CN109174176B - Basic ionic liquid catalyst and preparation method thereof - Google Patents
Basic ionic liquid catalyst and preparation method thereof Download PDFInfo
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- C07C68/065—Preparation of esters of carbonic or haloformic acids from organic carbonates from alkylene carbonates
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- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
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Abstract
The invention relates to a preparation method of a basic ionic liquid catalyst for methanol ester exchange reaction, in particular to a preparation method of a methoxylated alkyl imidazole ionic liquid catalyst. In the preparation process of the catalyst, firstly, halogenated alkyl imidazole ionic liquid is synthesized, and then halogen anions are replaced by active methoxy anions through a displacement reaction to synthesize the methoxylated alkyl imidazole ionic liquid. The ionic liquid catalyst has the same ionic effect and synergistic effect with a methanol raw material, and has a very strong catalytic effect in a methanol ester exchange reaction. The generated dimethyl carbonate can form an azeotrope with methanol, the azeotrope is distilled in the reaction process, and the methanol raw material is supplemented, so that the static balance can be broken, the reaction is promoted to move towards the positive direction, a new dynamic reaction balance is formed, and the continuous industrial production is further realized.
Description
Technical Field
The invention relates to a preparation method of a basic ionic liquid catalyst for methanol ester exchange reaction, in particular to a preparation method of a methoxylated alkyl imidazole ionic liquid catalyst.
Background
Dimethyl carbonate is a green solvent with excellent properties and an important organic synthesis intermediate, and can replace highly toxic methylating reagents or hydroxylating reagents such as phosgene, methyl chloroformate, dimethyl sulfate and the like due to no toxicity and harmlessness, so that the dimethyl carbonate is widely applied to the fields of spinning, printing and dyeing, leather, synthetic fibers, papermaking, mechanical industry and the like, and is known as a new base block in the organic synthesis field of the 21 st century. With the progress of scientific and technological means and the popularization of high-grade electronic products, the demand of dimethyl carbonate is increasing continuously, and in the aspect of industrial production, dimethyl carbonate can replace virulent phosgene to be used as a hydroxylation reagent to synthesize engineering materials such as polycarbonate and the like; in the aspect of production process, the allyl diglycol carbonate thermosetting resin with excellent performance can be synthesized and used for development and application of photoelectric materials. Therefore, the dimethyl carbonate has higher added value and development potential.
The industrial production in the early years in China uses the phosgene methanol method to synthesize the dimethyl carbonate, and uses CO and Cl2Phosgene is generated under the action of the catalyst, and then the phosgene reacts with methanol or sodium methoxide to generate dimethyl carbonate, but the phosgene is extremely toxic and inconvenient to transport, so that the catalyst has certain limitation.
In recent years, the industrial production in China is explored and developed to carry out the methanol transesterification reaction, and cyclic carbonate ester and methanol are used for carrying out the transesterification reaction to generate dimethyl carbonate. At present, sodium methoxide is used as a catalyst in most production workshops, so that the catalytic effect is good, a static reaction is adopted, the conversion rate is low, a dynamic reaction is adopted, the conversion rate is improved, the catalyst is large in using amount, side reactions are easy to occur, the catalyst is inactivated, sodium salt is generated to block a reaction pipeline, and the sodium methoxide inactivation and the relevant reactions for blocking the pipeline are as follows.
In recent years, a large number of research reports about the use of ionic liquid as a new catalytic system appear, the development prospect of the ionic liquid catalyst is widely concerned by all countries in the world, compared with the traditional catalysts such as sodium methoxide and the like, the ionic liquid catalyst shows better catalytic performance, and the problems of inactivation and pipeline blockage of the traditional catalyst are expected to be solved.
The use of supported ionic liquids for the catalytic synthesis of dimethyl carbonate was first proposed by zhaxiangya et al in 2006 in the thirteenth national catalytic academic conference. Researches find that the newly synthesized quaternary ammonium bromide ionic liquid reacts with some anionic acid or salt to catalyze the reaction of carbon dioxide and methanol to synthesize dimethyl carbonate.
