CATALYST FOR ALKYLENE OXIDE ADDITION REACTION AND APPLICATION THEREOF

Abstract

The present invention provides a catalyst for an addition reaction of alkylene oxide, the catalyst comprises a nanocomposite ion-exchange resin having a structural formula of P-Im.sup.+-M.sup.−, wherein P is a nanocomposite resin matrix, Im.sup.+ is a cation derived from 5-6 membered heterocycle containing at least one nitrogen atom such as imidazolium cation, pyrazolium cation, pyrrolidinium cation, piperidinium cation, piperazinium cation, pyrimidinium cation, pyrazinium cation, pyridazinium cation, triazinium cation, and M.sup.− is an anion. The catalyst of the present invention can be used in the addition reaction of alkylene oxide and carbon dioxide. The catalyst has high wear resistance, high swelling resistance, and high activity. The products after the reaction are easy to separate, and the catalyst can be used continuously many times.

Claims

1. A catalyst for addition reaction of alkylene oxide, comprising a nanocomposite ion-exchange resin having a structural formula of P-Im.sup.+-M.sup.−, wherein P is a nanocomposite resin matrix, Im.sup.+ is a cation derived from 5-6 membered heterocycle containing at least one nitrogen atom, M.sup.− is an anion.

2. The catalyst according to claim 1, which is characterized in that wherein the nanocomposite resin matrix comprises a structure fragment represented by formula I and a structure fragment of —CH(POSS)-CH.sub.2—, ##STR00016## in formula I, R.sub.1-R.sub.8 are identical to or different from each other, and each independently selected from hydrogen and C.sub.1-C.sub.6 alkyl; POSS is a polyhedral oligomeric silsesquioxane, which has a general formula of (—SiO1.5)m, and m is 6, 8, 10, or 12.

3. The catalyst according to claim 1, wherein the catalyst comprises the following structure: ##STR00017## wherein R.sub.1-R.sub.3 are identical to or different from each other, and each independently selected from hydrogen and C.sub.1-C.sub.6 alkyl; R.sub.4-R.sub.8 are each independently selected from hydrogen, C.sub.1-C.sub.6 alkyl, and CH.sub.2Im.sup.+-M.sup.−, and at least one of R.sub.4-R.sub.8 is CH.sub.2Im.sup.+-M.sup.−.

4. The catalyst according to claim 1, wherein said M.sup.− is one or more of halide ions and organic acid radical ions; and/or, a mass content of POSS in the nanocomposite resin matrix P is 0.1-10%.

5. A process for preparing a catalyst as claimed in claim 1, comprising the following steps: S1: polymerizing a styrene-based monomer, a cross-linking agent, and a polyhedral oligomeric silsesquioxane in the presence of an initiator to obtain a nanocomposite resin matrix P; S2: subjecting the nanocomposite resin matrix P obtained in step S1 to a chloromethylation reaction, an imidazolation reaction, and an ion-exchange reaction.

6. The process according to claim 5, wherein said styrene-based monomer is one or more of styrene-based monomers represented by formula II; ##STR00018## In formula II, R.sub.1-R.sub.8 are identical to or different from each other, and each independently selected from hydrogen and C.sub.1-C.sub.6 alkyl; and/or, said polyhedral oligomeric silsesquioxane is one or more of a vinyl-containing silsesquioxane, a hydrogen-containing polysilsesquioxane, an alkoxy-containing polysilsesquioxane, and an epoxy-containing polysilsesquioxane; and/or, said cross-linking agent is one or more of ethylene glycol bismethacrylate, dipropenylbenzene, divinylphenylmethane, and divinylbenzene; and/or, said initiator is at least one of benzoyl peroxide, azodiisobutyronitrile, azodiisoheptylonitrile, lauroyl peroxide, and cumene hydroperoxide, and/or, in step S1, based on the total weight of raw materials, a mass of said styrene-based monomer is 85-95%, a mass of the cross-linking agent is 1-6%, a mass of said polyhedral oligomeric silsesquioxane is 0.1-10%, and a mass of the initiator is 0.1-5%.

7. A method for an addition reaction of alkylene oxide and carbon dioxide, which comprises reacting alkylene oxide and carbon dioxide in the presence of the catalyst according to claim 1.

8. The method according to claim 7, wherein the alkylene oxide has a general formula of ##STR00019## wherein, R.sub.9-R.sub.12 are identical to or different from each other and each independently selected from hydrogen, C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10 aryl; and/or, a mass ratio of the catalyst to the alkylene oxide is (0.001-1):1.

9. The method according to claim 7, wherein a reaction temperature is 60-180° C.; and/or a reaction pressure is 0.1-10.0 MPa; and/or, a reaction time is 1-8 hours.

10. (canceled)

11. The catalyst according to claim 1, wherein Im.sup.+ is an imidazolium cation, pyrazolium cation, pyrrolidinium cation, piperidinium cation, piperazinium cation, pyrimidinium cation, pyrazinium cation, pyridazinium cation, or triazinium cation.

12. The catalyst according to claim 1, wherein the C.sub.1-C.sub.6 alkyl is hydrogen, methyl, ethyl, propyl, or butyl.

13. The catalyst according to claim 1, wherein the M.sup.− is one or more of a fluoride ion, a chloride ion, a bromide ion, an iodide ion, an acetate group, a formate group, and a bioxalate group.

14. The method according to claim 6, wherein the vinyl-containing silsesquioxane is an octavinylsilsesquioxane.

15. A method for an addition reaction of alkylene oxide and carbon dioxide, which comprises reacting alkylene oxide and carbon dioxide in the presence of a catalyst prepared with the method according to claim 5.

