CN105503811A - Preparation method of ethylene carbonate - Google Patents
Preparation method of ethylene carbonate Download PDFInfo
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- CN105503811A CN105503811A CN201410497643.1A CN201410497643A CN105503811A CN 105503811 A CN105503811 A CN 105503811A CN 201410497643 A CN201410497643 A CN 201410497643A CN 105503811 A CN105503811 A CN 105503811A
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Abstract
The invention relates to a preparation method of ethylene carbonate, and mainly solves the problems of low activity and easy inactivation of catalysts in the prior. According to a technical scheme, ethylene oxide and carbon dioxide are adopted as the raw materials, under the conditions of a reaction temperature of 60-200DEG C, a reaction pressure of 0.1-10.0MPa, and a catalyst/ethylene oxide weight ratio of 0.001-1, the reaction raw materials and the catalyst contact to generate ethylene carbonate; and the catalyst is halogen composite imidazolyl resin. The method well solves the problems, and can be used for the industrial production of ethylene carbonate from ethylene oxide and carbon dioxide.
Description
Technical field
The present invention relates to a kind of method preparing NSC 11801.
Background technology
NSC 11801 is a kind of solvent and fine-chemical intermediate of excellent property, is the potential basic material of organic chemical industry.CO simultaneously
2be a kind of greenhouse gases, how effectively fix and become one of challenging problem of most in this century, and by oxyethane and CO
2reactive Synthesis NSC 11801 is exactly wherein a kind of well fixing means.Along with being recently that raw material co-producing dimethyl carbonate and glycol reaction receive publicity, day by day by cyclic carbonate fixation of C O with NSC 11801
2approach also receive increasing attention.
The method majority of the production cyclic carbonate reported at present is the binary homogeneous catalyst using Lewis acid metal compound and Lewis alkali composition, the Lewis acid metal compound wherein used comprises alkali (soil) metal halide, transition metal salt, transition metal or Main group metal complexes, the Lewis alkali used has organic bases (as DMF, DMAP etc.), quaternary ammonium salt, quaternary alkylphosphonium salt, imidazole salts, crown ether etc.These catalyst system perhaps active, selectivity is not high, or employs the very strong organic solvent of toxicity, and there is the shortcoming that catalyzer is difficult to be separated in homogeneous catalysis system.And use more heterogeneous catalysis system to comprise metal oxide system (as CeO at present
2-ZrO
2, GreenChem.2004,6,206-214), basic zeolite system (as Cs/KX, J.Catal.2001,199,85-91) etc., these active catalyst system are low, and the required reaction times is longer.Xia Chungu etc. are by ZnCl
2immobilized on chitin carrier, although achieve higher catalytic activity, after catalyzer applies mechanically 5 times, activity reduces about 8%, infers that possible reason is the loss (Appl.Catal.A2005,279,125-129) of catalyst activity component.Therefore, develop a kind of easily separated, activity is high, reaction conditions is gentle, not the catalyst system of easy in inactivation seem very important.
