80°C for 16 hours, and cool to room temperature , Filtered, washed sequentially with ethyl acetate, 0.1 mol/L HCl, deionized water, methanol, and then vacuum-baked at 60°C for 12 hours to obtain composite imidazole microspheres B1.
  • the upper liquid was poured out, washed with hot water at 85°C, then washed with cold water, then filtered, dried in an oven at 80°C, sieved, and collected composite microspheres with a particle size in the range of 0.35 ⁇ 0.60 mm C1.
  • Chloromethylation of composite microspheres In a 250 ml three-necked flask, add 20 grams of composite microspheres C1 and 100 ml of 1,4-dichloromethoxybutane, let stand at room temperature for 6 hours, and add 8 grams of chlorinated Zinc as a catalyst, start stirring, heat up to 30°C for 12 hours, cool to room temperature after chloromethylation, filter out the chlorination mother liquor, repeatedly wash with methanol, and dry at 100°C for 8 hours to obtain composite chlorine ball C1 .
  • Imidazolation add 20 grams of composite chlorine ball C1 (chlorine content 1.5mmol Cl/g), 1-ethylimidazole (30.0mmol) and 150ml acetonitrile in a 250ml three-necked flask, react at 90°C for 16 hours, and cool to room temperature , Filtered, washed with ethyl acetate, 0.1 mol/L HCl, deionized water, methanol, and then vacuum-baked at 60°C for 12 hours to obtain composite imidazole microspheres C1.
  • Ion exchange In a 500ml three-necked flask, add 20g of composite imidazole microspheres C1, 300ml of 0.5mol/L NaBr deionized aqueous solution, stir at room temperature for 12 hours; then wash with deionized water until washing The pH of the solution is 7, and the ion exchange resin catalyst is obtained after vacuum drying, denoted as Cat-C1, and the structural formula is as follows:
  • the upper liquid was poured out, washed with hot water at 85°C, then washed with cold water, then filtered, dried in an oven at 80°C, sieved, and collected composite microspheres with a particle size in the range of 0.35 ⁇ 0.60mm A2.
  • Chloromethylation of composite microspheres In a 500ml three-necked flask, add 40 grams of composite microspheres A2 and 250ml of chloromethyl ether, let stand at room temperature for 3 hours, start stirring, add 10 grams of zinc chloride as a catalyst, and heat up to 60°C After reacting for 10 hours, cooling to room temperature after chloromethylation is completed, the chlorination mother liquor is filtered out, washed repeatedly with methanol, and dried at 100° C. for 8 hours to obtain composite chlorine ball A2.
  • Imidazolation Add 30 grams of composite chlorine ball A2 (chlorine content 3.6mmol Cl/g), 1-methylimidazole (108.0mmol) and 200ml acetonitrile into a 500ml three-necked flask, react at 60°C for 24 hours, and cool to room temperature , Filtered, washed with ethyl acetate, 0.1 mol/L HCl, deionized water, methanol, and then dried under vacuum at 60°C for 12 hours to obtain composite imidazole microspheres A2.
  • a 500 ml three-necked flask was charged with a monomer mixture solution containing initiator (60.0 g styrene, 1.0 g divinylbenzene, 1.6 g octavinyl silsesquioxane and 1.0 g benzoyl peroxide).
  • initiator 60.0 g styrene, 1.0 g divinylbenzene, 1.6 g octavinyl silsesquioxane and 1.0 g benzoyl peroxide.
  • start the stirrer add a mixed solution of 200ml deionized water and 4g polyvinyl alcohol, heat up to 85°C, react for 3 hours, then heat up to 90°C, react for 9 hours, and finally heat up To 100°C, react for 10 hours.
  • the upper liquid was poured out, washed with hot water at 85°C, then washed with cold water, then filtered, dried in an oven at 80°C, sieved, and collected composite microspheres with a particle size in the range of 0.35 ⁇ 0.60 mm B2.
  • Chloromethylation of composite microspheres In a 500 ml three-necked flask, add 50 grams of composite microspheres B2 and 200 ml of chloromethyl ether, let stand at room temperature for 6 hours, add 30 grams of zinc chloride as a catalyst, and start stirring. The temperature was raised to 50°C for reaction for 30 hours, and after the chloromethylation was completed, it was cooled to room temperature, the chlorination mother liquor was filtered out, washed repeatedly with methanol, and dried at 100°C for 8 hours to obtain a composite chlorine ball B2.
  • Imidazolation add 50 grams of composite chlorine ball B2 (chlorine content of 4.7mmol Cl/g), 1-butylimidazole (235.0mmol) and 300ml acetonitrile in a 500ml three-necked flask, react at 80°C for 16 hours, and cool to room temperature , Filtered, washed sequentially with ethyl acetate, 0.1 mol/L HCl, deionized water, methanol, and then vacuum-baked at 60°C for 12 hours to obtain composite imidazole microspheres B2.
  • the upper liquid was poured out, washed with hot water at 85°C, then washed with cold water, then filtered, dried in an oven at 80°C, sieved, and collected composite microspheres with a particle size in the range of 0.35 ⁇ 0.60 mm C2.
  • Chloromethylation of composite microspheres In a 250 ml three-necked flask, add 20 grams of composite microspheres C2 and 100 ml of 1,4-dichloromethoxybutane, let stand at room temperature for 6 hours, and add 8 grams of chlorinated Zinc is the catalyst, start stirring, heat up to 30°C and react for 12 hours. After the chloromethylation is finished, cool to room temperature, filter out the chlorination mother liquor, wash it repeatedly with methanol, and dry it at 100°C for 8 hours to obtain composite chlorine ball C2 .
  • Imidazolation add 20 grams of composite chlorine ball C2 (chlorine content 1.6mmol Cl/g), 1-methylimidazole (32.0mmol) and 150ml acetonitrile into a 250ml three-necked flask, react at 90°C for 16 hours, and cool to room temperature , Filtered, washed with ethyl acetate, 0.1 mol/L HCl, deionized water, methanol, and then vacuum-baked at 60°C for 12 hours to obtain composite imidazole microspheres C2.
  • the upper liquid was poured out, washed with hot water at 85°C, then washed with cold water, then filtered, dried in an oven at 80°C, sieved, and collected composite microspheres with a particle size in the range of 0.35 ⁇ 0.60 mm A3.
  • Chloromethylation of composite microspheres In a 500ml three-necked flask, add 40 grams of composite microspheres A3 and 250ml of chloromethyl ether, let stand at room temperature for 3 hours, start stirring, add 10 grams of zinc chloride as a catalyst, and heat to 60°C After reacting for 10 hours, after the chloromethylation is completed, it is cooled to room temperature, the chlorination mother liquor is filtered out, washed repeatedly with methanol, and dried at 100° C. for 8 hours to obtain the composite chlorine ball A3.
  • Imidazolation Add 30 grams of composite chlorine ball A3 (chlorine content 3.4mmol Cl/g), 1-methylimidazole (102.0mmol) and 200ml acetonitrile into a 500ml three-necked flask, react at 60°C for 24 hours, and cool to room temperature , Filtered, washed with ethyl acetate, 0.1 mol/L HCl, deionized water, methanol, and then dried under vacuum at 60°C for 12 hours to obtain composite imidazole microspheres A3.
  • Ion exchange In a 1000ml three-necked flask, add 30g of composite imidazole microspheres A3, 500ml of 0.1mol/L NaBr deionized aqueous solution, stir at room temperature for 24 hours; then wash with deionized water until washed The pH of the solution is 7, and the ion exchange resin catalyst is obtained after vacuum drying, denoted as Cat-A3, and the structural formula is as follows:
  • the upper liquid was poured out, washed with hot water at 85°C, then washed with cold water, then filtered, dried in an oven at 80°C, sieved, and collected composite microspheres with a particle size in the range of 0.35 ⁇ 0.60 mm A5.
  • Chloromethylation of composite microspheres In a 500ml three-necked flask, add 40 grams of composite microspheres A4 and 250ml of chloromethyl ether, let stand at room temperature for 3 hours, start stirring, add 10 grams of zinc chloride as a catalyst, and heat to 60°C After reacting for 10 hours, after the chloromethylation is completed, it is cooled to room temperature, the chlorination mother liquor is filtered out, washed repeatedly with methanol, and dried at 100° C. for 8 hours to obtain composite chlorine ball A4.