16. The method according to claim 8, wherein the C.sub.6-C.sub.10 aryl is phenyl.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0063] FIG. 1: Infrared spectrum of the ion-exchange resin of Example 1.

DETAILED DESCRIPTION

[0064] The present invention will be further described below through examples, but it should be pointed out that the protection scope of the present invention is not limited thereto, but is determined by the appended claims.

[0065] It should be particularly noted that two or more aspects (or embodiments) disclosed in the context of this specification can be combined with each other arbitrarily, and the technical solutions formed thereby belong to a part of the original disclosure of this specification, and also falls within the protection scope of the present invention.

[0066] Raw Materials:

[0067] Styrene: analytically pure, purchased from Sinopharm, used after removing a polymerization inhibitor;

[0068] Divinylbenzene: analytically pure, purchased from Sinopharm, used after removing a polymerization inhibitor;

[0069] Octavinylsilsesquioxane: analytically pure, purchased from Sinopharm, used directly;

[0070] Benzoyl peroxide: analytically pure, purchased from Sinopharm, used after recrystallization;

[0071] Polyvinyl alcohol\gelatin: analytically pure, purchased from Sinopharm, used directly;

[0072] Chloromethyl ether\chloromethyl ethyl ether\1,4-dichloromethoxybutane: analytically pure, purchased from Sinopharm, used directly;

[0073] 1-methylimidazole \1-butylimidazole\imidazole: analytically pure, purchased from Sinopharm, used directly;

[0074] Acetonitrile: analytically pure, purchased from Sinopharm, used directly;

[0075] Other unmentioned reagents used in the examples are commercially available, and were analytically pure, purchased from Sinopharm, and used directly.

[Example 1] Preparation of Ion-Exchange Resin

[0076] To a 500 mL three-necked flask were added 65.0 g of styrene, 1.0 g of divinylbenzene, 3.0 g of octavinylsilsesquioxane, and 1.0 g of benzoyl peroxide, a stirrer was started, and the mixture was stirred for 0.5 hours; a mixed solution of 200 mL of deionized water and 4 g of polyvinyl alcohol was added, the mixture was stirred for 2 hours. Then, the mixture was gradually warmed up to 75° C. and reacted for 5 hours, then warmed up to 90° C. and reacted for 10 hours, and finally warmed up to 100° C. and reacted for 10 hours. After the completion of the reaction, the supernatant liquid was poured out, washed with hot water at 85° C., then washed with cold water, then filtered, put into an oven and dried at 80° C., sieved to collect composite microspheres A1 with a particle size in the range of 0.35-0.60 mm.

[0077] Chloromethylation of composite microspheres: To a 500 mL three-necked flask were added 40 g of composite microspheres A1 and 250 mL of chloromethyl ether; after standing for 3 hours at room temperature, the stirring was started; 10 g of zinc chloride was added as the catalyst; the mixture was warmed up to 60° C. and reacted for 10 hours, and then cooled to room temperature after the completion of the chloromethylation; the chlorination mother liquor was filtered out, washed with methanol repeatedly, and dried at 100° C. for 8 hours to obtain chloromethylated composite spheres A1.

[0078] Imidazolation: To a 500 mL three-necked flask were added 30 g of chloromethylated composite spheres A1 (having a chlorine content of 3.4 mmol Cl/g), 1-methylimidazole (102.0 mmol), and 200 mL of acetonitrile; the mixture was reacted at 60° C. for 24 hours, cooled to room temperature, filtered, washed with ethyl acetate, 0.1 mol/L HCl, deionized water, and methanol successively, and then dried under vacuum at 60° C. for 12 hours to obtain imidazolated composite microspheres A1.

[0079] Ion-exchange: To a 1000 mL three-necked flask were added 30 g of imidazolated composite microspheres A1, and 500 mL of a solution of NaBr in deionized water having a concentration of 0.1 mol/L; the mixture was stirred at room temperature to perform an ion-exchange reaction for 24 hours, then washed with deionized water until the pH of the washing liquor was 7, and dried under vacuum to obtain an ion-exchange resin catalyst, which was denoted as Cat-A1, and had the following structural formula:

##STR00005##

[Example 2] Preparation of Ion-Exchange Resin

[0080] To a 500 mL three-necked flask was added a monomer mixture solution containing an initiator (60.0 g of styrene, 1.0 g of divinylbenzene, 1.6 g of octavinylsilsesquioxane, and 1.0 g of benzoyl peroxide, this solution was firstly reacted under stirring at 70° C. for 0.5 hours), a stirrer was started, a mixed solution of 200 mL of deionized water and 4 g of polyvinyl alcohol was added, the mixture was warmed up to 85° C. and reacted for 3 hours, then warmed up to 90° C. and reacted for 9 hours, and finally warmed up to 100° C. and reacted for 10 hours. After the completion of the reaction, the supernatant liquid was poured out, washed with hot water at 85° C., then washed with cold water, then filtered, put into an oven and dried at 80° C., sieved to collect composite microspheres B1 with a particle size in the range of 0.35-0.60 mm.

[0081] Chloromethylation of composite microspheres: To a 500 mL three-necked flask were added 50 g of composite microspheres B1 and 200 mL of chloromethyl ethyl ether; after standing for 6 hours at room temperature, 30 g of zinc chloride was added as the catalyst and the stirring was started; the mixture was warmed up to 50° C. and reacted for 30 hours, and then cooled to room temperature after the completion of the chloromethylation; the chlorination mother liquor was filtered out, washed with methanol repeatedly, and dried at 100° C. for 8 hours to obtain chloromethylated composite spheres B1.