Summary of the invention
Technical problem to be solved by this invention is the problem that prior art exists low, the easy inactivation of catalyst activity, provides a kind of method preparing NSC 11801 newly.The method has catalyst activity feature that is high, not easy in inactivation.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method preparing NSC 11801, with oxyethane and carbonic acid gas for raw material, it is 60 ~ 200 DEG C in temperature of reaction, reaction pressure is 0.1 ~ 10.0 MPa, the weight ratio of catalyzer and oxyethane is under the condition of 0.001 ~ 1, reaction raw materials and catalyst exposure Formed vinyl acetate; Described catalyzer is halogen-type compound imidazolyl resin, and its preparation method comprises the following steps:
1) auxiliary agent one is made into water solution A; By monomer, comonomer, nano material, initiator and auxiliary agent two wiring solution-forming B;
Described monomer is selected from least one in methyl methacrylate, butyl acrylate, vinylbenzene, alpha-methyl styrene, 4-butylstyrene or vinyl cyanide; Described comonomer is selected from least one in ethyleneglycol dimethyacrylate, diallyl benzene, divinyl phenylmethane or Vinylstyrene; Described nano material is selected from least one in multi-walled carbon nano-tubes, Single Walled Carbon Nanotube, C60 or C70 soccerballene; Described initiator is selected from least one in benzoyl peroxide, Diisopropyl azodicarboxylate, lauroyl peroxide or isopropyl benzene hydroperoxide; Described auxiliary agent one is selected from least one in polyvinyl alcohol, gelatin, starch, methylcellulose gum, wilkinite or calcium carbonate; Described auxiliary agent two is selected from least one in aliphatic hydrocarbon, polystyrene, gasoline, lipid acid or paraffin;
Wherein, by weight percentage, the consumption of monomer is 85 ~ 95%, and the consumption of comonomer is 2 ~ 5%, and the consumption of nano material is 0.1 ~ 3%, and the consumption of initiator is 0.1 ~ 10%; The consumption of auxiliary agent one is 150 ~ 400% of monomer consumption, and the consumption of auxiliary agent two is 50 ~ 100% of monomer consumption;
2) solution B is mixed with solution A, be obtained by reacting complex microsphere;
3) in described complex microsphere, add chloromethylation reagents and zinc chloride, obtain compound chlorine ball;
4) chlorine type compound imidazolyl resin is obtained add imdazole derivatives reaction in described compound chlorine ball after; Described imdazole derivatives structural formula is
wherein R is methyl, ethyl, propyl group, sec.-propyl, propenyl, normal-butyl or n-pentyl;
5) add in described chlorine type compound imidazolyl resin after metal halide solution exchanges and obtain described halogen-type compound imidazolyl resin.
In technique scheme, preferably, the weight percent concentration of described water solution A is 0.5 ~ 2%.
In technique scheme, preferably, step 2) reaction process is: solution B, 60 ~ 75 DEG C of prepolymerizations 0.5 ~ 2.5 hour, then mixes with solution A by solution B, be warming up to 70 ~ 90 DEG C of reactions 5 ~ 15 hours, then be warming up to 90 ~ 100 DEG C of reactions 5 ~ 15 hours; After reaction terminates, through extracting, washing, filtration, drying, sieve, obtain the complex microsphere of particle size range 0.35 ~ 0.60 millimeter.
In technique scheme, preferably, step 3) reaction process is: in described complex microsphere, add the chloromethylation reagents being equivalent to complex microsphere weight 200 ~ 500%, and be equivalent to the zinc chloride catalyst of complex microsphere weight 20 ~ 70%, react 8 ~ 30 hours at 30 ~ 60 DEG C, after filtration, washing obtain compound chlorine ball, dry to constant weight; Described chloromethylation reagents is selected from least one in chloromethyl ether or Isosorbide-5-Nitrae-dichloro methyl butyl ether.
In technique scheme, preferably, step 4) reaction process is: adds in described compound chlorine ball and is equivalent to the organic solvent of complex microsphere weight 200 ~ 700%, the imdazole derivatives of 30 ~ 300%, react 4 ~ 30 hours under reflux state, after washing, oven dry, obtain described chlorine type compound imidazolyl resin; Wherein, described organic solvent is selected from least one in acetonitrile, cyanobenzene, toluene, tetrahydrofuran (THF), dimethyl formamide, chloroform or ethylene dichloride.
In technique scheme, preferably, step 5) reaction process is: adds in described chlorine type compound imidazolyl resin and is equivalent to the metal halide of chlorine type compound imidazolyl weight resin 20 ~ 200%, the water of 200 ~ 2000%, at room temperature stir 1 ~ 20 hour, after filtration, wash and obtain described halogen-type compound imidazolyl resin after oven dry; Wherein, described metal halide comprises NaBr, KBr, LiBr, NaI, KI, LiI, MgBr
2, MgI
2, CaBr
2, CaI
2, SrBr
2, SrI
2, BaBr
2or BaI
2in at least one.