  • Imidazolation Add 30 grams of composite chlorine ball A4 (chlorine content 3.4mmol Cl/g), 1-methylimidazole (102.0mmol) and 200ml acetonitrile into a 500ml three-necked flask, react at 60°C for 24 hours, and cool to room temperature , Filtered, washed with ethyl acetate, 0.1 mol/L HCl, deionized water, methanol, and then vacuum-baked at 60°C for 12 hours to obtain composite imidazole microspheres A4.
  • Ion exchange In a 1000ml three-necked flask, add 30g of composite imidazole microspheres A4, 500ml of 0.1mol/L NaBr deionized aqueous solution, stir at room temperature for 24 hours; then wash with deionized water until washed The pH of the solution is 7, and the ion exchange resin catalyst is obtained after vacuum drying, denoted as Cat-A4, and the structural formula is as follows:
  • the upper liquid was poured out, washed with hot water at 85°C, then washed with cold water, then filtered, dried in an oven at 80°C, sieved, and collected composite microspheres with a particle size in the range of 0.35 ⁇ 0.60 mm A5.
  • Chloromethylation of composite microspheres In a 500ml three-necked flask, add 40 grams of composite microspheres A5 and 250ml of chloromethyl ether, let stand at room temperature for 3 hours, start stirring, add 10 grams of zinc chloride as a catalyst, and heat up to 60°C After reacting for 10 hours, after the chloromethylation is completed, it is cooled to room temperature, the chlorination mother liquor is filtered out, washed repeatedly with methanol, and dried at 100° C. for 8 hours to obtain composite chlorine ball A5.
  • Imidazolation Add 30 grams of composite chlorine ball A5 (chlorine content 3.4mmol Cl/g), 1-methylimidazole (102.0mmol) and 200ml acetonitrile into a 500ml three-necked flask, react at 60°C for 24 hours, and cool to room temperature , Filtered, washed with ethyl acetate, 0.1 mol/L HCl, deionized water, methanol, and then vacuum-baked at 60°C for 12 hours to obtain composite imidazole microspheres A5.
  • the upper liquid was poured out, washed with hot water at 85°C, then washed with cold water, then filtered, dried in an oven at 80°C, sieved, and collected microspheres A6 with a particle size in the range of 0.35 ⁇ 0.60 mm .
  • Microsphere chloromethylation In a 500ml three-necked flask, add 40 grams of Microsphere A6 and 250ml of chloromethyl ether, let stand at room temperature for 3 hours, start stirring, add 10 grams of zinc chloride as a catalyst, and heat up to 60°C for reaction 10 After hours, the chloromethylation is completed and cooled to room temperature, the chlorination mother liquor is filtered out, washed repeatedly with methanol, and dried at 100° C. for 8 hours to obtain chlorine balls A6.
  • Imidazolation Add 30 grams of chlorine ball A6 (chlorine content 3.4mmol Cl/g), 1-methylimidazole (102.0mmol) and 200ml acetonitrile into a 500ml three-necked flask, react at 60°C for 24 hours, and cool to room temperature. After filtering, washing with ethyl acetate, 0.1 mol/L HCl, deionized water, methanol, and then drying under vacuum at 60° C. for 12 hours to obtain imidazole microspheres A6.
  • the upper liquid was poured out, washed with hot water at 85°C, then washed with cold water, then filtered, dried in an oven at 80°C, sieved, and collected microspheres A7 with a particle size in the range of 0.35 ⁇ 0.60 mm .
  • Chloromethylation of microspheres In a 500ml three-necked flask, add 40 grams of microspheres A1 and 250ml of chloromethyl ether, let stand at room temperature for 3 hours, start stirring, add 10 grams of zinc chloride as a catalyst, and heat to 60°C for reaction 10 After hours, the chloromethylation is finished and cooled to room temperature, the chlorination mother liquor is filtered out, washed repeatedly with methanol, and dried at 100° C. for 8 hours to obtain chlorine balls A7.
  • Imidazolation Add 30 grams of chlorine ball A7 (chlorine content 3.4mmol Cl/g), imidazole (102.0mmol) and 200ml acetonitrile into a 500ml three-necked flask, react at 80°C for 24 hours, cool to room temperature, filter, and use in sequence It was washed with ethyl acetate, 0.1 mol/L HCl, deionized water, methanol, and then dried under vacuum at 60° C. for 12 hours to obtain imidazole microspheres A7.
  • Ion exchange In a 1000ml three-necked flask, add 30g of imidazole/POSS microspheres A7, 500ml of 0.1mol/L NaBr deionized aqueous solution, stir at room temperature for 24 hours; then wash with deionized water until The pH of the washing liquid is 7, and the ion exchange resin catalyst is obtained after vacuum drying, denoted as Cat-A7, and the structural formula is as follows:
  • the ion exchange resin prepared in [Example 1] was used for the addition reaction of alkylene oxide and carbon dioxide.
  • the experimental conditions were as follows: under the protection of high-purity nitrogen, 50.0 grams of ethylene oxide and 7.5 grams of resin catalyst Cat-A1 were added A 300ml autoclave was filled with 1.0MPa CO 2 , heated to 120°C, and then filled with CO 2 to maintain the reaction pressure at 2.0 MPa. After 4 hours of reaction, the catalyst was filtered and removed. The ethylene oxide conversion rate C EO was measured to be 96.7 %, the ethylene carbonate selectivity S EC is 99.3%.
  • the catalyst Cat-A1 used in [Example 12] was filtered, washed, dried, and then again in accordance with the reaction steps and conditions in [Example 12] to catalyze the reaction of ethylene oxide and carbon dioxide to obtain the catalyst for recycling 2
  • the results of this time are shown in Table 2.
  • the catalytic reactions were carried out with 3 to 5 cycles respectively, and the results are shown in Table 2.
  • the catalyst prepared in [Example 1] was used for the addition reaction of other alkylene oxides and carbon dioxide under the following conditions: under the protection of high-purity nitrogen, 50.0 grams of alkylene oxide and 7.5 grams of resin catalyst were put into a 300 ml autoclave , Charged with 1.0MPa CO 2 , heated to 120°C, then charged with CO 2 to maintain the reaction pressure at 2.0 MPa, filtered to remove the catalyst after 4 hours of reaction, and measured the conversion rate of alkylene oxide and the selectivity of the obtained carbonate. The results are shown in Table 3.
  • the catalyst SiO 2 -ethane-Br was prepared and used for the addition reaction of styrene oxide and carbon dioxide under the following conditions: Under nitrogen protection, add 50.0 g of styrene oxide and 7.5 g of catalyst into a 300 ml autoclave, fill with 1.0 MPa CO 2 , raise the temperature to 120 °C, and then fill with CO 2 to maintain the reaction pressure at 2.0 MPa, and filter after 4 hours of reaction The catalyst was removed, and the conversion rate of styrene oxide and the selectivity of the obtained styrene cyclic carbonate were measured. The results are shown in Table 4.
  • the catalyst SBA-15-IL3Br was prepared and used for the addition reaction of propylene oxide and carbon dioxide.
  • the conditions were as follows: under the protection of high-purity nitrogen, 50.0 grams of ring Propylene oxide and 7.5 grams of catalyst were put into a 300 ml autoclave, filled with 1.0 MPa CO 2 , heated to 120° C, and then filled with CO 2 to maintain the reaction pressure at 2.0 MPa. After reacting for 4 hours, the catalyst was filtered and removed, and the propylene oxide content was measured. Conversion rate, and the selectivity of the resulting propylene carbonate. The results are shown in Table 4.
  • the catalyst Poly[bvbim]Cl was prepared and used for the addition reaction of styrene oxide with carbon dioxide.
  • the conditions were as follows: under the protection of high-purity nitrogen, Put 50.0 g of styrene oxide and 7.5 g of catalyst into a 300 ml autoclave, fill with 1.0 MPa CO 2 , raise the temperature to 120°C, and then fill with CO 2 to maintain the reaction pressure at 2.0 MPa. After reacting for 4 hours, filter to remove the catalyst. The conversion rate of styrene oxide and the selectivity of the resulting styrene cyclic carbonate. The results are shown in Table 4.
  • the drum is placed on the ball mill, and the resin is rotated at a speed of 125r/min for 20 minutes;
  • the dried sample is placed in an enamel tray, slightly tilted to make the spherical particles roll down, and the broken particles are brushed to the upper right corner. In the two parts of the sample, the remaining sample of the other sample is less than 50 particles, and the separation is complete;
  • the drum is placed on the ball mill, and the resin is rotated at a speed of 125r/min for 30 minutes;
  • the sphere rate after grinding of the catalyst Cat A1 of the present invention is 65.3%, and the sphere rate after permeation is 37.6%.
