CN102416347B - Multi-ionic liquid catalyst and application thereof in synthesizing acrylate compounds - Google Patents
Multi-ionic liquid catalyst and application thereof in synthesizing acrylate compounds Download PDFInfo
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Abstract
The invention discloses a multi-ionic liquid catalyst, comprising multiple central ions, wherein, cations are multiple quarternary ammonium ions, and anions are strong acid group anions. Compared with present ionic liquid with single central ion, the multi-ionic liquid catalyst has higher catalytic activity, and can be used for catalyzing the esterification of polyfunctional alcohols and polyfunctional acids at low temperatures. The invention further discloses a synthetic method of acrylate compounds, characterized in that: the multi-ionic liquid is used as the catalyst and the reaction medium, and high-efficient synthesis of various acrylate compounds can be realized at low temperatures. According to the invention, the advantages of high yield, easy separation of products, long service life of the catalyst, wide applicable scope, and the like are achieved.
Description
Technical field
The present invention relates to a kind of polybasic ion liquid catalyst and the application in acrylic ester compound is synthetic thereof.
Background technology
Ionic liquid refers to that mainly they have the incomparable special performance of a lot of molecular solvent by organic cation and inorganic or organic anion forms in room temperature or be bordering on the organic salt compound that is in a liquid state under room temperature.Result of study shows, ionic liquid has good catalytic activity to esterification.The method not only can obtain higher transformation efficiency and productive rate, and with traditional method, compare, also have two obvious advantages: 1, reaction product (ester class) is insoluble to ionic liquid, in reaction process, product and reaction system are separated automatically, are conducive to promote molecular balance to carry out to positive reaction on the one hand, on the other hand, after reaction was completed, product can be separated expediently by standing and demixing from catalyst system, enhance productivity; 2, the ionic-liquid catalyst after the use can be in the situation that use without any processing direct circulation, and keep higher catalytic activity, still can be after processed even if through the ionic-liquid catalyst catalytic activity that repeatedly recycles, reduced, recover its catalytic activity, further the work-ing life of extending catalyst.
The ionic liquid that is applied to the earliest Esterification catalytic reaction is acid aluminum chloride ionic liquid, but due to water generates being arranged in esterification process, the aluminum chloride ionic liquid can be subjected to destruction to a certain extent unavoidably, causes shorten the work-ing life of catalyzer.Developed into afterwards by sulfonate ion, sulfate ion are replaced the chlorate ions, and obtained meeting the stable Bronsted acidic ion liquid of water, it shows certain activity when the multiple esterification reaction of catalysis.The people such as Trissa use 1-butyl-3-Methylimidazole tosilate ionic-liquid catalyst, the esterification of having studied acetic acid and phenylcarbinol is synthetic, reacted 2 hours, maximum conversion rate and product selectivity all reach 100%, and product easily separates, the rear catalyst that dewaters is reused 4 times, and transformation efficiency is still greater than 85%.In recent years, the application of ionic liquid in esterification that also there have been a large amount of patent reports in China, for example CN1405140 and CN101172253 have introduced respectively the esterification by 1-methyl-3-hexyl imidazoles ionic liquid-catalyzed aliphatic or aromatic acid of tetrafluoride boron and straight chain alcohol; CN1554638 discloses multiple negatively charged ion and (has comprised CF
3SO
3 -, CF
3COO
-, HSO
3 -, CH
3COO
-Deng) synthetic method of the ionic liquid that forms with the alkyl pyridine cationoid, and to the catalytic activity of small molecules esterification reaction; CN1880295, CN101024612, CN101255111, CN101024613, CN101049573 etc. have also introduced the synthetic method of alkyl pyrrolidine ketone acidic ion liquid and the application in catalytic esterification at ambient temperature thereof, all show excellent catalytic activity and reusability.
Acrylic ester compound is photocuring thinner commonly used in photo-cured coating, main products comprises Glycerin triacrylate, ethylene glycol dimethacrylate, butylene glycol dimethacrylate, hexanediol dimethacrylate, methacrylic acid benzyl ester etc., along with the continuous expansion in photo-cured coating market, the consumption of acrylic ester compound is also in continuous expansion.At present, acrylic ester compound is mainly to obtain through the high temperature dehydration reaction under the effect of strong acid catalyst by acrylic or methacrylic acid and polyvalent alcohol.Because acrylic ester compound contains unsaturated double-bond, under hot conditions, easy polymerization reaction take place, cause unstable product quality; In addition, the strongly acidic catalyst that uses has stronger corrodibility to conversion unit, causes cost of equipment maintenance high; Moreover, this required temperature of reaction higher (120 ℃～200 ℃) of reaction and needing by azeotropic water removing, cause production energy consumption high, easily environment is brought negative impact.