[0082] Imidazolation: To a 500 mL three-necked flask were added 50 g of chloromethylated composite spheres B1 (having a chlorine content of 4.6 mmol Cl/g), 1-methylimidazole (230.0 mmol), and 300 mL of acetonitrile; the mixture was reacted at 80° C. for 16 hours, cooled to room temperature, filtered, washed with ethyl acetate, 0.1 mol/L HCl, deionized water, and methanol successively, and then dried under vacuum at 60° C. for 12 hours to obtain imidazolated composite microspheres B 1.

[0083] Ion-exchange: To a 1000 mL three-necked flask were added 40 g of imidazolated composite microspheres B 1, and 400 mL of a solution of NaBr in deionized water having a concentration of 0.1 mol/L; the mixture was stirred at room temperature to perform an ion-exchange reaction for 12 hours, then washed with deionized water until the pH of the washing liquor was 7, and dried under vacuum to obtain an ion-exchange resin catalyst, which was denoted as Cat-B1, and had the following structural formula:

##STR00006##

[Example 3] Preparation of Ion-Exchange Resin

[0084] To a 500 mL three-necked flask was added a monomer mixture solution containing an initiator (42.5 g of styrene, 2.5 g of divinylbenzene, 0.1 g of octavinylsilsesquioxane, and 2.0 g of benzoyl peroxide, this solution was firstly reacted under stirring at 70° C. for 1.5 hours), a mixed solution of 200 mL of deionized water and 4 g of polyvinyl alcohol was added, the mixture was warmed up to 85° C. and reacted for 3 hours, then warmed up to 90° C. and reacted for 9 hours, and finally warmed up to 100° C. and reacted for 10 hours. After the completion of the reaction, the supernatant liquid was poured out, washed with hot water at 85° C., then washed with cold water, then filtered, put into an oven and dried at 80° C., sieved to collect composite microspheres C1 with a particle size in the range of 0.35-0.60 mm.

[0085] Chloromethylation of composite microspheres: To a 250 mL three-necked flask were added 20 g of composite microspheres C1 and 100 mL of 1,4-dichloromethoxybutane; after standing for 6 hours at room temperature, 8 g of zinc chloride was added as the catalyst and the stirring was started; the mixture was warmed up to 30° C. and reacted for 12 hours, and then cooled to room temperature after the completion of the chloromethylation; the chlorination mother liquor was filtered out, washed with methanol repeatedly, and dried at 100° C. for 8 hours to obtain chloromethylated composite spheres C1.

[0086] Imidazolation: To a 250 mL three-necked flask were added 20 g of chloromethylated composite spheres C1 (having a chlorine content of 1.5 mmol Cl/g), 1-ethylimidazole (30.0 mmol), and 150 mL of acetonitrile; the mixture was reacted at 90° C. for 16 hours, cooled to room temperature, filtered, washed with ethyl acetate, 0.1 mol/L HCl, deionized water, and methanol successively, and then dried under vacuum at 60° C. for 12 hours to obtain imidazolated composite microspheres C1.

[0087] Ion-exchange: To a 500 mL three-necked flask were added 20 g of imidazolated composite microspheres C1, and 300 mL of a solution of NaBr in deionized water having a concentration of 0.5 mol/L; the mixture was stirred at room temperature to perform an ion-exchange reaction for 12 hours, then washed with deionized water until the pH of the washing liquor was 7, and dried under vacuum to obtain an ion-exchange resin catalyst, which was denoted as Cat-C1, and had the following structural formula:

##STR00007##

[Example 4] Preparation of Ion-Exchange Resin

[0088] To a 500 mL three-necked flask were added 47.0 g of styrene, 2.3 g of divinylbenzene, and 1.6 g of benzoyl peroxide (as an initiator); the mixture was reacted under stirring at 60° C. for 2.0 hours; then 0.6 g of octavinylsilsesquioxane was added, the stirring was continued for 1 hour to perform the pre-polymerization. 260 mL of a solution of 2.0 g of gelatin dissolved in deionized water was added. The stirring speed was adjusted, while the mixture was gradually warmed up to 80° C. and reacted for 5 hours; then warmed up to 90° C. and reacted for 5 hours, and finally warmed up to 98° C. and reacted for 6 hours. After the completion of the reaction, the supernatant liquid was poured out, washed with hot water at 85° C., then washed with cold water, then filtered, put into an oven and dried at 80° C., sieved to collect composite microspheres A2 with a particle size in the range of 0.35-0.60 mm.

[0089] Chloromethylation of composite microspheres: To a 500 mL three-necked flask were added 40 g of composite microspheres A2 and 250 mL of chloromethyl ether; after standing for 3 hours at room temperature, the stirring was started; 10 g of zinc chloride was added as the catalyst; the mixture was warmed up to 60° C. and reacted for 10 hours, and then cooled to room temperature after the completion of the chloromethylation; the chlorination mother liquor was filtered out, washed with methanol repeatedly, and dried at 100° C. for 8 hours to obtain chloromethylated composite spheres A2.

[0090] Imidazolation: To a 500 mL three-necked flask were added 30 g of chloromethylated composite spheres A2 (having a chlorine content of 3.6 mmol Cl/g), 1-methylimidazole (108.0 mmol), and 200 mL of acetonitrile; the mixture was reacted at 60° C. for 24 hours, cooled to room temperature, filtered, washed with ethyl acetate, 0.1 mol/L HCl, deionized water, and methanol successively, and then dried under vacuum at 60° C. for 12 hours to obtain imidazolated composite microspheres A2.