In technique scheme, preferably, described monomer is selected from vinylbenzene.
In technique scheme, preferably, described comonomer is selected from Vinylstyrene.
In technique scheme, preferably, described nano material is selected from multi-walled carbon nano-tubes.
In technique scheme, preferably, described initiator is selected from benzoyl peroxide.
In technique scheme, preferably, described auxiliary agent one is selected from polyvinyl alcohol.
In technique scheme, preferably, described auxiliary agent two is selected from polystyrene.
In technique scheme, preferably, temperature of reaction is 80 ~ 160 DEG C, and reaction pressure is 0.5 ~ 8.0 MPa, and the weight ratio of catalyzer and oxyethane is 0.005 ~ 0.5.
The inventive method adopts halogen-type compound imidazolyl resin to be catalyzer, owing to being mixed with the nano material of high strength in resin base material, thus enhances the swelling resistance performance of resin, prevents catalyzer due to swelling and inactivation that is that cause.Catalyzer of the present invention is 120 DEG C in temperature of reaction, reaction pressure is 2.0MPa, 3 hours are reacted when the weight ratio of catalyzer and oxyethane is 0.02, the transformation efficiency of oxyethane is 95.6%, the selectivity of NSC 11801 is 99.7%, apply mechanically 5 times after catalyst separating, active reduction is less than 5%, achieves good technique effect.
Below by embodiment, the invention will be further elaborated.Be necessary to herein means out be following examples only for further illustrating of the present invention, can not limiting the scope of the invention be interpreted as.
Embodiment
[embodiment 1]
In 500 milliliters of there-necked flasks, add 58.0 grams of vinylbenzene, 0.6 gram of Vinylstyrene, 30 grams of polystyrene and 0.6 gram of benzoyl peroxide initiator, stir 2.0 hours at 60 DEG C; Then add 2.8 grams of multi-walled carbon nano-tubes, continue stirring and carry out prepolymerization in 1 hour.Add the 260 ml deionized water solution being dissolved with 2.5 grams of polyvinyl alcohol.Regulate stirring velocity, be progressively warming up to 80 DEG C simultaneously, react 5 hours; Be warmed up to 90 DEG C again, react 5 hours, be finally warming up to 98 DEG C, react 6 hours.After reaction terminates, pour out supernatant liquid, with 85 DEG C of hot washes, then use cold water washing, then filter, put into the oven dry of 80 DEG C, baking oven, sieve, the complex microsphere A of collection cut size within the scope of 0.35 ~ 0.60 millimeter.
The chloromethylation of complex microsphere: in the there-necked flask of 500 milliliters, add 50 grams of complex microsphere A and 250 milliliter chloromethyl ethers, room temperature leaves standstill 4 hours, starts to stir, and adding 15 grams of zinc chloride is catalyzer, be warming up to 50 DEG C of reactions 8 hours, be cooled to room temperature after chlorination terminates, leach chlorination mother solution, use methyl alcohol repetitive scrubbing, dry 8 hours at 100 DEG C, obtain compound chlorine ball A.
The imidazoles salinization of compound chlorine ball: in 500 milliliters of there-necked flasks, add 20 grams of compound chlorine ball A, 100 milliliters of tetrahydrofuran (THF)s, 8 grams of N-Methylimidazoles, stirring reaction 12 hours at reflux, reaction terminates rear mistake and filters mother liquor, uses methylene dichloride, acetone and water washing successively respectively, dries to obtain chlorine type compound imidazolyl Resin A 1 under vacuo.
The transition of chlorine type compound imidazolyl resin: in 200 ml beakers, add 10 grams of chlorine type compound imidazolyl Resin A, 1,3 grams of NaBr and 180 gram deionized waters, stirring at room temperature is after 2 hours, filter, after deionized water wash, repeat said process 2 times, filter, with deionized water wash, dry under vacuo and obtain halogen-type compound imidazolyl Resin A 2.