Therefore, adopt the synthetic of ionic liquid-catalyzed acrylic ester compound, reduce temperature of reaction, have important practical significance.The ionic-liquid catalyst of now having reported has higher catalytic activity and repeat performance for the monobasic alcoholic acid esterification, can be used for the synthetic of single functionality acrylic ester compound, as vinylformic acid benzyl ester and methacrylic acid benzyl ester, yet, its catalyzing esterification activity to polyfunctional acrylic ester compounds (referring to contain the acrylic ester compound of two or more unsaturated double-bonds) is not high, and product yield is low.
For this reason, the present invention aims to provide a kind of efficient ionic-liquid catalyst and at acrylic ester compound, and the especially application of polyfunctional acrylic ester compounds in synthetic, to overcome the deficiencies in the prior art.
Summary of the invention
The object of the present invention is to provide a kind of polybasic ion liquid catalyst, it contains a plurality of ions center, and the ionic liquid of comparing existing single ionic center has higher catalytic activity, can be at lower temperature catalysis polyfunctionality alcohol, sour esterification.
Another object of the present invention is to provide a kind of synthetic method of acrylic ester compound, the method is take above-mentioned polybasic ion liquid as catalyzer and reaction media, can realize the efficient synthetic of multiple acrylic ester compound under lower temperature condition, have that productive rate is high, product is easy to separate, catalyzer long service life and an advantage such as applied widely.
The objective of the invention is to be achieved through the following technical solutions:
A kind of polybasic ion liquid catalyst, it contains two or more ions center, its positively charged ion is polynary quaternary ammonium ion, comprise Tetramethyl Ethylene Diamine positively charged ion, tetramethyl butane diamine positively charged ion, 4-methyl hexamethylene diamine positively charged ion, triethylenediamine positively charged ion, vulkacit H positively charged ion etc., preferably the vulkacit H positively charged ion; Its negatively charged ion is the strong acid radical ion, comprise alkyl sulfonate ion (such as methanesulfonate ions, ethylsulfonic acid radical ion, propyl sulfonic acid radical ion, butyl sulfonic acid radical ion etc.), acetate ion, hydrogen sulfate ion, phosphate anion or nitrate ion etc., preferably alkyl sulfonate ion.
The preparation method of described polybasic ion liquid catalyst is:, take polynary tertiary amine and strong acid as raw material, at 30 ℃～60 ℃ lower stirring reactions, formed in 2～6 hours.Wherein, the mol ratio between the nitrogen-atoms in described strong acid and described polynary tertiary amine is 1: 0.8～12, preferably 1: 0.95～1.05.Described polynary tertiary amine comprises Tetramethyl Ethylene Diamine, tetramethyl butane diamine, 4-methyl hexamethylene diamine, triethylenediamine, vulkacit H etc.; Described strong acid comprises alkylsulphonic acid, acetic acid, sulfuric acid, phosphoric acid or nitric acid etc., preferably alkylsulphonic acid.
A kind of synthetic method of acrylic ester compound, take acrylic or methacrylic acid with polyvalent alcohol as raw material, take described polybasic ion liquid as catalyzer and reaction media carry out esterification, temperature of reaction is 20 ℃～100 ℃, preferably 50 ℃～80 ℃, reaction times is 1～7 hour, the mol ratio of the carboxyl in the hydroxyl in described polyvalent alcohol and described acrylic or methacrylic acid is 1: 1～1.2, the addition of described ionic-liquid catalyst be polyvalent alcohol and acrylic or methacrylic acid gross weight 10%～30%.Reacted complete rear standing 10～30 minutes, the system AUTOMATIC ZONING, esterification products floats on upper strata because its density is less, the solution that polybasic ion liquid catalyst and water byproduct form is sunken to greatly lower floor because of density, namely obtain the esterification crude product after upper materials is separated, lower floor's material can be directly used in next catalytic cycle.