  • the CNT-based catalyst (refer to CN109569717A) has a sphericity rate of 54.2% after grinding, and a sphere rate of 25.5% for infiltration grinding.

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Abstract

一种用于环氧烷烃加成反应的催化剂，所述催化剂包括结构式为P-Im +-M -的纳米复合离子交换树脂，其中P为纳米复合树脂基体，Im +为5-6元含至少1个氮原子的杂环阳离子如咪唑阳离子、吡唑阳离子、吡咯烷阳离子、哌啶阳离子、哌嗪阳离子、嘧啶阳离子、吡嗪阳离子、哒嗪阳离子、三嗪阳离子，M -为阴离子，该催化剂用于环氧烷烃与二氧化碳的加成反应中，催化剂的耐磨性高、耐溶胀性高且活性高，反应后产物易分离，催化剂可连续使用多次。

Description

环氧烷烃加成反应催化剂及其应用 技术领域
本发明涉及一种环氧烷烃加成反应催化剂及其应用，具体涉及一种纳米复合离子交换树脂催化剂。
背景技术
碳酸亚烷酯如碳酸乙烯酯和碳酸丙烯酯是一种性能优良的溶剂和精细化工中间体，具有广泛用途。碳酸乙烯酯作为一种优良的高沸点溶剂和有机合成中间体，广泛用于纺织、印刷、高分子合成及电化学方面的溶剂，也可作为化妆品和药物的原料以及相应二元醇的中间体。近年来，碳酸乙烯酯应用于锂电池电解液、碳酸二甲酯的生产，脂肪族聚碳酸酯及其各种共聚物作为可降解生物材料的使用，使其工业化生产备受重视。
碳酸乙烯酯的传统生产方法为光气法。光气毒性高，污染严重，且该工艺存在流程长、收率低、成本高等缺点。而以二氧化碳和环氧乙烷为原料，在相应催化剂的作用下直接制备碳酸乙烯酯则是一种绿色环保新途径。该工艺可直接利用二氧化碳这种温室气体，缓解二氧化碳排放问题。
目前已知的可用于二氧化碳与环氧化合物加成反应的均相催化剂体系有季铵盐、季鏻盐、过渡金属配合物、主族元素配合物和碱金属盐、离子液体、超临界二氧化碳等催化体系。
何良年等人(Green Chem.,2003,5,92-94)开发了一类鏻盐催化剂，在超临界二氧化碳中以Rf 3RPI(Rf＝R＝C 4F 9C 2H 4；Rf＝R＝C 6F 13C 2H 4；Rf＝C 6F 13C 2H 4，R＝Me；Rf＝C 8F 17C 2H 4，R＝Me；P为磷，I为碘)为催化剂合成碳酸乙烯酯，催化剂含有较长的氟链，对二氧化碳具有较好的溶解度，而在产物中的溶解度较小，有利于产物分离。催化剂在超临界状态下实现了催化剂原位再生和循环使用，且可以循环使用，碳酸乙烯酯的产率达到90％以上，但是反应周期过长，需要24小时。
Kim等人研究了卤化锌与1-烷基-3-甲基-咪唑鎓卤化物和含膦配体等均相催化体系对于反应的影响(Angew.Chem.Int.Ed.39(2000)4096-4098，Chem.Eur.J.9(2003)678-686，J.Catal.232(2005)80-84)。反应过后，均相催化剂需要进行与产物的分离，而通过蒸馏使产物与 均相催化剂分离会使碳酸亚烷酯严重分解。
均相催化体系本身的特性决定了均相工艺存在产物分离困难，催化剂用量大且不易回收利用，环境污染等缺点。相对于均相催化剂，非均相催化剂有利于后续产物与催化剂的分离，催化剂易再生且可以多次重复利用。作为非均相催化体系的载体，常见的有分子筛、硅胶、离子交换树脂、聚乙二醇、聚(4-乙烯基吡啶)、壳聚糖等。
Xiao等人在Appl.Catal.A 279(2005)125-129中报道了负载的卤化锌催化剂，载体是聚(4-乙烯基吡啶)或者壳聚糖。该体系中也必须使用均相1-丁基-3-甲基咪唑鎓溴作为助催化剂，且经套用后催化活性下降明显。Van Kruchten等人在CN 101511810A中报道了负载于固体载体上的卤化锌催化剂，载体是季鏻型或季铵型离子交换树脂，该催化体系经套用后活性下降较快。
吕小兵等人研究了硅胶MCM-41负载的Salen(Co)为催化剂的碳酸乙烯酯固定床连续工艺。在添加正丁基溴化铵为共催化剂的条件下，环氧乙烷转化率可达到85.6％。
由此可见，非均相催化体系虽然有诸多优点，但在催化剂的耐磨性、耐溶胀性和活性方面仍有待进一步提高，研究开发一种高活性且易分离的催化体系显得十分重要。
发明内容
为了解决现有技术中存在的问题，本发明第一方面提供了一种用于环氧烷烃加成反应的催化剂，所述催化剂包括结构式为P-Im +-M -的纳米复合离子交换树脂，其中P为纳米复合树脂基体，Im +为5-6元含至少1个氮原子的杂环阳离子如咪唑阳离子、吡唑阳离子、吡咯烷阳离子、哌啶阳离子、哌嗪阳离子、嘧啶阳离子、吡嗪阳离子、哒嗪阳离子、三嗪阳离子(例如5-6元含至少1个氮原子的杂芳烃阳离子，如咪唑阳离子、吡唑阳离子、嘧啶阳离子、吡嗪阳离子、哒嗪阳离子、三嗪阳离子)，M -为阴离子，本发明的催化剂用于环氧烷烃与二氧化碳的加成反应中，催化剂的耐磨性高、耐溶胀性高且活性高，反应后产物易分离，催化剂可连续使用多次。
本发明的第二方面提供了一种环氧烷烃与二氧化碳加成反应的方法。
根据本发明的第一方面，所述催化剂包括结构式为P-Im +-M -的纳米复合离子交换树脂，其中P为纳米复合树脂基体，Im +为5-6元含至少1个氮原子的杂环阳离子如咪唑阳离子、吡唑阳离子、吡咯烷阳离子、哌啶阳离子、哌嗪阳离子、嘧啶阳离子、吡嗪阳离子、哒嗪阳离子、三嗪阳离子(例如5-6元含至少1个氮原子的杂芳烃阳离子，如咪唑阳离子、吡唑阳离子、嘧啶阳离子、吡嗪阳离子、哒嗪阳离子、三嗪阳离子)，M -为阴离子。
根据本发明的一些实施方式，所述纳米复合树脂基体包括式I所示的结构片段和-CH(POSS)-CH 2-结构片段，
Figure PCTCN2020117335-appb-000001
式I中R 1-R 8相同或不同，各自独立选自氢和C 1-C 6烷基，优选选自氢、甲基、乙基、丙基和丁基；
POSS为笼型倍半硅氧烷，所述笼型倍半硅氧烷通式为(-SiO 1.5)m，m为6、8、10或12。
根据本发明的一些实施方式，所述催化剂包括如下结构：
Figure PCTCN2020117335-appb-000002
其中R 1-R 3相同或不同，各自独立选自氢和C 1-C 6烷基；
R 4-R 8选自氢、C 1-C 6烷基和CH 2Im +-M -，并且R 4-R 8中至少其中之一为CH 2Im +-M -，优选地，R 4-R 8选自氢和CH 2Im +-M -，并且R 4-R 8中至少其中之一为CH 2Im +-M -。
根据本发明的一些实施方式，所述催化剂包括-CH-(Ph-CH 2-Im +-M -)-CH 2-结构片段。
根据本发明的一些实施方式，所述M -选自卤离子和有机酸根离子 中的一种或多种。
根据本发明的一些实施方式，所述M -选自氟离子、氯离子、溴离子、碘离子、乙酸根、甲酸根和草酸氢根中的一种或多种。
根据本发明的一些实施方式，所述纳米复合树脂基体P中POSS的质量含量为0.1-10％，例如0.1％、0.2％、0.5％、1.0％、1.2％、1.5％、2.0％、2.5％、3.0％、3.5％、4.0％、4.3％、4.5％、5.0％、5.5％、6.0％、7.0％、8.0％、9.1％、9.5％、10％以及它们之间的任意值。