[embodiment 2]
In 500 milliliters of there-necked flasks, add the compound chlorine ball A of 20 grams of [embodiment 1] gained, 150 milliliters of toluene, 35.0 grams of N-allyl imidazole, stirring reaction 30 hours at reflux, reaction terminates rear mistake and filters mother liquor, uses methylene dichloride, acetone and water washing successively respectively, dries to obtain chlorine type compound imidazolyl Resin A 3 under vacuo.
The transition of chlorine type compound imidazolyl resin: in 200 ml beakers, add 10 grams of chlorine type compound imidazolyl Resin A, 3,20 grams of KI and 40 gram deionized waters, stirring at room temperature is after 18 hours, filter, after deionized water wash, repeat said process 2 times, filter, with deionized water wash, dry under vacuo and obtain halogen-type compound imidazolyl Resin A 4.
[embodiment 3]
Monomer mixture solution (60.0 grams of vinylbenzene, 1.7 grams of Vinylstyrenes, the 60 grams of polystyrene containing initiator are added in 500 milliliters of there-necked flasks, 1.6 grams of multi-walled carbon nano-tubes and 1.0 grams of benzoyl peroxides, this solution was prior to 70 DEG C of stirring reactions 0.5 hour), start agitator, add the mixing solutions of 200 ml deionized water and 5 grams of gelatin, be warming up to 85 DEG C, react 3 hours, then be warmed up to 90 DEG C, react 9 hours, finally be warming up to 100 DEG C, react 10 hours.After reaction terminates, pour out supernatant liquid, with 85 DEG C of hot washes, then use cold water washing, then filter, put into the oven dry of 80 DEG C, baking oven, sieve, the complex microsphere B of collection cut size within the scope of 0.35 ~ 0.60 millimeter.
The chloromethylation of complex microsphere: in the there-necked flask of 500 milliliters, add 50 grams of complex microsphere B and 150 milliliter chloromethyl ethers, room temperature leaves standstill 6 hours, starts to stir, and adding 30 grams of zinc chloride is catalyzer, be warming up to 50 DEG C of reactions 24 hours, be cooled to room temperature after chlorination terminates, leach chlorination mother solution, use methyl alcohol repetitive scrubbing, dry 8 hours at 100 DEG C, obtain compound chlorine ball B.
The imidazoles salinization of compound chlorine ball: in 500 milliliters of there-necked flasks, add 20 grams of compound chlorine ball B, 150 milliliters of tetrahydrofuran (THF)s, 30.0 grams of N-propyl imidazoles, stirring reaction 24 hours at reflux, reaction terminates rear mistake and filters mother liquor, uses methylene dichloride, acetone and water washing successively respectively, dries to obtain chlorine type compound imidazolyl resin B 1 under vacuo.
The method of chlorine type compound imidazolyl resin B 1 described in [embodiment 2] is made the transition, obtains halogen-type compound imidazolyl resin B 2.
[embodiment 4]
In 500 milliliters of there-necked flasks, add the compound chlorine ball B of 15 grams of [embodiment 3] gained, 150 milliliters of tetrahydrofuran (THF)s, 35.0 grams of N-butylimidazolium, stirring reaction 10 hours at reflux, reaction terminates rear mistake and filters mother liquor, uses methylene dichloride, acetone and water washing successively respectively, dries to obtain chlorine type compound imidazolyl resin B 3 under vacuo.
The method of chlorine type compound imidazolyl resin B 3 described in [embodiment 2] is made the transition, obtains halogen-type compound imidazolyl resin B 4.
[embodiment 5]
Change monomer mixture solution (the 76.0 grams of alpha-methyl styrenes in [embodiment 3], 3.5 grams of Vinylstyrenes, 75 grams of gasoline, 2.4 grams of multi-walled carbon nano-tubes and 1.4 grams of benzoyl peroxides), all the other preparation conditions are identical with [embodiment 3], obtain complex microsphere C.