In the same year, Chuazhiz et al (chemical engineering progress, 2006(05): 546-550.) examined the effect of several ionic liquids on synthesizing dimethyl carbonate, most of which have no obvious catalytic effect, and only the ionic liquid of bromo-1-ethyl-3-methylimidazolium salt [ Emim ] Br is used for catalytic reaction, so that the mass yield of DMC is improved by about 1%.
In 2009 Fabris Massimo et al (Chemistry: a European Journal,2009,15 (45)) synthesized methylammonium and phosphorus based ionic liquids by anion exchange for the catalytic synthesis of dimethyl carbonate. The ionic liquid has high catalytic performance and can be applied to green synthesis reaction through experimental representation.
The [ Bmim ] OH ionic liquid is firstly used for catalyzing ester exchange to synthesize dipropyl carbonate in 2012 Lujunmin et al (university of Qingdao science, 2012,33(06):556 and 559+ 563). Meanwhile, the catalyst performance, reaction conditions, repeatability, stability and other factors are considered, so that under the optimal reaction conditions that the reaction temperature is 130 ℃, the reaction time is 3 hours, the dosage of n (catalyst) = n (DMC) =0.007:0.1 and n (n-PrOH) = n (DMC) =4:1, the selectivity of MPC and DPC is high, and the yield of dipropyl carbonate reaches about 11.4%.
The methylated alkyl imidazole ionic liquid designed by the patent is prepared by reacting N-methylimidazole with halogenated alkane to synthesize a halogenated alkyl imidazole ionic liquid intermediate, and then reacting the halogenated alkyl imidazole ionic liquid intermediate with sodium methoxide, wherein the prepared methoxylated imidazole ionic liquid releases methoxy anions in the catalysis process to promote ester exchange reaction. The ionic liquid is more beneficial to the activation and ring opening of the ethylene carbonate through the same ion effect and synergistic effect, further improves the catalytic activity and selectivity, solves the problem that the traditional catalyst blocks a reaction pipeline, reduces the dosage of the catalyst, can realize recycling, greatly reduces the cost, and has good industrial application prospect.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a catalyst for preparing dimethyl carbonate by ester exchange of cyclic carbonate and methanol.
The technical scheme is as follows:
a basic ionic liquid catalyst is used for methanol ester exchange reaction, and is characterized in that: the liquid catalyst is a methoxylated alkyl imidazole ionic liquid catalyst, and the structural general formula of the liquid catalyst is as follows:
wherein R is-CH3R' is an alkyl side chain-CnH2n+1，n=1,2,3……18。
The preparation method of the basic ionic liquid catalyst is characterized by comprising the following steps:
the method comprises the following steps:
step one, adding halogenated alkane and N-methylimidazole into a container according to a molar ratio of 1:1.2, condensing and refluxing, adding magnetons, stirring at a rotating speed of 150-200 r/min, condensing and refluxing, reacting at 80 ℃ for 48 hours, and taking out;
step two, washing the cooled mixture with ethyl acetate for three times to obtain light yellow viscous liquid, performing rotary evaporation at 70 ℃ and under the reduced pressure of 0.08MPa, and placing the liquid in a vacuum drying oven for drying for 24 hours at 70 ℃ to obtain a halogenated alkyl imidazole ionic liquid intermediate [ CnMIM ] X;
step three, taking a proper amount of intermediate [ CnMIM]Dissolving X in 50mL of methanol, mixing uniformly, adding equimolar solid sodium methoxide, refluxing and condensing, stirring at room temperature for 10h, and then heating and preserving heat for 6h in stages to obtain NaX crystals and [ CnMIM]CH3A mixture of O;
removing sodium halide NaX by using a suction filtration device, and then removing methanol by carrying out reduced pressure rotary evaporation at 55 ℃ and 0.08 MPa;
step five, drying the product in vacuum at 65 ℃ to constant weight to obtain brown yellow viscous liquidThe product is methylated 1-butyl-3-methylimidazole ionic liquid [ CnMIM]CH3O。
The preparation method of the basic ionic liquid catalyst is characterized by comprising the following steps: the reaction was carried out under nitrogen.