Polyvalent alcohol of the present invention comprises ethylene glycol, hexylene glycol, TriMethylolPropane(TMP), tetramethylolmethane, neopentyl glycol etc.
Polybasic ion liquid catalyst of the present invention contains a plurality of ions center, than existing monobasic ionic-liquid catalyst, has higher catalytic activity.It is not only applicable to monohydroxy-alcohol and monacid esterification, can synthesize acetic ester, acrylate of single functionality etc.; Also be applicable to simultaneously the larger polyvalent alcohol of esterification difficulty and the esterification between vinylformic acid, synthesize the polyfunctional acrylic ester compounds, such as ethylene glycol bisthioglycolate (methyl) acrylate, butyleneglycol two (methyl) acrylate, hexylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane two (methyl) acrylate etc.
polybasic ion liquid of the present invention can synthesize the efficient of catalysis polyfunctional acrylic ester compounds under lower temperature conditions, transformation efficiency reaches more than 90%, do not need in reaction process to add azeotropic solvent to carry out processed, energy consumption is low, and can prevent unsaturated link(age) occurs under hot conditions polyreaction, and react complete after, product and catalyst system AUTOMATIC ZONING, process and can obtain esterification products by simple separatory, but through the polybasic ion liquid catalyst direct circulation utilization of reclaiming, and can keep higher catalytic activity, has long work-ing life.
Embodiment
Embodiment 1～8 is the preparation method of polybasic ion liquid of the present invention, and embodiment 9～16 is the synthetic method of acrylic ester compound of the present invention.
Embodiment 1
Take N, N, N ', N '-Tetramethyl Ethylene Diamine 116.21g, the volume of packing into are 500ml, in four neck round-bottomed flasks with condensation and whipping appts, pass into nitrogen, be warming up to 40 ℃, after stirring 10min, take methylsulphonic acid 192.2g, the constant pressure funnel of packing into, be incubated 40 ℃, drips methylsulphonic acid in four neck flasks, dropwise in 1h, in the dropping process, heat release is obvious.Be warming up to 60 ℃ after dropwising, after insulation reaction 3h, namely obtain ionic-liquid catalyst N, N, N ', N '-Tetramethyl Ethylene Diamine dimethyl methyl hydrochlorate, its productive rate is 98%, stable to empty G﹠W, density is 1.208g/cm
3, fusing point is 28 ℃.
Embodiment 2
Take N, N, N ', N '-Tetramethyl Ethylene Diamine 116.21g, the volume of packing into are 500ml, in four neck round-bottomed flasks with condensation and whipping appts, pass into nitrogen, be warming up to 40 ℃, after stirring 10min, take propyl sulfonic acid 248.3g, the constant pressure funnel of packing into, be incubated 40 ℃, drips propyl sulfonic acid in four neck flasks, dropwise in 1h, in the dropping process, heat release is obvious.Be warming up to 60 ℃ after dropwising, after insulation reaction 3h, namely obtain ionic-liquid catalyst N, N, N ', N '-Tetramethyl Ethylene Diamine dipropyl sulfonate, its productive rate is 98%, stable to empty G﹠W, density is 1.179g/cm
3, fusing point is 19.7 ℃.
Embodiment 3
Take N, N, N ', N '-4-methyl hexamethylene diamine 172.3g, the volume of packing into are 500ml, in four neck round-bottomed flasks with condensation and whipping appts, pass into nitrogen, be warming up to 40 ℃, after stirring 10min, take methylsulphonic acid 192.2g, the constant pressure funnel of packing into, be incubated 40 ℃, drips methylsulphonic acid in four neck flasks, dropwise in 1h, in the dropping process, heat release is obvious.Be warming up to 60 ℃ after dropwising, after insulation reaction 3h, namely obtain ionic-liquid catalyst N, N, N ', N '-4-methyl hexamethylene diamine dimethyl methyl hydrochlorate, its productive rate is 97%, stable to empty G﹠W, density is 1.221g/cm
3, fusing point is 20 ℃.