[0091] Ion-exchange: To a 1000 mL three-necked flask were added 30 g of imidazolated composite microspheres A2, and 500 mL of a solution of NaBr in deionized water having a concentration of 0.1 mol/L; the mixture was stirred at room temperature to perform an ion-exchange reaction for 24 hours, then washed with deionized water until the pH of the washing liquor was 7, and dried under vacuum to obtain an ion-exchange resin catalyst, which was denoted as Cat-A2, and had the following structural formula:

##STR00008##

[Example 5] Preparation of Ion-Exchange Resin

[0092] To a 500 mL three-necked flask was added a monomer mixture solution containing an initiator (60.0 g of styrene, 1.0 g of divinylbenzene, 1.6 g of octavinylsilsesquioxane, and 1.0 g of benzoyl peroxide, this solution was firstly reacted under stirring at 70° C. for 0.5 hours), a stirrer was started, a mixed solution of 200 mL of deionized water and 4 g of polyvinyl alcohol was added, the mixture was warmed up to 85° C. and reacted for 3 hours, then warmed up to 90° C. and reacted for 9 hours, and finally warmed up to 100° C. and reacted for 10 hours. After the completion of the reaction, the supernatant liquid was poured out, washed with hot water at 85° C., then washed with cold water, then filtered, put into an oven and dried at 80° C., sieved to collect composite microspheres B2 with a particle size in the range of 0.35-0.60 mm.

[0093] Chloromethylation of composite microspheres: To a 500 mL three-necked flask were added 50 g of composite microspheres B2 and 200 mL of chloromethyl ethyl ether; after standing for 6 hours at room temperature, 30 g of zinc chloride was added as the catalyst and the stirring was started; the mixture was warmed up to 50° C. and reacted for 30 hours, and then cooled to room temperature after the completion of the chloromethylation; the chlorination mother liquor was filtered out, washed with methanol repeatedly, and dried at 100° C. for 8 hours to obtain chloromethylated composite spheres B2.

[0094] Imidazolation: To a 500 mL three-necked flask were added 50 g of chloromethylated composite spheres B2 (having a chlorine content of 4.7 mmol Cl/g), 1-butylimidazole (235.0 mmol), and 300 mL of acetonitrile; the mixture was reacted at 80° C. for 16 hours, cooled to room temperature, filtered, washed with ethyl acetate, 0.1 mol/L HCl, deionized water, and methanol successively, and then dried under vacuum at 60° C. for 12 hours to obtain imidazolated composite microspheres B2.

[0095] Ion-exchange: To a 1000 mL three-necked flask were added 40 g of imidazolated composite microspheres B2, and 400 mL of a solution of NaBr in deionized water having a concentration of 0.1 mol/L; the mixture was stirred at room temperature to perform an ion-exchange reaction for 12 hours, then washed with deionized water until the pH of the washing liquor was 7, and dried under vacuum to obtain an ion-exchange resin catalyst, which was denoted as Cat-B2, and had the following structural formula:

##STR00009##

[Example 6] Preparation of Ion-Exchange Resin

[0096] To a 500 mL three-necked flask was added a monomer mixture solution containing an initiator (42.5 g of styrene, 2.5 g of divinylbenzene, 0.1 g of octavinylsilsesquioxane and 2.0 g of benzoyl peroxide, this solution was firstly reacted under stirring at 70° C. for 1.5 hours), a mixed solution of 200 mL of deionized water and 4 g of polyvinyl alcohol was added, the mixture was warmed up to 85° C. and reacted for 3 hours, then warmed up to 90° C. and reacted for 9 hours, and finally warmed up to 100° C. and reacted for 10 hours. After the completion of the reaction, the supernatant liquid was poured out, washed with hot water at 85° C., then washed with cold water, then filtered, put into an oven and dried at 80° C., sieved to collect composite microspheres C2 with a particle size in the range of 0.35-0.60 mm.

[0097] Chloromethylation of composite microspheres: To a 250 mL three-necked flask were added 20 g of composite microspheres C2 and 100 mL of 1,4-dichloromethoxybutane; after standing for 6 hours at room temperature, 8 g of zinc chloride was added as the catalyst and the stirring was started; the mixture was warmed up to 30° C. and reacted for 12 hours, and then cooled to room temperature after the completion of the chloromethylation; the chlorination mother liquor was filtered out, washed with methanol repeatedly, and dried at 100° C. for 8 hours to obtain chloromethylated composite spheres C2.

[0098] Imidazolation: To a 250 mL three-necked flask were added 20 g of chloromethylated composite spheres C2 (having a chlorine content of 1.6 mmol Cl/g), 1-methylimidazole (320 mmol), and 150 mL of acetonitrile; the mixture was reacted at 90° C. for 16 hours, cooled to room temperature, filtered, washed with ethyl acetate, 0.1 mol/L HCl, deionized water, and methanol successively, and then dried under vacuum at 60° C. for 12 hours to obtain imidazolated composite microspheres C2.

[0099] Ion-exchange: To a 500 mL three-necked flask were added 20 g of imidazolated composite microspheres C2, and 300 mL of a solution of NaBr in deionized water having a concentration of 0.5 mol/L; the mixture was stirred at room temperature to perform an ion-exchange reaction for 12 hours, then washed with deionized water until the pH of the washing liquor was 7, and dried under vacuum to obtain an ion-exchange resin catalyst, which was denoted as Cat-C2, and had the following structural formula:

##STR00010##

[Example 7] Preparation of Ion-Exchange Resin

[0100] To a 500 mL three-necked flask were added 65.0 g of styrene, 1.0 g of divinylbenzene, 0.07 g of octavinylsilsesquioxane and 1.0 g of benzoyl peroxide, a stirrer was started, and the mixture was stirred for 0.5 hours; a mixed solution of 200 mL of deionized water and 4 g of polyvinyl alcohol was added, the mixture was stirred for 2 hours. Then, the mixture was gradually warmed up to 75° C. and reacted for 5 hours, then warmed up to 90° C. and reacted for 10 hours, and finally warmed up to 100° C. and reacted for 10 hours. After the completion of the reaction, the supernatant liquid was poured out, washed with hot water at 85° C., then washed with cold water, then filtered, put into an oven and dried at 80° C., sieved to collect composite microspheres A3 with a particle size in the range of 0.35-0.60 mm.