根据本发明的一些实施方式，所述纳米复合树脂基体P中POSS的质量含量为0.2-5％。
据本发明的一些实施方式，所述纳米复合树脂基体P中POSS的质量含量为2-5％。
在本发明中，结构式P-Im +-M -表示采用Im +和M -修饰的纳米复合树脂基体P。
根据本发明的一些实施方式，所述纳米复合树脂基体P的红外光谱中，1111cm -1处的特征吸收峰归属于倍半硅氧烷中Si-O-Si骨架的伸缩振动吸收峰。
根据本发明的一些实施方式，所述催化剂的制备包括以下步骤：
S1：将苯乙烯类单体、交联剂和笼型倍半硅氧烷在引发剂存在的条件下进行聚合得到纳米复合树脂基体P；
S2：将步骤S1所得纳米复合树脂基体P进行氯甲基化反应、咪唑化反应和离子交换反应。
根据本发明的一些实施方式，所述纳米复合树脂基体P为苯乙烯类单体、交联剂和纳米材料经原位共聚得到的纳米复合共聚物。
根据本发明的一些实施方式，所述纳米材料选自含乙烯基倍半硅氧烷、含氢基聚倍半硅氧烷、含烷氧基聚倍半硅氧烷和含环氧基聚倍半硅氧烷中的至少一种。
根据本发明的一些实施方式，所述苯乙烯类单体选自式II所示的苯乙烯类单体中的一种或多种；
Figure PCTCN2020117335-appb-000003
式II中R 1-R 8相同或不同，各自独立选自氢和C 1-C 6烷基，优选选自氢、甲基、乙基、丙基和丁基。
根据本发明的一些实施方式，所述苯乙烯类单体选自苯乙烯、α-甲基苯乙烯或4-丁基苯乙烯中的至少一种，优选苯乙烯。
根据本发明的一些实施方式，所述笼型倍半硅氧烷选自含乙烯基倍半硅氧烷、含氢基聚倍半硅氧烷、含烷氧基聚倍半硅氧烷和含环氧基聚倍半硅氧烷中的一种或多种。
根据本发明的一些实施方式，所述含乙烯基倍半硅氧选自八乙烯基倍半硅氧烷，
根据本发明的一些实施方式，所述交联剂选自双甲基丙烯酸乙二醇酯、二丙烯基苯、二乙烯基苯基甲烷或二乙烯基苯中的一种或多种。
根据本发明的一些实施方式，所述引发剂选自过氧化苯甲酰、偶氮二异丁腈、偶氮二异庚腈、过氧化月桂酰或异丙苯过氧化氢中的至少一种。
根据本发明的一些实施方式，在步骤S1中，以原料总重计，所述苯乙烯单体的质量为85-95％。
根据本发明的一些实施方式，在步骤S1中，以原料总重计，所述交联剂的质量为1-6％。
根据本发明的一些实施方式，在步骤S1中，以原料总重计，所述笼型倍半硅氧烷的质量为0.1-10％，例如0.1％、0.2％、0.5％、1.0％、1.2％、1.5％、2.0％、2.5％、3.0％、3.5％、4.0％、4.3％、4.5％、5.0％、5.5％、6.0％、7.0％、8.0％、9.1％、9.5％、10％以及它们之间的任意值。
根据本发明的一些实施方式，在步骤S1中，以原料总重计，所述笼型倍半硅氧烷的质量为0.2-5％。
根据本发明的一些实施方式，在步骤S1中，以原料总重计，所述笼型倍半硅氧烷的质量为2-5％。
根据本发明的一些实施方式，在步骤S1中，以原料总重计，所述 引发剂的质量为0.1-5％。
根据本发明的一些实施方式，以重量份数计，苯乙烯单体的用量为85-95份，交联剂的用量为2-5份，纳米材料的用量为0.1-10份，引发剂的用量为0.1-5份。
在本发明的一些优选实施方式中，所述催化剂的制备方法包括以下步骤：
a)将助剂配成重量百分比浓度为0.5～3％的水溶液A，将苯乙烯类单体、交联剂、纳米材料、引发剂配成溶液B；其中，所述助剂选自聚乙烯醇、明胶、淀粉、甲基纤维素、膨润土或碳酸钙中的至少一种；所述苯乙烯类单体选自苯乙烯、α-甲基苯乙烯或4-丁基苯乙烯中的至少一种；所述交联剂选自双甲基丙烯酸乙二醇酯、二丙烯基苯、二乙烯基苯基甲烷或二乙烯基苯中的至少一种；所述纳米材料选自含乙烯基倍半硅氧烷、含氢基聚倍半硅氧烷、含烷氧基聚倍半硅氧烷和含环氧基聚倍半硅氧烷中的至少一种；所述引发剂选自过氧化苯甲酰、偶氮二异丁腈、偶氮二异庚腈、过氧化月桂酰或异丙苯过氧化氢中的至少一种；以重量份数计，苯乙烯单体的用量为85～95份，交联剂的用量为2～5份，纳米材料的用量为0.1～10份，引发剂的用量为0.1～5份；助剂的用量为单体用量的150～400％；
b)将溶液B与溶液A混合，常温下搅拌1-3小时，混合均匀。然后在60～75℃聚合反应0.5～5小时，逐渐升温至70～90℃反应5～15小时，再升温至90～100℃反应5～15小时；反应结束后，经抽提、洗涤、过滤、干燥、过筛，得到粒径范围0.35～0.60毫米的复合微球；
c)在复合微球中加入相当于复合微球重量200～500％的氯甲基化试剂，以及相当于复合微球重量20～70％的氯化锌催化剂，在30～60℃下反应8～30小时，经过滤、洗涤得到复合氯球；所述氯甲基化试剂选自氯甲醚，氯甲基乙醚或1,4-二氯甲氧基丁烷中的至少一种；
d)将所述复合氯球、N-甲基咪唑的混合物，在60～90℃下反应10～48小时，反应结束后经过滤、洗涤得到复合咪唑微球；所述混合物中，复合氯球、N-烷基咪唑和N,N-二甲基甲酰胺的摩尔比为1:(1～5):(10～50)；
f)所述复合咪唑微球用盐溶液洗涤，其中复合咪唑微球与盐溶液的摩尔比为(1:1)～(1:10)；盐溶液的浓度为0.1～1mol/L；洗涤完毕后 用去离子水洗涤至pH＝7，得到所述离子交换树脂。所述盐溶液选自氟离子、氯离子、溴离子、碘离子、乙酸根、甲酸根、草酸氢根盐溶液中的至少一种。
根据本发明的第二方面，所述环氧烷烃与二氧化碳加成反应的方法包括在上述催化剂存在的条件下，使环氧烷烃和二氧化碳进行反应。
根据本发明的一些实施方式，所述环氧烷烃具有如下通式：
Figure PCTCN2020117335-appb-000004
其中，R 9-R 12相同或不同，各自独立选自氢和C 1-C 6烷基和C 6-C 10芳基，优选选自氢、甲基、乙基、丙基、丁基和苯基。
根据本发明的一些实施方式，所述环氧烷烃选自环氧乙烷、环氧丙烷或氧化苯乙烯。
根据本发明的一些实施方式，所述催化剂与所述环氧烷烃的质量比为(0.001-1):1，优选为(0.1-0.3)：1。
根据本发明的一些实施方式，所述反应的温度为60-180℃，例如60℃、70℃、80℃、90℃、100℃、110℃、120℃、130℃、140℃、150℃、160℃、170℃、1800℃以及它们之间的任意值。
根据本发明的一些实施方式，所述反应的温度为100-160℃。
根据本发明的一些实施方式，所述反应的压力为0.1-10.0MPa，例如0.1MPa、0.5MPa、1MPa、2MPa、3MPa、4MPa、5MPa、6MPa、7MPa、8MPa、9MPa、10MPa以及它们之间的任意值。
根据本发明的一些实施方式，所述反应的压力为2-5MPa。
根据本发明的一些实施方式，所述反应的时间为1-8小时，优选为3-6小时。
本发明的纳米复合离子交换树脂催化剂用于环氧烷烃与二氧化碳的加成反应中，催化剂的耐磨性高、耐溶胀性高且活性高，反应后产物易分离，催化剂可连续使用多次。
附图说明
图1：实施例1中离子交换树脂的红外光谱图。
具体实施方式
下面通过实施例对本发明作进一步的阐述，但是需要指出的是， 本发明的保护范围并不受这此限制，而是由附录的权利要求书来确定。
需要特别说明的是，在本说明书的上下文中公开的两个或多个方面(或实施方式)可以彼此任意组合，由此而形成的技术方案属于本说明书原始公开内容的一部分，同时也落入本发明的保护范围之内。
原料：
苯乙烯：分析纯，国药购买，除去阻聚剂后使用；