Embodiment 4
Take triethyl diamines 112.17g, deionized water 60g, the volume of packing into are 500ml, in four neck round-bottomed flasks with condensation and whipping appts, pass into nitrogen, be warming up to 50 ℃, after stirring 10min, take methylsulphonic acid 192.2g, the constant pressure funnel of packing into, be incubated 50 ℃, drips methylsulphonic acid in four neck flasks, dropwise in 1h, in the dropping process, heat release is obvious.Be warming up to 60 ℃ after dropwising, after insulation reaction 3h, namely obtain ionic-liquid catalyst triethyl diamines dimethyl methyl hydrochlorate, its non-volatile component content is 83.1%, and productive rate is 98%, and stable to empty G﹠W, density is 1.283g/cm
3
Embodiment 5
Take vulkacit H 140.20g, deionized water 100g, the volume of packing into are 1000ml, in four neck round-bottomed flasks with condensation and whipping appts, pass into nitrogen, be warming up to 50 ℃, after stirring 10min, take butyl sulfonic acid 552.7g, the constant pressure funnel of packing into, be incubated 50 ℃, drips butyl sulfonic acid in four neck flasks, dropwise in 1h, in the dropping process, heat release is obvious.Be warming up to 60 ℃ after dropwising, after insulation reaction 3h, namely obtain ionic-liquid catalyst vulkacit H tetrabutyl sulfonate, its non-volatile component content is 87.3%, and productive rate is 98%, and stable to empty G﹠W, density is 1.206g/cm
3
Embodiment 6
Take N, N, N ', N '-Tetramethyl Ethylene Diamine 116.21g, the volume of packing into are 500ml, in four neck round-bottomed flasks with condensation and whipping appts, pass into nitrogen, be warming up to 40 ℃, after stirring 10min, take the vitriol oil (massfraction is 98.3%) 199.4g, the constant pressure funnel of packing into, be incubated 40 ℃, drips the vitriol oil in four neck flasks, dropwise in 1h, in the dropping process, heat release is obvious.Be warming up to 60 ℃ after dropwising, after insulation reaction 3h, namely obtain ionic-liquid catalyst N, N, N ', N '-Tetramethyl Ethylene Diamine dithionate, its productive rate are 97.1%, stable to empty G﹠W, density is 1.217g/cm
3, fusing point is 31 ℃.
Embodiment 7
Take N, N, N ', N '-Tetramethyl Ethylene Diamine 116.21g, the volume of packing into are 500ml, in four neck round-bottomed flasks with condensation and whipping appts, pass into nitrogen, be warming up to 40 ℃, after stirring 10min, take phosphoric acid (massfraction is 80%) 245.3g, the constant pressure funnel of packing into, be incubated 40 ℃, drips the vitriol oil in four neck flasks, dropwise in 1h, in the dropping process, heat release is obvious.Be warming up to 60 ℃ after dropwising, after insulation reaction 3h, rotary evaporation (60 ℃) dewaters, and namely obtains ionic-liquid catalyst N, N, and N ', N '-Tetramethyl Ethylene Diamine diphosphate, its productive rate are 92.4%, stable to empty G﹠W, density is 1.223g/cm
3, fusing point is 32 ℃.
Embodiment 8
Take N, N, N ', N '-Tetramethyl Ethylene Diamine 116.21g, the volume of packing into are 500ml, in four neck round-bottomed flasks with condensation and whipping appts, pass into nitrogen, be warming up to 60 ℃, after stirring 10min, take Glacial acetic acid 120.2g, the constant pressure funnel of packing into, be incubated 60 ℃, drips the vitriol oil in four neck flasks, dropwise in 1h, in the dropping process, heat release is obvious.Be warming up to 80 ℃ after dropwising, after insulation reaction 3h, namely obtain ionic-liquid catalyst N, N, N ', N '-Tetramethyl Ethylene Diamine two Glacial acetic acid salt, its productive rate is 91.6%, stable to empty G﹠W, density is 1.201g/cm
3, fusing point is 29 ℃.
Embodiment 9
Toward the ionic-liquid catalyst 120g that adds successively benzylalcohol 432.5g, methacrylic acid 361.6g (excessive 5%) in the 2000ml four neck round-bottomed flasks that prolong and whipping appts are housed and by embodiment 1, made (this addition be benzylalcohol and methacrylic acid gross weight 15%), stirring is warming up to 40 ℃, standing 10min after insulation reaction 5h, make the reaction system AUTOMATIC ZONING, emit lower floor's catalyzer and water, supernatant liquid is methacrylic acid benzyl ester crude product, its productive rate is 92%, and refractive index is n20/D1.513.