[0101] Chloromethylation of composite microspheres: To a 500 mL three-necked flask were added 40 g of composite microspheres A3 and 250 mL of chloromethyl ether; after standing for 3 hours at room temperature, the stirring was started; 10 g of zinc chloride was added as the catalyst; the mixture was warmed up to 60° C. and reacted for 10 hours, and then cooled to room temperature after the completion of the chloromethylation; the chlorination mother liquor was filtered out, washed with methanol repeatedly, and dried at 100° C. for 8 hours to obtain chloromethylated composite spheres A3.

[0102] Imidazolation: To a 500 mL three-necked flask were added 30 g of chloromethylated composite spheres A3 (having a chlorine content of 3.4 mmol Cl/g), 1-methylimidazole (102.0 mmol), and 200 mL of acetonitrile; the mixture was reacted at 60° C. for 24 hours, cooled to room temperature, filtered, washed with ethyl acetate, 0.1 mol/L HCl, deionized water, and methanol successively, and then dried under vacuum at 60° C. for 12 hours to obtain imidazolated composite microspheres A3.

[0103] Ion-exchange: To a 1000 mL three-necked flask were added 30 g of imidazolated composite microspheres A3, and 500 mL of a solution of NaBr in deionized water having a concentration of 0.1 mol/L; the mixture was stirred at room temperature to perform an ion-exchange reaction for 24 hours, then washed with deionized water until the pH of the washing liquor was 7, and dried under vacuum to obtain an ion-exchange resin catalyst, which was denoted as Cat-A3, and had the following structural formula:

##STR00011##

[Example 8] Preparation of Ion-Exchange Resin

[0104] To a 500 mL three-necked flask were added 65.0 g of styrene, 1.0 g of divinylbenzene, 7.5 g of octavinylsilsesquioxane and 1.0 g of benzoyl peroxide, a stirrer was started, and the mixture was stirred for 0.5 hours; a mixed solution of 200 mL of deionized water and 4 g of polyvinyl alcohol was added, the mixture was stirred for 2 hours. Then, the mixture was gradually warmed up to 75° C. and reacted for 5 hours, then warmed up to 90° C. and reacted for 10 hours, and finally warmed up to 100° C. and reacted for 10 hours. After the completion of the reaction, the supernatant liquid was poured out, washed with hot water at 85° C., then washed with cold water, then filtered, put into an oven and dried at 80° C., sieved to collect composite microspheres A5 with a particle size in the range of 0.35-0.60 mm.

[0105] Chloromethylation of composite microspheres: To a 500 mL three-necked flask were added 40 g of composite microspheres A4 and 250 mL of chloromethyl ether; after standing for 3 hours at room temperature, the stirring was started; 10 g of zinc chloride was added as the catalyst; the mixture was warmed up to 60° C. and reacted for 10 hours, and then cooled to room temperature after the completion of the chloromethylation; the chlorination mother liquor was filtered out, washed with methanol repeatedly, and dried at 100° C. for 8 hours to obtain chloromethylated composite spheres A4.

[0106] Imidazolation: To a 500 mL three-necked flask were added 30 g of chloromethylated composite spheres A4 (having a chlorine content of 3.4 mmol Cl/g), 1-methylimidazole (102.0 mmol), and 200 mL of acetonitrile; the mixture was reacted at 60° C. for 24 hours, cooled to room temperature, filtered, washed with ethyl acetate, 0.1 mol/L HCl, deionized water, and methanol successively, and then dried under vacuum at 60° C. for 12 hours to obtain imidazolated composite microspheres A4.

[0107] Ion-exchange: To a 1000 mL three-necked flask were added 30 g of imidazolated composite microspheres A4, and 500 mL of a solution of NaBr in deionized water having a concentration of 0.1 mol/L; the mixture was stirred at room temperature to perform an ion-exchange reaction for 24 hours, then washed with deionized water until the pH of the washing liquor was 7, and dried under vacuum to obtain an ion-exchange resin catalyst, which was denoted as Cat-A4, and had the following structural formula:

##STR00012##

[Example 9] Preparation of Ion-Exchange Resin

[0108] To a 500 mL three-necked flask were added 65.0 g of styrene, 1.0 g of divinylbenzene, 11.8 g of octavinylsilsesquioxane, and 1.0 g of benzoyl peroxide, a stirrer was started, and the mixture was stirred for 0.5 hours; a mixed solution of 200 mL of deionized water and 4 g of polyvinyl alcohol was added, the mixture was stirred for 2 hours. Then, the mixture was gradually warmed up to 75° C. and reacted for 5 hours, then warmed up to 90° C. and reacted for 10 hours, and finally warmed up to 100° C. and reacted for 10 hours. After the completion of the reaction, the supernatant liquid was poured out, washed with hot water at 85° C., then washed with cold water, then filtered, put into an oven and dried at 80° C., sieved to collect composite microspheres A5 with a particle size in the range of 0.35-0.60 mm.

[0109] Chloromethylation of composite microspheres: To a 500 mL three-necked flask were added 40 g of composite microspheres A5 and 250 mL of chloromethyl ether; after standing for 3 hours at room temperature, the stirring was started; 10 g of zinc chloride was added as the catalyst; the mixture was warmed up to 60° C. and reacted for 10 hours, and then cooled to room temperature after the completion of the chloromethylation; the chlorination mother liquor was filtered out, washed with methanol repeatedly, and dried at 100° C. for 8 hours to obtain chloromethylated composite spheres A5.