The advantages and effects are as follows:
(1) through the bonding of the methoxy anion and the alkyl imidazole, the novel functional ionic liquid is formed. The active methoxy group in the structure has the homoionic effect and the synergistic effect with the raw material methanol, thereby obviously improving the conversion rate, reducing the side reaction and improving the selectivity.
(2) The catalyst has less consumption, high utilization rate of radicals, high conversion frequency and easy separation and purification of the product after the reaction.
(3) The catalyst has high cycle efficiency, realizes the cycle use of the catalyst and the raw material methanol while ensuring high selectivity and conversion rate, and obviously reduces the production cost.
(4) The methoxy anion has higher catalytic activity, can catalyze the ester exchange reaction to be carried out efficiently, and overcomes the phenomena of inactivation of sodium alkoxide and pipeline blockage in the prior production process.
(5) The azeotropic distillation of the methanol raw material and the dimethyl carbonate product is realized by supplementing methanol, the reaction is promoted to move towards the positive direction, the static balance in the catalytic process is changed into dynamic balance, the continuous industrial production is realized, and the reaction process is environment-friendly and efficient.
Drawings
FIG. 1 is a schematic diagram of preparation of a methoxylated alkyl imidazole ionic liquid catalyst;
FIG. 2 is a schematic illustration of the catalytic mechanism;
FIG. 3 is a diagram showing a methanol transesterification reaction apparatus;
Detailed Description
The preparation method of the catalyst provided by the invention comprises the following steps:
1) adding certain mass of halogenated alkane and N-methylimidazole into a 250mL round-bottom flask according to the molar ratio of 1:1.2, stirring, condensing and refluxing at the rotation speed of 150-200 r/min, reacting at 80 ℃ for 48 hours, and taking out.
2) Washing with ethyl acetate for three times to obtain a pale yellow viscous liquid, performing rotary evaporation at 70 ℃ under the reduced pressure of 0.08MPa, and placing in a vacuum drying oven for drying at 70 ℃ for 24h to obtain the [ CnMIM ] X ionic liquid intermediate.
3) Taking a proper amount of ionic liquid intermediate [ CnMIM ]]X is dissolved in 50mL of methanol and mixed well. Adding equimolar solid sodium methoxide, stirring at room temperature for 10h, and then heating and preserving heat for 6h in stages to obtain NaX and [ CnMIM]CH3And (3) O mixture.
4) Removing NaX precipitate with suction filtration device, and rotary evaporating at 55 deg.C under reduced pressure of 0.08MPa to remove methanol.
5) Vacuum drying the crude product obtained in the step 4) at 65 ℃ to constant weight to obtain brown yellow viscous liquid, namely methoxylated alkyl imidazole ionic liquid [ CnMIM]CH3O。
In the preparation process of the catalyst, firstly, halogenated alkyl imidazole ionic liquid is synthesized, and then halogen anions are replaced by active methoxy anions through a displacement reaction to synthesize the methoxylated alkyl imidazole ionic liquid. The ionic liquid catalyst has the same ionic effect and synergistic effect with a methanol raw material, and has a very strong catalytic effect in a methanol ester exchange reaction. The generated dimethyl carbonate and methanol can form an azeotrope, the azeotrope is distilled in the reaction process, and the methanol raw material is supplemented, so that the static balance can be broken, the reaction is promoted to move towards the positive direction, a new dynamic reaction balance is formed, and further, the continuous production is realized. Taking bromo-1-butyl-3-methylimidazole as an example, the preparation process of the methoxylated alkyl imidazole ionic liquid catalyst is shown in figure 1.