Embodiment 10
Toward the ionic-liquid catalyst 146g that adds successively ethylene glycol 248.2g, methacrylic acid 723.2g (excessive 5%) in the 2000ml four neck round-bottomed flasks that prolong and whipping appts are housed and by embodiment 1, made (this addition be ethylene glycol and methacrylic acid gross weight 15%), stirring is warming up to 50 ℃, standing 10min after insulation reaction 5h, make the reaction system AUTOMATIC ZONING, emit lower floor's catalyzer and water, supernatant liquid is the ethylene glycol dimethacrylate crude product, its productive rate is 91.3%, and refractive index is n20/D1.456.
Embodiment 11
Toward the ionic-liquid catalyst 146g that adds successively ethylene glycol 248.2g, methacrylic acid 723.2g (excessive 5%) in the 2000ml four neck round-bottomed flasks that prolong and whipping appts are housed and by embodiment 6, made (this addition be ethylene glycol and methacrylic acid gross weight 15%), stirring is warming up to 50 ℃, standing 10min after insulation reaction 5h, make the reaction system AUTOMATIC ZONING, emit lower floor's catalyzer and water, supernatant liquid is the ethylene glycol dimethacrylate crude product, its productive rate is 88.4%, and refractive index is n20/D1.456.
Embodiment 12
Toward the ionic-liquid catalyst 146g that adds successively ethylene glycol 248.2g, methacrylic acid 723.2g (excessive 5%) in the 2000ml four neck round-bottomed flasks that prolong and whipping appts are housed and by embodiment 7, made (this addition be ethylene glycol and methacrylic acid gross weight 15%), stirring is warming up to 60 ℃, standing 10min after insulation reaction 5h, make the reaction system AUTOMATIC ZONING, emit lower floor's catalyzer and water, supernatant liquid is the ethylene glycol dimethacrylate crude product, its productive rate is 68.4%, and refractive index is n20/D1.456.
Embodiment 13
Toward the ionic-liquid catalyst 146g that adds successively ethylene glycol 248.2g, methacrylic acid 723.2g (excessive 5%) in the 2000ml four neck round-bottomed flasks that prolong and whipping appts are housed and by embodiment 8, made (this addition be ethylene glycol and methacrylic acid gross weight 15%), stirring is warming up to 80 ℃, standing 10min after insulation reaction 5h, make the reaction system layering obvious, emit lower floor's catalyzer and water, supernatant liquid is the ethylene glycol dimethacrylate crude product, its productive rate is 43.4%, and refractive index is n20/D1.456.
Embodiment 14
Toward the ionic-liquid catalyst 180g that adds successively hexylene glycol 472.6g, methacrylic acid 723.2g (excessive 5%) in the 2000ml four neck round-bottomed flasks that prolong and whipping appts are housed and by embodiment 1, made (this addition be hexylene glycol and methacrylic acid gross weight 15%), stirring is warming up to 50 ℃, standing 10min after insulation reaction 5h, make the reaction system AUTOMATIC ZONING, emit lower floor's catalyzer and water, supernatant liquid is the hexanediol dimethacrylate crude product, its productive rate is 92.6%, and refractive index is n20/D 1.458.
Embodiment 15
add successively TriMethylolPropane(TMP) 536.6g in the 2000ml four neck round-bottomed flasks that prolong and whipping appts are housed, vinylformic acid 907.9g (excessive 5%), the ionic-liquid catalyst 217g that is made by embodiment 1 (this addition be TriMethylolPropane(TMP) and vinylformic acid gross weight 15%) and stopper p methoxy phenol 0.5g, stirring is warming up to 70 ℃, standing 10min after insulation reaction 6h, make the reaction system AUTOMATIC ZONING, emit lower floor's catalyzer and water, supernatant liquid is the Viscoat 295 crude product, its productive rate is 87.6%, refractive index is n20/D 1.475.
Embodiment 16
add successively tetramethylolmethane 544.6g in the 2000ml four neck round-bottomed flasks that prolong and whipping appts are housed, vinylformic acid 907.9g (excessive 5%), the ionic-liquid catalyst 218g that is made by embodiment 5 (this addition be tetramethylolmethane and vinylformic acid gross weight 15%) and stopper p methoxy phenol 1.0g, stirring is warming up to 80 ℃, standing 10min after insulation reaction 8h, make the reaction system AUTOMATIC ZONING, emit lower floor's catalyzer and water, supernatant liquid is the pentaerythritol triacrylate crude product, its productive rate is 88.4%, the content of pentaerythritol triacrylate is 78%, refractive index is n20/D1.482.