[0110] Imidazolation: To a 500 mL three-necked flask were added 30 g of chloromethylated composite spheres A5 (having a chlorine content of 3.4 mmol Cl/g), 1-methylimidazole (102.0 mmol), and 200 mL of acetonitrile; the mixture was reacted at 60° C. for 24 hours, cooled to room temperature, filtered, washed with ethyl acetate, 0.1 mol/L HCl, deionized water, and methanol successively, and then dried under vacuum at 60° C. for 12 hours to obtain imidazolated composite microspheres A5.

[0111] Ion-exchange: To a 1000 mL three-necked flask were added 30 g of imidazolated composite microspheres A5, and 500 mL of a solution of NaBr in deionized water having a concentration of 0.1 mol/L; the mixture was stirred at room temperature to perform an ion-exchange reaction for 24 hours, then washed with deionized water until the pH of the washing liquor was 7, and dried under vacuum to obtain an ion-exchange resin catalyst, which was denoted as Cat-A5, and had the following structural formula:

##STR00013##

[Comparative Example 10] Preparation of Ion-Exchange Resin

[0112] To a 500 mL three-necked flask were added 65.0 g of styrene, 1.0 g of divinylbenzene, and 1.0 g of benzoyl peroxide, a stirrer was started, and the mixture was stirred for 0.5 hours; a mixed solution of 200 mL of deionized water and 4 g of polyvinyl alcohol was added, the mixture was stirred for 2 hours. Then, the mixture was gradually warmed up to 75° C. and reacted for 5 hours, then warmed up to 90° C. and reacted for 10 hours, and finally warmed up to 100° C. and reacted for 10 hours. After the completion of the reaction, the supernatant liquid was poured out, washed with hot water at 85° C., then washed with cold water, then filtered, put into an oven and dried at 80° C., sieved to collect microspheres A6 with a particle size in the range of 0.35-0.60 mm.

[0113] Chloromethylation of microspheres: To a 500 mL three-necked flask were added 40 g of microspheres A6 and 250 mL of chloromethyl ether; after standing for 3 hours at room temperature, the stirring was started; 10 g of zinc chloride was added as the catalyst; the mixture was warmed up to 60° C. and reacted for 10 hours, and then cooled to room temperature after the completion of the chloromethylation; the chlorination mother liquor was filtered out, washed with methanol repeatedly, and dried at 100° C. for 8 hours to obtain chloromethylated spheres A6.

[0114] Imidazolation: To a 500 mL three-necked flask were added 30 g of chloromethylated spheres A6 (having a chlorine content of 3.4 mmol Cl/g), 1-methylimidazole (102.0 mmol), and 200 mL of acetonitrile; the mixture was reacted at 60° C. for 24 hours, cooled to room temperature, filtered, washed with ethyl acetate, 0.1 mol/L HCl, deionized water, and methanol successively, and then dried under vacuum at 60° C. for 12 hours to obtain imidazolated microspheres A6.

[0115] Ion-exchange: To a 1000 mL three-necked flask were added 30 g of imidazolated microspheres A6, and 500 mL of a solution of NaBr in deionized water having a concentration of 0.1 mol/L; the mixture was stirred at room temperature to perform an ion-exchange reaction for 24 hours, then washed with deionized water until the pH of the washing liquor was 7, and dried under vacuum to obtain an ion-exchange resin catalyst, which was denoted as Cat-A6, and had the following structural formula:

##STR00014##

[Comparative Example 11] Preparation of Ion-Exchange Resin

[0116] To a 500 mL three-necked flask were added 65.0 g of styrene, 1.0 g of divinylbenzene, and 1.0 g of benzoyl peroxide, a stirrer was started, and the mixture was stirred for 0.5 hours; a mixed solution of 200 mL of deionized water and 4 g of polyvinyl alcohol was added, the mixture was stirred for 2 hours. Then, the mixture was gradually warmed up to 75° C. and reacted for 5 hours, then warmed up to 90° C. and reacted for 10 hours, and finally warmed up to 100° C. and reacted for 10 hours. After the completion of the reaction, the supernatant liquid was poured out, washed with hot water at 85° C., then washed with cold water, then filtered, put into an oven and dried at 80° C., sieved to collect microspheres A7 with a particle size in the range of 0.35-0.60 mm.

[0117] Chloromethylation of microspheres: To a 500 mL three-necked flask were added 40 g of microspheres A7 and 250 mL of chloromethyl ether; after standing for 3 hours at room temperature, the stirring was started; 10 g of zinc chloride was added as the catalyst; the mixture was warmed up to 60° C. and reacted for 10 hours, and then cooled to room temperature after the completion of the chloromethylation; the chlorination mother liquor was filtered out, washed with methanol repeatedly, and dried at 100° C. for 8 hours to obtain chloromethylated spheres A7.

[0118] Imidazolation: To a 500 mL three-necked flask were added 30 g of chloromethylated spheres A7 (having a chlorine content of 3.4 mmol Cl/g), imidazole (102.0 mmol), and 200 mL of acetonitrile; the mixture was reacted at 80° C. for 24 hours, cooled to room temperature, filtered, washed with ethyl acetate, 0.1 mol/L HCl, deionized water, and methanol successively, and then dried under vacuum at 60° C. for 12 hours to obtain imidazole microspheres A7.

[0119] POSS-incorporated: To a 500 mL three-necked flask were added 30 g of imidazole microspheres A7 (having an imidazole group content of 3.1 mmol/g), 9.3 g of octachloromethyl silsesquioxane, and 300 mL of tetrahydrofuran; the mixture was reacted at 100° C. for 24 hours, filtered after the reaction, washed with tetrahydrofuran and deionized water successively to obtain imidazole/POSS microspheres A7.