The chloromethylation of complex microsphere: in the there-necked flask of 500 milliliters, add 40 grams of complex microsphere C and 150 milliliter Isosorbide-5-Nitrae-dichloro methyl butyl ether, room temperature leaves standstill 6 hours, start to stir, adding 25 grams of zinc chloride is catalyzer, is warming up to 50 DEG C of reactions 24 hours, is cooled to room temperature after chlorination terminates, leach chlorination mother solution, use methyl alcohol repetitive scrubbing, dry 8 hours at 100 DEG C, obtain compound chlorine ball C.
The imidazoles salinization of compound chlorine ball: in 500 milliliters of there-necked flasks, add 30 grams of compound chlorine ball C, 150 milliliters of tetrahydrofuran (THF)s, 20.0 grams of N-vinyl imidazoles, stirring reaction 12 hours at reflux, reaction terminates rear mistake and filters mother liquor, uses methylene dichloride, acetone and water washing successively respectively, dries to obtain chlorine type compound imidazolyl resin C1 under vacuo.
The method of chlorine type compound imidazolyl resin C1 described in [embodiment 2] is made the transition, obtains halogen-type compound imidazolyl resin C2.
[embodiment 6]
According to the step of [embodiment 4], imidazoles salinization reaction is carried out to compound chlorine ball C, obtain chlorine type compound imidazolyl resin C3.
The method of chlorine type compound imidazolyl resin C3 described in [embodiment 2] is made the transition, obtains halogen-type compound imidazolyl resin C4.
[comparative example 1]
The preparation process of catalyzer is identical with [embodiment 1], does not just add multi-walled carbon nano-tubes, obtains chlorine type imidazolyl resin CA1 and halogen-type imidazolyl resin CA2 respectively.
[embodiment 7]
Catalyzer halogen-type compound imidazolyl Resin A 2 obtained by [embodiment 1] is used as the catalyzer of oxyethane and carbon dioxide reaction Formed vinyl acetate, reaction conditions is as follows: in 300mL autoclave, add 150.0g oxyethane and 3.0g catalyzer, be filled with 1.0MPaCO
2, be warming up to 120 DEG C, then be filled with CO
2, maintain reaction pressure at 2.0MPa, react after 3 hours and cool, open reactor, liquid form and aspect chromatogram is analyzed, and records oxyethane transformation efficiency (C
eObe %) 95.6%, NSC 11801 (S
eC%) selectivity is 99.7%, the swelling capacity S of resin catalyst
sWELLbe 4.6%.
[comparative example 2]
Catalyst activity test condition is identical with [embodiment 7], and just catalyzer used is halogen-type imidazolyl resin CA2, and the transformation efficiency obtaining oxyethane is 96.1%, and the selectivity of NSC 11801 is 98.5%, and the swelling capacity of resin catalyst is S
sWELLbe 23.5%.
[embodiment 8-12]
Change the strong base compound imidazolyl resin types that uses, identical with described in [embodiment 7] of all the other conditions, the result obtained is as shown in table 1.
Table 1
[embodiment 13-17]
Use A2 as catalyzer, change the mass ratio of temperature of reaction, reaction pressure catalyzer and oxyethane, other condition is all identical with [embodiment 7], and catalyst activity and selectivity is as shown in table 2.
Table 2
[embodiment 18]
After [embodiment 7] reaction terminates, by catalyst separating out, again react at identical conditions, so recycling five times, result shows that loss of catalyst activity is less than 5%, as shown in table 3.
Table 3
| Apply mechanically number of times | C EO％ | S EC％ |
| 1 | 95.2 | 99.7 |
| 2 | 94.6 | 99.6 |
| 3 | 94.3 | 99.5 |
| 4 | 94.0 | 99.1 |
| 5 | 93.6 | 99.4 |
[comparative example 3]
Catalyzer after [comparative example 2] reaction being terminated applies mechanically 5 times by same reaction conditions, and activity obviously declines.Reaction result is shown in Table 4.