二乙烯基苯：分析纯，国药购买，除去阻聚剂用使用；
八乙烯基倍半硅氧烷：分析纯，国药购买，直接使用；
过氧化苯甲酰：分析纯，国药购买，重结晶后使用；
聚乙烯醇\明胶：分析纯，国药购买，直接使用；
氯甲醚\氯甲基乙醚\1,4-二氯甲氧基丁烷：分析纯，国药购买，直接使用；
1-甲基咪唑\1-丁基咪唑\咪唑：分析纯，国药购买，直接使用；
乙腈：分析纯，国药购买，直接使用；
实施例中使用的其他未提及的试剂，均为市售可得，纯度为分析纯，国药购买，直接使用。
【实施例1】离子交换树脂制备
在500毫升三口烧瓶内加入65.0克苯乙烯，1.0克二乙烯基苯，3.0克八乙烯基倍半硅氧烷和1.0克过氧化苯甲酰，开动搅拌器搅拌0.5小时；加入200毫升去离子水和4克聚乙烯醇的混合溶液，搅拌2小时。随后逐渐升温至75℃，反应5小时，再升温到90℃，反应10小时，最后升温至100℃，反应10小时。反应结束后，倾倒出上层液体，用85℃热水洗涤，再用冷水洗涤，然后过滤，放入烘箱内80℃烘干，过筛，收集粒径在0.35～0.60毫米范围内的复合微球A1。
复合微球氯甲基化：在500ml的三口烧瓶内，加入40克复合微球A1和250ml氯甲醚，室温静置3小时，开始搅拌，加入10克氯化锌为催化剂，升温至60℃反应10小时，氯甲基化结束后冷却至室温，滤出氯化母液，用甲醇反复洗涤，在100℃下烘干8小时，得到复合氯球A1。
咪唑化：在500ml三口瓶中加入30克复合氯球A1(氯含量为3.4mmol Cl/g)、1-甲基咪唑(102.0mmol)与200ml乙腈，在60℃下反应24小时，冷却至室温，过滤，依次用乙酸乙酯、0.1mol/L的HCl、去 离子水、甲醇洗涤，然后真空60℃烘12小时得到复合咪唑微球A1。
离子交换：在1000ml三口烧瓶中，加入30克复合咪唑微球A1，500ml浓度为0.1mol/L的NaBr的去离子水溶液在室温下搅拌进行离子交换反应24小时；随后用去离子水洗涤直至洗液pH＝7，真空干燥后得到离子交换树脂催化剂，记为Cat-A1，结构式如下：
Figure PCTCN2020117335-appb-000005
【实施例2】离子交换树脂制备
在500毫升三口烧瓶内加入含有引发剂的单体混合物溶液(60.0克苯乙烯，1.0克二乙烯基苯，1.6克八乙烯基倍半硅氧烷和1.0克过氧化苯甲酰，该溶液先于70℃搅拌反应0.5小时)，开动搅拌器，加入200毫升去离子水和4克聚乙烯醇的混合溶液，升温至85℃，反应3小时，再升温到90℃，反应9小时，最后升温至100℃，反应10小时。反应结束后，倾倒出上层液体，用85℃热水洗涤，再用冷水洗涤，然后过滤，放入烘箱内80℃烘干，过筛，收集粒径在0.35～0.60毫米范围内的复合微球B1。
复合微球的氯甲基化：在500毫升的三口烧瓶内，加入50克复合微球B1和200毫升氯甲基乙醚，室温静置6小时，加入30克氯化锌为催化剂，开始搅拌，升温至50℃反应30小时，氯甲基化结束后冷却至室温，滤出氯化母液，用甲醇反复洗涤，在100℃下烘干8小时，得到复合氯球B1。
咪唑化：在500ml三口瓶中加入50克复合氯球B1(氯含量为4.6mmol Cl/g)、1-甲基咪唑(230.0mmol)与300ml乙腈，在80℃下反应16小时，冷却至室温，过滤，依次用乙酸乙酯、0.1mol/L的HCl、去离子水、甲醇洗涤，然后真空60℃烘12小时得到复合咪唑微球B1。
离子交换：在1000ml三口烧瓶中，加入40克复合咪唑微球B1，400ml浓度为1.0mol/L的NaBr的去离子水溶液在室温下搅拌进行离子交换反应12小时；随后用去离子水洗涤直至洗液pH＝7，真空干燥后得到离子交换树脂催化剂，记为Cat-B1，结构式如下：
Figure PCTCN2020117335-appb-000006
【实施例3】离子交换树脂制备
在500毫升三口烧瓶内加入含有引发剂的单体混合物溶液(42.5克苯乙烯，2.5克二乙烯基苯，0.1克八乙烯基倍半硅氧烷和2.0克过氧化苯甲酰，该溶液先于70℃搅拌反应1.5小时)，加入200毫升去离子水和4克聚乙烯醇的混合溶液，升温至85℃，反应3小时，再升温到90℃，反应9小时，最后升温至100℃，反应10小时。反应结束后，倾倒出上层液体，用85℃热水洗涤，再用冷水洗涤，然后过滤，放入烘箱内80℃烘干，过筛，收集粒径在0.35～0.60毫米范围内的复合微球C1。
复合微球的氯甲基化：在250毫升的三口烧瓶内，加入20克复合微球C1和100毫升1,4-二氯甲氧基丁烷，室温静置6小时，加入8克氯化锌为催化剂，开始搅拌，升温至30℃反应12小时，氯甲基化结束后冷却至室温，滤出氯化母液，用甲醇反复洗涤，在100℃下烘干8小时，得到复合氯球C1。
咪唑化：在250ml三口瓶中加入20克复合氯球C1(氯含量为1.5mmol Cl/g)、1-乙基咪唑(30.0mmol)与150ml乙腈，在90℃下反应16小时，冷却至室温，过滤，依次用乙酸乙酯、0.1mol/L的HCl、去离子水、甲醇洗涤，然后真空60℃烘12小时得到复合咪唑微球C1。
离子交换：在500ml三口烧瓶中，加入20克复合咪唑微球C1，300ml浓度为0.5mol/L的NaBr的去离子水溶液在室温下搅拌进行离子交换反应12小时；随后用去离子水洗涤直至洗液pH＝7，真空干燥后得到离子交换树脂催化剂，记为Cat-C1，结构式如下：
Figure PCTCN2020117335-appb-000007
【实施例4】离子交换树脂制备
在500毫升三口烧瓶内加入47.0克苯乙烯，2.3克二乙烯基苯和1.6克过氧化苯甲酰引发剂，于60℃下搅拌反应2.0小时；然后加入0.6克八乙烯基倍半硅氧烷，继续搅拌1小时进行预聚合。加入已溶解有2.0克明胶的260毫升去离子水溶液。调节搅拌速度，同时逐步升温至80℃，反应5小时；再升温到90℃，反应5小时，最后升温至98℃，反应6小时。反应结束后，倾倒出上层液体，用85℃热水洗涤，再用冷水洗涤，然后过滤，放入烘箱内80℃烘干，过筛，收集粒径在0.35～0.60mm范围内的复合微球A2。
复合微球氯甲基化：在500ml的三口烧瓶内，加入40克复合微球A2和250ml氯甲醚，室温静置3小时，开始搅拌，加入10克氯化锌为催化剂，升温至60℃反应10小时，氯甲基化结束后冷却至室温，滤出氯化母液，用甲醇反复洗涤，在100℃下烘干8小时，得到复合氯球A2。
咪唑化：在500ml三口瓶中加入30克复合氯球A2(氯含量为3.6mmol Cl/g)、1-甲基咪唑(108.0mmol)与200ml乙腈，在60℃下反应24小时，冷却至室温，过滤，依次用乙酸乙酯、0.1mol/L的HCl、去离子水、甲醇洗涤，然后真空60℃烘12小时得到复合咪唑微球A2。
离子交换：在1000ml三口烧瓶中，加入30克复合咪唑微球A2，500ml浓度为0.1mol/L的NaBr的去离子水溶液在室温下搅拌进行离子交换反应24小时；随后用去离子水洗涤直至洗液pH＝7，真空干燥后得到离子交换树脂催化剂，记为Cat-A2，结构式如下：
Figure PCTCN2020117335-appb-000008
【实施例5】离子交换树脂制备