[0120] Ion-exchange: To a 1000 mL three-necked flask were added 30 g of imidazole/POSS microspheres A7, and 500 mL of a solution of NaBr in deionized water having a concentration of 0.1 mol/L; the mixture was stirred at room temperature to perform an ion-exchange reaction for 24 hours, then washed with deionized water until the pH of the washing liquor was 7, and dried under vacuum to obtain an ion-exchange resin catalyst, which was denoted as Cat-A7, and had the following structural formula:

##STR00015##

Example 12

[0121] 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, to a 300 mL autoclave were added 50.0 g of ethylene oxide and 7.5 g of resin catalyst Cat-A1, filled with CO.sub.2 at 1.0 MPa, warmed up to 120° C., refilled with CO.sub.2 to maintain the reaction pressure at 2.0 MPa, reacted for 4 hours and filtered to remove the catalyst. As measured, the ethylene oxide conversion C.sub.EO was 96.7%, and the ethylene carbonate selectivity S.sub.EC was 99.3%.

Examples 13-27

[0122] The type of the resin catalyst and the reaction temperature and pressure were changed, and other reaction conditions were identical to those in [Example 12]. The catalytic reaction of ethylene oxide and carbon dioxide was performed and the analysis results after the reaction were shown in Table 1.

TABLE-US-00001 TABLE 1 Catalyst Reaction Ex. Catalyst Amount/g Temp/° C. Time/h Pressure/MPa C.sub.EO, % S.sub.EC, % 12 Cat-A2 7.5 120 4 2.0 96.9 99.2 13 Cat-B1 7.5 120 4 2.0 95.5 98.9 14 Cat-B2 7.5 120 4 2.0 95.7 99.1 15 Cat-C1 7.5 120 4 2.0 95.3 99.3 16 Cat-C2 7.5 120 4 2.0 95.6 98.9 17 Cat-A3 7.5 120 4 2.0 92.9 98.9 18 Cat-A4 7.5 120 4 2.0 94.6 98.7 19 Cat-A5 7.5 120 4 2.0 92.8 98.5 20 Cat-A6 7.5 120 4 2.0 89.5 98.6 21 Cat-A7 7.5 120 4 2.0 80.3 95.1 22 Cat-A1 7.5 160 4 2.0 99.4 99.3 23 Cat-A1 7.5 100 4 2.0 94.5 99.2 24 Cat-A1 7.5 180 4 2.0 99.4 99.3 25 Cat-A1 7.5 120 4 0.1 20.2 98.6 26 Cat-A1 7.5 120 4 5 96.8 99.2 27 Cat-A1 7.5 120 4 10.0 95.5 99.1

Example 28

[0123] The catalyst Cat-A1 used in [Example 12] was filtered, washed, and dried, and then the catalytic reactions of ethylene oxide and carbon dioxide were performed according to the reaction steps and conditions in [Example 12]. The results for which the catalysts were used in two circulations were shown in Table 2. By analogy, the catalytic reactions in which the catalysts were used in 3-5 circulations were performed respectively, and the results were shown in Table 2.

TABLE-US-00002 TABLE 2 Circulation Number C.sub.EO % S.sub.EC % 2 95.6 99.0 3 95.9 99.1 4 95.5 99.2 5 95.3 98.9

Examples 29-32

[0124] The catalyst prepared in [Example 1] was used for the addition reaction of other alkylene oxides and carbon dioxide. The experimental conditions were as follows: under the protection of high-purity nitrogen, to a 300 mL autoclave were added 50.0 g of alkylene oxide and 7.5 g of resin catalyst, filled with CO.sub.2 at 1.0 MPa, warmed up to 120° C., refilled with CO.sub.2 to maintain the reaction pressure at 2.0 MPa, reacted for 4 hours and filtered to remove the catalyst. The alkylene oxide conversion and the obtained carbonate selectivity were measured. The results were shown in Table 3.

TABLE-US-00003 TABLE 3 Alkylene Catalyst Reaction Examples Oxide Catalyst Amount/g Temp/° C. Time/hr Pressure/MPa C.sub.on, % S.sub.ec, % 29 Propylene Cat-A1 7.5 120 4 2.0 93.5 98.5 oxide 30 Styrene Cat-A1 7.5 120 4 2.0 60.3 98.5 oxide 31 Propylene Cat-B1 7.5 120 4 2.0 90.2 99.0 oxide 32 Styrene Cat-B1 7.5 120 4 2.0 56.5 99.1 oxide

Reference Example 1

[0125] According to the preparation method disclosed in the article of Catal. Sci. Technol., 2014, 4, 1598-1607, the catalyst SiO.sub.2-ethane-Br was prepared. That catalyst was used for the addition reaction of styrene oxide and carbon dioxide. The experimental conditions were as follows: under the protection of high-purity nitrogen, to a 300 mL autoclave were added 50.0 g of styrene oxide and 7.5 g of catalyst, filled with CO.sub.2 at 1.0 MPa, warmed up to 120° C., refilled with CO.sub.2 to maintain the reaction pressure at 2.0 MPa, reacted for 4 hours and filtered to remove the catalyst. The styrene oxide conversion and the obtained cyclic styrene carbonate selectivity were measured. The results were shown in Table 4.

Reference Example 2

[0126] According to the preparation method disclosed in the article of Catalysis Today 2013, 200, 117-124, the catalyst SBA-15-IL3Br was prepared. That catalyst was used for the addition reaction of propylene oxide and carbon dioxide. The experimental conditions were as follows: under the protection of high-purity nitrogen, to a 300 mL autoclave were added 50.0 g of propylene oxide and 7.5 g of catalyst, filled with CO.sub.2 at 1.0 MPa, warmed up to 120° C., refilled with CO.sub.2 to maintain the reaction pressure at 2.0 MPa, reacted for 4 hours and filtered to remove the catalyst. The propylene oxide conversion and the obtained propylene carbonate selectivity were measured. The results were shown in Table 4.