Table 4
| Apply mechanically number of times | C EO％ | S EC％ |
| 1 | 92.5 | 99.7 |
| 2 | 86.2 | 99.6 |
| 3 | 83.6 | 99.7 |
| 4 | 80.5 | 99.6 |
| 5 | 75.8 | 99.4 |
Claims (9)
1. prepare the method for NSC 11801 for one kind, with oxyethane and carbonic acid gas for raw material, be 60 ~ 200 DEG C in temperature of reaction, reaction pressure is 0.1 ~ 10.0 MPa, the weight ratio of catalyzer and oxyethane is under the condition of 0.001 ~ 1, reaction raw materials and catalyst exposure Formed vinyl acetate; Described catalyzer is halogen-type compound imidazolyl resin, and its preparation method comprises the following steps:
1) auxiliary agent one is made into water solution A; By monomer, comonomer, nano material, initiator and auxiliary agent two wiring solution-forming B;
Described monomer is selected from least one in methyl methacrylate, butyl acrylate, vinylbenzene, alpha-methyl styrene, 4-butylstyrene or vinyl cyanide; Described comonomer is selected from least one in ethyleneglycol dimethyacrylate, diallyl benzene, divinyl phenylmethane or Vinylstyrene; Described nano material is selected from least one in multi-walled carbon nano-tubes, Single Walled Carbon Nanotube, C60 or C70 soccerballene; Described initiator is selected from least one in benzoyl peroxide, Diisopropyl azodicarboxylate, lauroyl peroxide or isopropyl benzene hydroperoxide; Described auxiliary agent one is selected from least one in polyvinyl alcohol, gelatin, starch, methylcellulose gum, wilkinite or calcium carbonate; Described auxiliary agent two is selected from least one in aliphatic hydrocarbon, polystyrene, gasoline, lipid acid or paraffin;
Wherein, by weight percentage, the consumption of monomer is 85 ~ 95%, and the consumption of comonomer is 2 ~ 5%, and the consumption of nano material is 0.1 ~ 3%, and the consumption of initiator is 0.1 ~ 10%; The consumption of auxiliary agent one is 150 ~ 400% of monomer consumption, and the consumption of auxiliary agent two is 50 ~ 100% of monomer consumption;
2) solution B is mixed with solution A, be obtained by reacting complex microsphere;
3) in described complex microsphere, add chloromethylation reagents and zinc chloride, obtain compound chlorine ball;
4) chlorine type compound imidazolyl resin is obtained add imdazole derivatives reaction in described compound chlorine ball after; Described imdazole derivatives structural formula is
wherein R is methyl, ethyl, propyl group, sec.-propyl, propenyl, normal-butyl or n-pentyl;
5) add in described chlorine type compound imidazolyl resin after metal halide solution exchanges and obtain described halogen-type compound imidazolyl resin.
2. prepare the method for NSC 11801 according to claim 1, it is characterized in that the weight percent concentration of described water solution A is 0.5 ~ 2%.
3. prepare the method for NSC 11801 according to claim 1, it is characterized in that step 2) reaction process is: solution B was 60 ~ 75 DEG C of prepolymerizations 0.5 ~ 2.5 hour, then solution B is mixed with solution A, be warming up to 70 ~ 90 DEG C of reactions 5 ~ 15 hours, then be warming up to 90 ~ 100 DEG C of reactions 5 ~ 15 hours; After reaction terminates, through extracting, washing, filtration, drying, sieve, obtain the complex microsphere of particle size range 0.35 ~ 0.60 millimeter.
4. prepare the method for NSC 11801 according to claim 1, it is characterized in that step 3) reaction process is: in described complex microsphere, add the chloromethylation reagents being equivalent to complex microsphere weight 200 ~ 500%, and be equivalent to the zinc chloride catalyst of complex microsphere weight 20 ~ 70%, react 8 ~ 30 hours at 30 ~ 60 DEG C, after filtration, washing obtain compound chlorine ball, dry to constant weight; Described chloromethylation reagents is selected from least one in chloromethyl ether or Isosorbide-5-Nitrae-dichloro methyl butyl ether.