在500毫升三口烧瓶内加入含有引发剂的单体混合物溶液(60.0克苯乙烯，1.0克二乙烯基苯，1.6克八乙烯基倍半硅氧烷和1.0克过氧化苯甲酰，该溶液先于70℃搅拌反应0.5小时)，开动搅拌器，加入200毫升去离子水和4克聚乙烯醇的混合溶液，升温至85℃，反应3小时，再升温到90℃，反应9小时，最后升温至100℃，反应10小时。反应结束后，倾倒出上层液体，用85℃热水洗涤，再用冷水洗涤，然后过滤，放入烘箱内80℃烘干，过筛，收集粒径在0.35～0.60毫米范围内的复合微球B2。
复合微球的氯甲基化：在500毫升的三口烧瓶内，加入50克复合微球B2和200毫升氯甲基乙醚，室温静置6小时，加入30克氯化锌为催化剂，开始搅拌，升温至50℃反应30小时，氯甲基化结束后冷却至室温，滤出氯化母液，用甲醇反复洗涤，在100℃下烘干8小时，得到复合氯球B2。
咪唑化：在500ml三口瓶中加入50克复合氯球B2(氯含量为4.7mmol Cl/g)、1-丁基咪唑(235.0mmol)与300ml乙腈，在80℃下反应16小时，冷却至室温，过滤，依次用乙酸乙酯、0.1mol/L的HCl、去 离子水、甲醇洗涤，然后真空60℃烘12小时得到复合咪唑微球B2。
离子交换：在1000ml三口烧瓶中，加入40克复合咪唑微球B2，400ml浓度为1.0mol/L的NaBr的去离子水溶液在室温下搅拌进行离子交换反应12小时；随后用去离子水洗涤直至洗液pH＝7，真空干燥后得到离子交换树脂催化剂，记为Cat-B2，结构式如下：
Figure PCTCN2020117335-appb-000009
【实施例6】离子交换树脂制备
在500毫升三口烧瓶内加入含有引发剂的单体混合物溶液(42.5克苯乙烯，2.5克二乙烯基苯，0.1克八乙烯基倍半硅氧烷和2.0克过氧化苯甲酰，该溶液先于70℃搅拌反应1.5小时)，加入200毫升去离子水和4克聚乙烯醇的混合溶液，升温至85℃，反应3小时，再升温到90℃，反应9小时，最后升温至100℃，反应10小时。反应结束后，倾倒出上层液体，用85℃热水洗涤，再用冷水洗涤，然后过滤，放入烘箱内80℃烘干，过筛，收集粒径在0.35～0.60毫米范围内的复合微球C2。
复合微球的氯甲基化：在250毫升的三口烧瓶内，加入20克复合微球C2和100毫升1,4-二氯甲氧基丁烷，室温静置6小时，加入8克氯化锌为催化剂，开始搅拌，升温至30℃反应12小时，氯甲基化结束后冷却至室温，滤出氯化母液，用甲醇反复洗涤，在100℃下烘干8小时，得到复合氯球C2。
咪唑化：在250ml三口瓶中加入20克复合氯球C2(氯含量为1.6mmol Cl/g)、1-甲基咪唑(32.0mmol)与150ml乙腈，在90℃下反应16小时，冷却至室温，过滤，依次用乙酸乙酯、0.1mol/L的HCl、去离子水、甲醇洗涤，然后真空60℃烘12小时得到复合咪唑微球C2。
离子交换：在500ml三口烧瓶中，加入20克复合咪唑/POSS微球C2，300ml浓度为0.5mol/L的NaBr的去离子水溶液在室温下搅拌进行离子交换反应12小时；随后用去离子水洗涤直至洗液pH＝7，真空干燥后得到离子交换树脂催化剂，记为Cat-C2，结构式如下：
Figure PCTCN2020117335-appb-000010
【实施例7】离子交换树脂制备
在500毫升三口烧瓶内加入65.0克苯乙烯，1.0克二乙烯基苯，0.07克八乙烯基倍半硅氧烷和1.0克过氧化苯甲酰，开动搅拌器搅拌0.5小时；加入200毫升去离子水和4克聚乙烯醇的混合溶液，搅拌2小时。随后逐渐升温至75℃，反应5小时，再升温到90℃，反应10小时，最后升温至100℃，反应10小时。反应结束后，倾倒出上层液体，用85℃热水洗涤，再用冷水洗涤，然后过滤，放入烘箱内80℃烘干，过筛，收集粒径在0.35～0.60毫米范围内的复合微球A3。
复合微球氯甲基化：在500ml的三口烧瓶内，加入40克复合微球A3和250ml氯甲醚，室温静置3小时，开始搅拌，加入10克氯化锌为催化剂，升温至60℃反应10小时，氯甲基化结束后冷却至室温，滤出氯化母液，用甲醇反复洗涤，在100℃下烘干8小时，得到复合氯球A3。
咪唑化：在500ml三口瓶中加入30克复合氯球A3(氯含量为3.4mmol Cl/g)、1-甲基咪唑(102.0mmol)与200ml乙腈，在60℃下反应24小时，冷却至室温，过滤，依次用乙酸乙酯、0.1mol/L的HCl、去离子水、甲醇洗涤，然后真空60℃烘12小时得到复合咪唑微球A3。
离子交换：在1000ml三口烧瓶中，加入30克复合咪唑微球A3，500ml浓度为0.1mol/L的NaBr的去离子水溶液在室温下搅拌进行离子交换反应24小时；随后用去离子水洗涤直至洗液pH＝7，真空干燥后得到离子交换树脂催化剂，记为Cat-A3，结构式如下：
Figure PCTCN2020117335-appb-000011
【实施例8】离子交换树脂制备
在500毫升三口烧瓶内加入65.0克苯乙烯，1.0克二乙烯基苯，7.5克八乙烯基倍半硅氧烷和1.0克过氧化苯甲酰，开动搅拌器搅拌0.5小时；加入200毫升去离子水和4克聚乙烯醇的混合溶液，搅拌2小时。随后逐渐升温至75℃，反应5小时，再升温到90℃，反应10小时，最后升温至100℃，反应10小时。反应结束后，倾倒出上层液体，用85℃热水洗涤，再用冷水洗涤，然后过滤，放入烘箱内80℃烘干，过筛，收集粒径在0.35～0.60毫米范围内的复合微球A5。
复合微球氯甲基化：在500ml的三口烧瓶内，加入40克复合微球A4和250ml氯甲醚，室温静置3小时，开始搅拌，加入10克氯化 锌为催化剂，升温至60℃反应10小时，氯甲基化结束后冷却至室温，滤出氯化母液，用甲醇反复洗涤，在100℃下烘干8小时，得到复合氯球A4。
咪唑化：在500ml三口瓶中加入30克复合氯球A4(氯含量为3.4mmol Cl/g)、1-甲基咪唑(102.0mmol)与200ml乙腈，在60℃下反应24小时，冷却至室温，过滤，依次用乙酸乙酯、0.1mol/L的HCl、去离子水、甲醇洗涤，然后真空60℃烘12小时得到复合咪唑微球A4。
离子交换：在1000ml三口烧瓶中，加入30克复合咪唑微球A4，500ml浓度为0.1mol/L的NaBr的去离子水溶液在室温下搅拌进行离子交换反应24小时；随后用去离子水洗涤直至洗液pH＝7，真空干燥后得到离子交换树脂催化剂，记为Cat-A4，结构式如下：
Figure PCTCN2020117335-appb-000012
【实施例9】离子交换树脂制备
在500毫升三口烧瓶内加入65.0克苯乙烯，1.0克二乙烯基苯，11.8克八乙烯基倍半硅氧烷和1.0克过氧化苯甲酰，开动搅拌器搅拌0.5小时；加入200毫升去离子水和4克聚乙烯醇的混合溶液，搅拌2小时。随后逐渐升温至75℃，反应5小时，再升温到90℃，反应10小时，最后升温至100℃，反应10小时。反应结束后，倾倒出上层液体，用85℃热水洗涤，再用冷水洗涤，然后过滤，放入烘箱内80℃烘干，过筛，收集粒径在0.35～0.60毫米范围内的复合微球A5。
复合微球氯甲基化：在500ml的三口烧瓶内，加入40克复合微球A5和250ml氯甲醚，室温静置3小时，开始搅拌，加入10克氯化锌为催化剂，升温至60℃反应10小时，氯甲基化结束后冷却至室温，滤出氯化母液，用甲醇反复洗涤，在100℃下烘干8小时，得到复合氯球A5。
咪唑化：在500ml三口瓶中加入30克复合氯球A5(氯含量为3.4mmol Cl/g)、1-甲基咪唑(102.0mmol)与200ml乙腈，在60℃下反应24小时，冷却至室温，过滤，依次用乙酸乙酯、0.1mol/L的HCl、去离子水、甲醇洗涤，然后真空60℃烘12小时得到复合咪唑微球A5。