Compared with other ionic liquid catalysts, the novel ionic liquid with the methoxyl anion group has the same methoxyl anion as the raw material methanol, activation and ring opening of ethylene carbonate are facilitated through the homoionic effect and the synergistic effect, the generation of byproducts is reduced, and the process of catalyzing the reaction of the ethylene carbonate and the methanol is shown in figure 2.
The invention has the following characteristics:
(1) through the bonding of the methoxy anion and the alkyl imidazole, the novel functional ionic liquid is formed. The active methoxy group in the structure has the homoionic effect and the synergistic effect with the raw material methanol, thereby obviously improving the conversion rate, reducing the side reaction and improving the selectivity.
(2) The catalyst dosage is less, the radical utilization rate is high, the conversion frequency is high, and the product is easy to separate and purify after the reaction is finished;
(3) the catalyst has high cycle efficiency, realizes the cycle use of the catalyst and the raw material methanol while ensuring high selectivity and conversion rate, and obviously reduces the production cost.
(4) The methoxy anion has higher catalytic activity, can catalyze the ester exchange reaction to be carried out efficiently, and overcomes the phenomena of inactivation of sodium alkoxide and pipeline blockage in the existing production process.
(5) The azeotropic distillation of the methanol raw material and the dimethyl carbonate product is realized by supplementing methanol, the reaction is promoted to move towards the positive direction, the static balance in the catalytic process is changed into dynamic balance, the continuous industrial production is realized, and the reaction process is environment-friendly and efficient.
The invention is illustrated by means of specific examples
Example 1
Firstly, adding a certain mass of N-butyl bromide and N-methylimidazole into a 250ml round-bottom flask according to a molar ratio of 1:1.2, carrying out condensation reflux, adding magnetons, stirring at a rotating speed of 150-200 r/min, carrying out condensation reflux, reacting at 80 ℃ for 48 hours, taking out, washing with ethyl acetate for three times to obtain a pale yellow viscous liquid, carrying out rotary evaporation at 70 ℃ under a reduced pressure of 0.08MPa to remove the ethyl acetate, and then placing into a vacuum drying oven for drying at 70 ℃ for 24 hours to obtain an ionic liquid intermediate [ Bmim ] Br.
Taking a proper amount of [ Bmim ]]Dissolving Br in 50mL of methanol, adding equimolar solid sodium methoxide, stirring at room temperature for 10h, slowly heating to 50 ℃ and keeping the temperature for 3h, and heating to 80 ℃ and keeping the temperature for 3h to obtain [ Bmim ]]CH3A mixture of O and NaBr. Then, NaBr precipitate was removed by a suction filtration apparatus, and methanol was removed by rotary evaporation under reduced pressure of 0.08MPa at 55 ℃. Finally, the product is dried in vacuum at 65 ℃ to constant weight to obtain brown yellow viscous liquid, namely the methoxylated 1-butyl-3-methylimidazole ionic liquid [ Bmim ]]CH3O。
Weighing methanol and ethylene carbonate raw materials with a molar ratio of 8:1, mixing and adding the raw materials into a three-neck flask with a distillation device, reacting at 85-90 ℃ as shown in figure 3, and adopting a dropping funnel to make up and drop methanol into a reaction system when liquid drops flow out from a distillation tube because a product dimethyl carbonate and the methanol are azeotropic and the reaction is easy to reach static balance, so that the static balance of the system is broken, the reaction moves to the positive direction, and the dynamic balance of a continuous reaction process is realized. When the reaction system has no distillate, which indicates that the ethylene carbonate has reacted completely, the mass of the distillate is weighed, the purity of the distillate is measured by gas chromatography, and the yield of the dimethyl carbonate is calculated to be 69.2%.
Example 2
In the same equipment and under the same conditions as those used in example 1, n-butyl bromide was changed to dodecane bromide to obtain methoxylated 1-dodecyl-3-methylimidazole ionic liquid [ C ]12MIM]CH3And O. The catalyst is used for catalyzing the ester exchange reaction of methanol and ethylene carbonate, and the yield of dimethyl carbonate is 71.6%.