5. prepare the method for NSC 11801 according to claim 1, it is characterized in that step 4) reaction process is: adds in described compound chlorine ball and is equivalent to the organic solvent of complex microsphere weight 200 ~ 700%, the imdazole derivatives of 30 ~ 300%, react 4 ~ 30 hours under reflux state, after washing, oven dry, obtain described chlorine type compound imidazolyl resin; Wherein, described organic solvent is selected from least one in acetonitrile, cyanobenzene, toluene, tetrahydrofuran (THF), dimethyl formamide, chloroform or ethylene dichloride.
6. prepare the method for NSC 11801 according to claim 1, it is characterized in that step 5) reaction process is: adds in described chlorine type compound imidazolyl resin and is equivalent to the metal halide of chlorine type compound imidazolyl weight resin 20 ~ 200%, the water of 200 ~ 2000%, at room temperature stir 1 ~ 20 hour, after filtration, wash and obtain described halogen-type compound imidazolyl resin after oven dry; Wherein, described metal halide comprises NaBr, KBr, LiBr, NaI, KI, LiI, MgBr
2, MgI
2, CaBr
2, CaI
2, SrBr
2, SrI
2, BaBr
2or BaI
2in at least one.
7. prepare the method for NSC 11801 according to claim 1, it is characterized in that described monomer is selected from vinylbenzene; Described comonomer is selected from Vinylstyrene; Described nano material is selected from multi-walled carbon nano-tubes; Described initiator is selected from benzoyl peroxide.
8. prepare the method for NSC 11801 according to claim 1, it is characterized in that described auxiliary agent one is selected from polyvinyl alcohol; Described auxiliary agent two is selected from polystyrene.
9. prepare the method for NSC 11801 according to claim 1, it is characterized in that temperature of reaction is 80 ~ 160 DEG C, reaction pressure is 0.5 ~ 8.0 MPa, and the weight ratio of catalyzer and oxyethane is 0.005 ~ 0.5.
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| CN109590029A (en) * | 2017-09-29 | 2019-04-09 | 中国石油化工股份有限公司 | Ion exchange resin and its purposes |
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| CN115960071A (en) * | 2023-01-04 | 2023-04-14 | 郑州中科新兴产业技术研究院 | Method for synthesizing cyclic carbonate in micro-channel reactor by eutectic ionic liquid under mild condition |
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| CN109575292A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | Ion exchange resin and application thereof |
| JP2022549663A (en) * | 2019-09-24 | 2022-11-28 | 中国石油化工股▲ふん▼有限公司 | Alkylene oxide addition reaction catalyst and its use |
| JP7490759B2 (en) | 2019-09-24 | 2024-05-27 | 中国石油化工股▲ふん▼有限公司 | Catalysts for alkylene oxide addition reactions and their uses |
| CN111804342A (en) * | 2020-09-09 | 2020-10-23 | 山东海科创新研究院有限公司 | Preparation method of supported metal ion liquid catalyst, product obtained by preparation method and application of supported metal ion liquid catalyst |
| CN114369080A (en) * | 2022-01-19 | 2022-04-19 | 凯瑞环保科技股份有限公司 | Device and method for synthesizing ethylene carbonate or propylene carbonate |
| CN114369080B (en) * | 2022-01-19 | 2024-03-29 | 凯瑞环保科技股份有限公司 | Device and method for synthesizing ethylene carbonate or propylene carbonate |
| CN114749213A (en) * | 2022-05-12 | 2022-07-15 | 中国科学院兰州化学物理研究所 | Modified polymer resin composite material, preparation method and application thereof, and preparation method of cyclic carbonate |
| CN115960071A (en) * | 2023-01-04 | 2023-04-14 | 郑州中科新兴产业技术研究院 | Method for synthesizing cyclic carbonate in micro-channel reactor by eutectic ionic liquid under mild condition |
| CN115960071B (en) * | 2023-01-04 | 2024-03-26 | 郑州中科新兴产业技术研究院 | Method for synthesizing cyclic carbonate from eutectic ionic liquid in micro-channel reactor under mild condition |
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