离子交换：在1000ml三口烧瓶中，加入30克复合咪唑微球A5，500ml浓度为0.1mol/L的NaBr的去离子水溶液在室温下搅拌进行离 子交换反应24小时；随后用去离子水洗涤直至洗液pH＝7，真空干燥后得到离子交换树脂催化剂，记为Cat-A5，结构式如下：
Figure PCTCN2020117335-appb-000013
【对比实施例10】离子交换树脂制备
在500毫升三口烧瓶内加入65.0克苯乙烯，1.0克二乙烯基苯和1.0克过氧化苯甲酰，开动搅拌器搅拌0.5小时；加入200毫升去离子水和4克聚乙烯醇的混合溶液，搅拌2小时。随后逐渐升温至75℃，反应5小时，再升温到90℃，反应10小时，最后升温至100℃，反应10小时。反应结束后，倾倒出上层液体，用85℃热水洗涤，再用冷水洗涤，然后过滤，放入烘箱内80℃烘干，过筛，收集粒径在0.35～0.60毫米范围内的微球A6。
微球氯甲基化：在500ml的三口烧瓶内，加入40克微球A6和250ml氯甲醚，室温静置3小时，开始搅拌，加入10克氯化锌为催化剂，升温至60℃反应10小时，氯甲基化结束后冷却至室温，滤出氯化母液，用甲醇反复洗涤，在100℃下烘干8小时，得到氯球A6。
咪唑化：在500ml三口瓶中加入30克氯球A6(氯含量为3.4mmol Cl/g)、1-甲基咪唑(102.0mmol)与200ml乙腈，在60℃下反应24小时，冷却至室温，过滤，依次用乙酸乙酯、0.1mol/L的HCl、去离子水、甲醇洗涤，然后真空60℃烘12小时得到咪唑微球A6。
离子交换：在1000ml三口烧瓶中，加入30克咪唑微球A6，500ml浓度为0.1mol/L的NaBr的去离子水溶液在室温下搅拌进行离子交换反应24小时；随后用去离子水洗涤直至洗液pH＝7，真空干燥后得到离子交换树脂催化剂，记为Cat-A6，结构式如下：
Figure PCTCN2020117335-appb-000014
【对比实施例11】离子交换树脂制备
在500毫升三口烧瓶内加入65.0克苯乙烯，1.0克二乙烯基苯和1.0克过氧化苯甲酰，开动搅拌器搅拌0.5小时；加入200毫升去离子水和4克聚乙烯醇的混合溶液，搅拌2小时。随后逐渐升温至75℃，反应5小时，再升温到90℃，反应10小时，最后升温至100℃，反应10小时。反应结束后，倾倒出上层液体，用85℃热水洗涤，再用 冷水洗涤，然后过滤，放入烘箱内80℃烘干，过筛，收集粒径在0.35～0.60毫米范围内的微球A7。
微球氯甲基化：在500ml的三口烧瓶内，加入40克微球A1和250ml氯甲醚，室温静置3小时，开始搅拌，加入10克氯化锌为催化剂，升温至60℃反应10小时，氯甲基化结束后冷却至室温，滤出氯化母液，用甲醇反复洗涤，在100℃下烘干8小时，得到氯球A7。
咪唑化：在500ml三口瓶中加入30克氯球A7(氯含量为3.4mmol Cl/g)、咪唑(102.0mmol)与200ml乙腈，在80℃下反应24小时，冷却至室温，过滤，依次用乙酸乙酯、0.1mol/L的HCl、去离子水、甲醇洗涤，然后真空60℃烘12小时得到咪唑微球A7。
POSS化：在500ml三口烧瓶中，加入30克咪唑微球A7(咪唑基团含量为3.1mmol/g)，9.3克八氯甲基倍半硅氧烷以及300ml四氢呋喃，于100℃下24小时，反应结束后过滤，用四氢呋喃、去离子水依次洗涤，得到咪唑/POSS微球A7。
离子交换：在1000ml三口烧瓶中，加入30克咪唑/POSS微球A7，500ml浓度为0.1mol/L的NaBr的去离子水溶液在室温下搅拌进行离子交换反应24小时；随后用去离子水洗涤直至洗液pH＝7，真空干燥后得到离子交换树脂催化剂，记为Cat-A7，结构式如下：
Figure PCTCN2020117335-appb-000015
【实施例12】
将【实施例1】制备的离子交换树脂用于环氧烷烃和二氧化碳的加成反应，实验条件如下：在高纯氮气保护下，将50.0克环氧乙烷、7.5克树脂催化剂Cat-A1加入300毫升高压釜中，充入1.0MPa CO 2，升温至120℃，再充入CO 2维持反应压力在2.0MPa，反应4小时后过滤除去催化剂，测得环氧乙烷转化率C EO为96.7％，碳酸乙烯酯选择性S EC为99.3％。
【实施例13～27】
改变树脂催化剂种类及反应温度与压力，其它反应条件与【实施例12】相同，进行环氧乙烷和二氧化碳的催化反应，反应后分析结果见表1。
表1
Figure PCTCN2020117335-appb-000016
【实施例28】
将【实施例12】中所使用的催化剂Cat-A1过滤，洗涤，干燥，然后再次按照【实施例12】中的反应步骤与条件，催化环氧乙烷和二氧化碳的反应，得到催化剂循环使用2次的结果，见表2。依此类推，分别进行循环次数为3～5次的催化反应，结果见表2。
表2
循环次数 C EO％ S EC％
2 95.6 99.0
3 95.9 99.1
4 95.5 99.2
5 95.3 98.9
【实施例29-32】
将【实施例1】中制备的催化剂用于其他环氧烷烃与二氧化碳的加成反应，条件如下：在高纯氮气保护下，将50.0克环氧烷烃、7.5 克树脂催化剂加入300毫升高压釜中，充入1.0MPa CO 2，升温至120℃，再充入CO 2维持反应压力在2.0MPa，反应4小时后过滤除去催化剂，测定环氧烷烃的转化率，以及所得碳酸酯的选择性。结果见表3。
表3
Figure PCTCN2020117335-appb-000017
【对照例1】
按照文献Catal.Sci.Technol.,2014,4,1598–1607的制备方法，制备催化剂SiO 2–ethane–Br，将其用于氧化苯乙烯与与二氧化碳的加成反应，条件如下：在高纯氮气保护下，将50.0克氧化苯乙烯、7.5克催化剂加入300毫升高压釜中，充入1.0MPa CO 2，升温至120℃，再充入CO 2维持反应压力在2.0MPa，反应4小时后过滤除去催化剂，测定氧化苯乙烯的转化率，以及所得苯乙烯环状碳酸酯的选择性。结果见表4。
【对照例2】
按照文献Catalysis Today 2013,200,117–124的制备方法，制备催化剂SBA-15-IL3Br，将其用于环氧丙烷与与二氧化碳的加成反应，条件如下：在高纯氮气保护下，将50.0克环氧丙烷、7.5克催化剂加入300毫升高压釜中，充入1.0MPa CO 2，升温至120℃，再充入CO 2维持反应压力在2.0MPa，反应4小时后过滤除去催化剂，测定环氧丙烷的转化率，以及所得碳酸丙烯酯的选择性。结果见表4。
【对照例3】
按照文献Green Chem.,2013,15,1584–1589的制备方法，制备催化剂Poly[bvbim]Cl，将其用于氧化苯乙烯与与二氧化碳的加成反应，条件如下：在高纯氮气保护下，将50.0克氧化苯乙烯、7.5克催化剂加入300毫升高压釜中，充入1.0MPa CO 2，升温至120℃，再充入CO 2维持反应压力在2.0MPa，反应4小时后过滤除去催化剂，测定氧 化苯乙烯的转化率，以及所得苯乙烯环状碳酸酯的选择性。结果见表4。
表4
Figure PCTCN2020117335-appb-000018
【实施例33：渗磨圆球率测定】