Example 3
In the same equipment and under the same conditions as those used in example 1, n-butyl bromide was changed to octadecylene bromide to obtain methoxylated 1-octadecyl-3-methylimidazole ionic liquid [ C ]18MIM]CH3And O. The catalyst is used for catalyzing the ester exchange reaction of methanol and ethylene carbonate, and the yield of dimethyl carbonate is 72.5%.
Example 4
In the same apparatus as used in example 3, except that the molar ratio of methanol to ethylene carbonate was changed to 10:1, under the same conditions, [ C ] was used18MIM]CH3The yield of dimethyl carbonate obtained by O-catalyzed methanol transesterification is 73.4%.
Example 5
In the same apparatus as used in example 3, except that the transesterification reaction temperature was changed to 75 ℃ under the same conditions, [ C ] was used18MIM]CH3The yield of dimethyl carbonate obtained by O-catalyzed methanol transesterification is 48.2%.
Example 6
In the same apparatus as used in example 4, except that the recovered ionic liquid catalyst was reused a plurality of times under the same conditions, the relationship between the number of times of reuse and the yield of dimethyl carbonate was as shown in the following table.
TABLE 1 influence of catalyst recycle times on DMC yield
The data in table 1 show that this type of ionic liquid catalyst can be recycled many times. With the increase of the using times, the conversion rate, the selectivity and the DMC yield are gradually reduced, but when the cyclic reaction is carried out for 5 times, each index is reduced to be smooth. The reaction is in a dynamic equilibrium continuous reaction process, so the change trend of the indexes does not influence the production process basically. The method proves that the active component of the catalyst is very stable, compared with the traditional sodium alkoxide catalyst, the continuous production of dynamic balance can be realized, the problems of inactivation of the sodium alkoxide catalyst and pipeline blockage caused by byproducts generated by the inactivation of the sodium alkoxide catalyst are solved, the production cost is reduced by recycling the ionic liquid, and the catalyst is energy-saving, consumption-saving, economic and environment-friendly and has good industrial application prospect.
Claims (2)
1. A preparation method of a basic ionic liquid catalyst is characterized by comprising the following steps:
the liquid catalyst is a methoxylated alkyl imidazole ionic liquid catalyst, is used for methanol ester exchange reaction, and has a structural general formula as follows:
wherein R is-CH3R' is an alkyl side chain-CnH2n+1，n=1,2,3……18；
The method comprises the following steps:
step one, adding halogenated alkane and N-methylimidazole into a container according to a molar ratio of 1:1.2, condensing and refluxing, adding magnetons, stirring at a rotating speed of 150-200 r/min, condensing and refluxing, reacting at 80 ℃ for 48 hours, and taking out;
step two, washing the cooled mixture with ethyl acetate for three times to obtain light yellow viscous liquid, performing rotary evaporation at 70 ℃ and under the reduced pressure of 0.08MPa, and placing the liquid in a vacuum drying oven for drying for 24 hours at 70 ℃ to obtain a halogenated alkyl imidazole ionic liquid intermediate [ CnMIM ] X;
step three, taking a proper amount of intermediate [ CnMIM]Dissolving X in 50mL of methanol, mixing uniformly, adding equimolar solid sodium methoxide, refluxing and condensing, stirring at room temperature for 10h, and then heating and preserving heat for 6h in stages to obtain NaX crystals and [ CnMIM]CH3A mixture of O;