Reference Example 3

[0127] According to the preparation method disclosed in the article of Green Chem., 2013, 15, 1584-1589, the catalyst Poly[bvbim]Cl was prepared. That catalyst was used for the addition reaction of styrene oxide and carbon dioxide. The experimental conditions were as follows: under the protection of high-purity nitrogen, to a 300 mL autoclave were added 50.0 g of styrene oxide and 7.5 g of catalyst, filled with CO.sub.2 at 1.0 MPa, warmed up to 120° C., refilled with CO.sub.2 to maintain the reaction pressure at 2.0 MPa, reacted for 4 hours and filtered to remove the catalyst. The styrene oxide conversion and the obtained cyclic styrene carbonate selectivity were measured. The results were shown in Table 4.

TABLE-US-00004 TABLE 4 Reference Alkylene Catalyst Reaction Example oxide Catalyst Amount/g Temp/° C. Time/hr Pressure/MPa C.sub.on, % S.sub.ec, % 1 Styrene SiO.sub.2- 7.5 120 4 2.0 42.1 98.6 oxide ethane-Br 2 Propylene SBA-15-IL3Br 7.5 120 4 2.0 73.5 97.0 oxide 3 Styrene Poly[bvbim]Cl 7.5 120 4 2.0 24.9 98.5 oxide

Example 33: Determination for Sphericity after Osmotic Attrition

[0128] 1. 16 mL of a sample was weighed and transferred to an organic glass exchange column, 25 mL of pure water was added; a solution of sodium hydroxide in deionized water (25 mL, 1 mol/L) was quickly poured and drained off within 10-15 seconds, the operation was repeated 5 times; then a solution of sodium hydroxide in deionized water (20 mL, 1 mol/L), no bubble was in the resin layer, 250 mL of pure water was added, and the deionized water was allowed to flow out evenly within 5 minutes;

[0129] 2. According to the method of (1), the sample was treated with a solution of HCl in deionized water (1 mol/L);

[0130] 3. To 15 mL of the above-treated sample was added a certain amount of deionized water so that the total volume was 50 mL, the mixture was transferred to a rotary drum, 10 ceramic balls were added, and the drum cover was tightened;

[0131] 4. The rotary drum was placed on a ball mill, and the resin was rotated at a speed of 125 r/min for 20 minutes;

[0132] 5. the treated resin was transferred to a screen cloth with pure water, and dried at 60° C. for 2-3 hours until the particles can roll freely;

[0133] 6. The dried sample was placed in an enamel tray, the tray was slightly inclined to allow the spherical particles to roll down, and the broken particles were brushed to the upper right corner. The sample was divided into two parts, i.e., the spherical particles and the broken particles. For each of two parts, the residual amount of another sample less than 50 particles means that the separation was complete;

[0134] 7. The masses of spherical particles and broken particles were respectively measured, and denoted as m1 and m2;

[0135] 8. Sphericity after osmotic attrition S=m1/(m1+m2)×100.

Example 34: Determination of Sphericity after Attrition

[0136] 1. 50 mL of an original sample was taken, and 5 mL of pure water was present on the resin layer;

[0137] 2. The resin was transferred to a rotary drum by using 145 mL of pure water, 10 ceramic balls were added, and the drum cover was tightened;

[0138] 3. The rotary drum was placed on a ball mill, and the resin was rotated at a speed of 125 r/min for 30 minutes;

[0139] 4. the treated resin was transferred to a screen cloth with pure water, and dried at 60° C. for 2-3 hours until the particles can roll freely;

[0140] 5. The dried sample was placed in an enamel tray, the tray was slightly inclined to allow the spherical particles to roll down, and the broken particles were brushed to the upper right corner. The sample was divided into two parts, i.e., the spherical particles and the broken particles. For each of two parts, the residual amount of another sample less than 50 particles means that the separation was complete;

[0141] 6. The masses of spherical particles and broken particles were respectively measured, and denoted as m3 and m4;

[0142] 7. Sphericity after attrition A=m3/(m3+m4)×100.

[0143] The catalyst of the present invention (Cat A1) had sphericity after attrition of 65.3%, and sphericity after osmotic attrition of 37.6%. The CNT-based catalyst (with reference to CN109569717A) had sphericity after attrition of 54.2% and sphericity after osmotic attrition of 25.5%.

[0144] The above experimental data showed that the nanocomposite resin catalyst of the present invention had higher strength.

Example 35: Determination for Swelling Ratio

[0145] Determination for Swelling Ratio:

[0146] 1. A certain volume of the catalyst was transferred to an organic glass exchange column, and the volume of the catalyst was recorded as V1;

[0147] 2. A certain amount of deionized water was poured into an organic-glass exchange column, and 5 mL of pure water was present on the resin layer;

[0148] 3. After standing at room temperature for 24 hours, the volume of the swelled catalyst was recorded, denoted as V2;

[0149] 4. The swelling ratio of the catalyst was calculated, S=(V2−V1)/V1×100%.

TABLE-US-00005 Catalyst Swelling Ratio (%) Cat-A6 (Comparative Example) 25.4 Cat-A1 33.2 CNT-based catalyst 27.6

[0150] It should be noted that the above-mentioned embodiments are only used to explain the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but it is to be understood that the words used therein are words of description and explanation, rather than words of limitation. The present invention may be modified within the scope of the claims of the present invention as specified and may be modified without departing from the scope and spirit of the present invention. Although the present invention described herein refers to the specific methods, materials, and embodiments, it is not intended to be limited to the specific examples disclosed therein, but rather, the present invention extends to all other methods and applications having the same function.