1.称取16mL样品转移至有机玻璃交换柱中，加入25mL纯水；迅速倒入25mL氢氧化钠的去离子水溶液(1mol/L)，在10～15s内排完，重复操作5次；然后再倒入20mL氢氧化钠的去离子水溶液(1mol/L)，树脂层无气泡，加入250mL纯水，使去离子水在5min内均匀流完；
2.按照(1)的方法，用1mol/L的HCl去离子水溶液处理样品；
3.取15ml上述处理过的样品，加入一定量去离子水，总体积为50ml，转移至滚筒中，加入10个瓷球，旋紧筒盖；
4.滚筒置于球磨机上，以125r/min的转速旋转树脂20min；
5.用纯水将处理后的树脂转移筛网布上，60℃烘干2～3h至颗粒能自由滚动；
6.烘干样品置于搪瓷盘中，略微倾斜使得圆球颗粒滚下，破碎颗粒刷至右上角，两部分样品中，另外一种样品残留量均小于50粒即分离完全；
7.分别称量圆球、破碎颗粒的质量，记为m1、m2；
8.渗磨圆球率S＝m1/(m1+m2)×100。
【实施例34：磨后圆球率测定】
1.称取50mL原样，树脂层上有5mL纯水；
2. 145mL纯水将树脂转移至滚筒内，加10个瓷球旋紧筒盖；
3.滚筒置于球磨机上，以125r/min的转速旋转树脂30min；
4.用纯水将处理后的树脂转移筛网布上，60℃烘干2～3h至颗粒能自由滚动；
5.烘干样品置于搪瓷盘中，略微倾斜使得圆球颗粒滚下，破碎颗粒刷至右上角，两部分样品中，另外一种样品残留量均小于50粒即分离完全；
6.分别称量圆球、破碎颗粒的质量，记为m3、m4；
7.磨后圆球率A＝m3/(m3+m4)×100。
本发明催化剂Cat A1的磨后圆球率为65.3％，渗磨圆球率为37.6％。而CNT-基催化剂(参考CN109569717A)的磨后圆球率为54.2％，渗磨圆球率为25.5％。
上述实验数据表明本发明纳米复合树脂催化剂具有更高的强度。
【实施例35：溶胀率测定】
溶胀率的测定：
1.将一定体积的催化剂转移至有机玻璃交换柱中，催化剂的体积记为V1；
2.将一定量的去离子水倒入有机玻璃交换柱内，树脂层上有5mL纯水；
3.室温下静置24小时后，记录催化剂溶胀后的体积，记为V2；
4.计算催化剂的溶胀率S＝(V 2-V 1)/V 1×100％。
催化剂 溶胀率(％)
Cat-A6(对比例) 25.4
Cat-A1 33.2
CNT-基催化剂 27.6
应当注意的是，以上所述的实施例仅用于解释本发明，并不对本发明构成任何限制。通过参照典型实施例对本发明进行了描述，但应当理解为其中所用的词语为描述性和解释性词汇，而不是限定性的词汇。可以按规定在本发明权利要求的范围内对本发明作出修改，以及 在不背离本发明的范围和精神内对本发明进行修订。尽管其中描述的本发明涉及特定的方法、材料和实施例，但是并不意味着本发明限于其中公开的特定例，相反，本发明可以扩展至其它所有具有相同功能的方法和应用。

Claims (10)

  1. 一种用于环氧烷烃加成反应的催化剂，包括结构式为P-Im +-M -的纳米复合离子交换树脂，其中P为纳米复合树脂基体，Im +为5-6元含至少1个氮原子的杂环阳离子如咪唑阳离子、吡唑阳离子、吡咯烷阳离子、哌啶阳离子、哌嗪阳离子、嘧啶阳离子、吡嗪阳离子、哒嗪阳离子、三嗪阳离子(例如5-6元含至少1个氮原子的杂芳烃阳离子，如咪唑阳离子、吡唑阳离子、嘧啶阳离子、吡嗪阳离子、哒嗪阳离子、三嗪阳离子)，M -为阴离子。
  2. 根据权利要求1所述的催化剂，其特征在于，所述纳米复合树脂基体包括式I所示的结构片段和-CH(POSS)-CH 2-结构片段，
    Figure PCTCN2020117335-appb-100001
    式I中R 1-R 8相同或不同，各自独立选自氢和C 1-C 6烷基，优选选自氢、甲基、乙基、丙基和丁基；
    POSS为笼型倍半硅氧烷，所述笼型倍半硅氧烷通式为(-SiO 1.5) m，m为6、8、10或12。
  3. 根据前述权利要求中任一项所述的催化剂，其特征在于，所述催化剂包括如下结构：
    Figure PCTCN2020117335-appb-100002
    其中R 1-R 3相同或不同，各自独立选自氢和C 1-C 6烷基；
    R 4-R 8选自氢、C 1-C 6烷基和CH 2Im +-M -，并且R 4-R 8中至少其中之一为CH 2Im +-M -，优选地，R 4-R 8选自氢和CH 2Im +-M -，并且R 4-R 8中至少其中之一为CH 2Im +-M -。
  4. 根据前述权利要求中任一项所述的催化剂，其特征在于，所述M -选自卤离子和有机酸根离子中的一种或多种，优选选自氟离子、氯离子、溴离子、碘离子、乙酸根、甲酸根和草酸氢根中的一种或多种；和/或，所述纳米复合树脂基体P中POSS的质量含量为0.1-10％，优选为0.2-5％，更优选为2-5％。
  5. 一种如权利要求1-4中任意一项所述的催化剂的制备方法，包括以下步骤：
    S1：将苯乙烯类单体、交联剂和笼型倍半硅氧烷在引发剂存在的条件下进行聚合得到纳米复合树脂基体P；
    S2：将步骤S1所得纳米复合树脂基体P进行氯甲基化反应、咪唑化反应和离子交换反应。
  6. 根据权利要求5所述的方法，其特征在于，所述苯乙烯类单体选自式II所示的苯乙烯类单体中的一种或多种；
    Figure PCTCN2020117335-appb-100003
    式II中，R 1-R 8相同或不同，各自独立选自氢和C 1-C 6烷基，优选选自氢、甲基、乙基、丙基和丁基；
    和/或，所述笼型倍半硅氧烷选自含乙烯基倍半硅氧烷、含氢基聚倍半硅氧烷、含烷氧基聚倍半硅氧烷和含环氧基聚倍半硅氧烷中的一种或多种，优选地，所述含乙烯基倍半硅氧选自八乙烯基倍半硅氧烷；
    和/或，所述交联剂选自双甲基丙烯酸乙二醇酯、二丙烯基苯、二乙烯基苯基甲烷或二乙烯基苯中的一种或多种；
    和/或，所述引发剂选自过氧化苯甲酰、偶氮二异丁腈、偶氮二异庚腈、 过氧化月桂酰或异丙苯过氧化氢中的至少一种，
    和/或，在步骤S1中，以原料总重计，所述苯乙烯单体的质量为85-95％，所述交联剂的质量为1-6％，所述笼型倍半硅氧烷的质量为0.1-10％，优选为0.2-5％，更优选为2-5％，所述引发剂的质量为0.1-5％。
  7. 一种环氧烷烃与二氧化碳加成反应的方法，包括在根据权利要求1-4中任一项所述的催化剂或权利要求5或6所述的方法制备的催化剂存在的条件下，使环氧烷烃和二氧化碳进行反应。
  8. 根据权利要求7中任意一项所述的方法，其特征在于，所述环氧烷烃具有如下通式：
    Figure PCTCN2020117335-appb-100004
    其中，R 9-R 12相同或不同，各自独立选自氢、C 1-C 6烷基和C 6-C 10芳基，优选选自氢、甲基、乙基、丙基、丁基和苯基；和/或，
    所述催化剂与所述环氧烷烃的质量比为(0.001-1):1，优选为(0.1-0.3):1。
  9. 根据权利要求7或8所述的方法，其特征在于，所述反应的温度为60-180℃，优选为100-160℃；和/或，所述反应的压力为0.1-10.0MPa，优选为2-5MPa；和/或，所述反应的时间为1-8小时，优选为3-6小时。
  10. 权利要求1-4中任意一项所述的催化剂或权利要求5或6所述的方法制备的催化剂在环氧烷烃加成反应中的应用。
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