removing sodium halide NaX by using a suction filtration device, and then removing methanol by carrying out reduced pressure rotary evaporation at 55 ℃ and 0.08 MPa;
step five, drying the product in vacuum at 65 ℃ to constant weight to obtain brown yellow viscous liquid, namely methylated 1-butyl-3-methylimidazole ionic liquid [ CnMIM]CH3O。
2. The method for preparing the basic ionic liquid catalyst according to claim 1, wherein: the reaction was carried out under nitrogen.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1416953A (en) * | 2002-12-06 | 2003-05-14 | 大连理工大学 | Double-function catalyst for synthesizing cyclic carbonate and methyl carbonate |
| CN101456810A (en) * | 2007-12-13 | 2009-06-17 | 中国科学院兰州化学物理研究所 | Method for synthesizing fatty acid ester by ester exchange reaction |
| CN101781200A (en) * | 2009-01-20 | 2010-07-21 | 中国石油化学工业开发股份有限公司 | Manufacturing method of organic carboxylic ester |
| CN102863339A (en) * | 2012-09-18 | 2013-01-09 | 常州大学 | Method for synthesizing methylethyl carbonate by ester exchange of dimethyl carbonate and diethyl carbonate |
| CN102875471A (en) * | 2012-10-23 | 2013-01-16 | 吴峰 | Alkali compound ion liquid and biodiesel preparation method |
| CN104016866A (en) * | 2014-05-20 | 2014-09-03 | 上海应用技术学院 | Method for preparing di-2-ethyhexyl carbonate |
| ES2553903A1 (en) * | 2014-06-10 | 2015-12-14 | Universidade Da Coruña | Ionic conductor in a rigid gel state (Machine-translation by Google Translate, not legally binding) |
| CN106268948A (en) * | 2016-07-22 | 2017-01-04 | 福州大学 | Immobilized ionic-liquid catalyst of triazol radical and its preparation method and application |
| CN106631776A (en) * | 2016-11-15 | 2017-05-10 | 广州印田新材料有限公司 | Green preparation process for synthesizing 12-carbon alcohol ester by double catalytic system |
| CN106674117A (en) * | 2016-11-30 | 2017-05-17 | 辽宁大学 | Selenium ionic liquid and preparation method thereof |
| CN107573497A (en) * | 2017-09-30 | 2018-01-12 | 中国科学院过程工程研究所 | A kind of method that makrolon is prepared based on ionic liquid efficient catalytic |
-
2018
- 2018-08-01 CN CN201810863967.0A patent/CN109174176B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1416953A (en) * | 2002-12-06 | 2003-05-14 | 大连理工大学 | Double-function catalyst for synthesizing cyclic carbonate and methyl carbonate |
| CN101456810A (en) * | 2007-12-13 | 2009-06-17 | 中国科学院兰州化学物理研究所 | Method for synthesizing fatty acid ester by ester exchange reaction |
| CN101781200A (en) * | 2009-01-20 | 2010-07-21 | 中国石油化学工业开发股份有限公司 | Manufacturing method of organic carboxylic ester |
| CN102863339A (en) * | 2012-09-18 | 2013-01-09 | 常州大学 | Method for synthesizing methylethyl carbonate by ester exchange of dimethyl carbonate and diethyl carbonate |
| CN102875471A (en) * | 2012-10-23 | 2013-01-16 | 吴峰 | Alkali compound ion liquid and biodiesel preparation method |
| CN104016866A (en) * | 2014-05-20 | 2014-09-03 | 上海应用技术学院 | Method for preparing di-2-ethyhexyl carbonate |
| ES2553903A1 (en) * | 2014-06-10 | 2015-12-14 | Universidade Da Coruña | Ionic conductor in a rigid gel state (Machine-translation by Google Translate, not legally binding) |
| CN106268948A (en) * | 2016-07-22 | 2017-01-04 | 福州大学 | Immobilized ionic-liquid catalyst of triazol radical and its preparation method and application |
| CN106631776A (en) * | 2016-11-15 | 2017-05-10 | 广州印田新材料有限公司 | Green preparation process for synthesizing 12-carbon alcohol ester by double catalytic system |
| CN106674117A (en) * | 2016-11-30 | 2017-05-17 | 辽宁大学 | Selenium ionic liquid and preparation method thereof |
| CN107573497A (en) * | 2017-09-30 | 2018-01-12 | 中国科学院过程工程研究所 | A kind of method that makrolon is prepared based on ionic liquid efficient catalytic |
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