Controlled trial
Synthesizing of triethylene tetramine formate ionic liquid: in being furnished with the round-bottomed flask of magnetic agitation, the triethylene tetramine that adds 14.7ml, then add the 50ml dehydrated alcohol, stir 30min under the ice-water bath condition, then dropwise add while stirring 85% formic acid solution 17.8ml, white precipitate occurs, continue to drip formic acid solution 2ml, react approximately and carry out suction filtration after 10min, the solid matter that leaches is triethylene tetramine formate ionic liquid.
Toward adding successively TriMethylolPropane(TMP) 536.6g, vinylformic acid 907.9g (excessive 5%), ionic-liquid catalyst triethylene tetramine formate 217g (this addition be TriMethylolPropane(TMP) and vinylformic acid gross weight 15%) and stopper p methoxy phenol 1.0g in the 2000ml four neck round-bottomed flasks that prolong and whipping appts are housed, stirring is warming up to 70 ℃, standing 10min after insulation reaction 6h, reaction system is without the AUTOMATIC ZONING phenomenon.
Experiment shows, by the ionic-liquid catalyst that polynary primary amine/secondary amine and weak acid reaction generate, is failed synthesizing of efficient catalytic polyfunctional acrylic ester compounds.
Claims (9)
1. one kind with the synthetic method of polybasic ion liquid as the acrylic ester compound of catalyzer, it is characterized in that: take acrylic or methacrylic acid with polyvalent alcohol as raw material, take polybasic ion liquid as catalyzer and reaction media carry out esterification; Described polybasic ion liquid contains two or more ions center, and its positively charged ion is polynary quaternary ammonium ion, and its negatively charged ion is the strong acid radical ion; Temperature of reaction is 20 ℃～100 ℃, and the reaction times is 1～7 hour.
2. synthetic method according to claim 1, it is characterized in that: described polynary quaternary ammonium ion comprises Tetramethyl Ethylene Diamine positively charged ion, tetramethyl butane diamine positively charged ion, 4-methyl hexamethylene diamine positively charged ion, triethylenediamine positively charged ion and vulkacit H positively charged ion.
3. synthetic method according to claim 1, it is characterized in that: described strong acid radical ion comprises alkyl sulfonate ion, hydrogen sulfate ion, phosphate anion and nitrate ion.
4. synthetic method claimed in claim 1, is characterized in that, the preparation process of described polybasic ion liquid comprises the following steps: take polynary tertiary amine and strong acid as raw material, 30 ℃～60 ℃ lower stirring reactions 2～6 hours; Wherein, the mol ratio between the nitrogen-atoms in described strong acid and described polynary tertiary amine is 1: 0.8～1.2.
5. synthetic method according to claim 4, it is characterized in that: described polynary tertiary amine comprises Tetramethyl Ethylene Diamine, tetramethyl butane diamine, 4-methyl hexamethylene diamine, triethylenediamine and vulkacit H, and described strong acid comprises alkylsulphonic acid, sulfuric acid, phosphoric acid and nitric acid.
6. synthetic method according to claim 1, it is characterized in that: the mol ratio of the carboxyl in the hydroxyl in described polyvalent alcohol and described acrylic or methacrylic acid is 1: 1～1.2.
7. synthetic method according to claim 1 is characterized in that: the addition of described ionic-liquid catalyst be described polyvalent alcohol and described acrylic or methacrylic acid total amount 10%～30%.
8. synthetic method according to claim 1, it is characterized in that: described polyvalent alcohol comprises ethylene glycol, hexylene glycol, TriMethylolPropane(TMP), tetramethylolmethane and neopentyl glycol.
9. synthetic method according to claim 1, is characterized in that: reacted complete rear static 10～30 minutes, and made the system AUTOMATIC ZONING, upper materials is separated and obtained the esterification crude product.
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| CN106622365B (en) * | 2016-12-26 | 2019-05-14 | 石家庄学院 | A kind of efficient homogeneous catalysis acidic ion liquid, preparation method and its application that can be reused |
| CN108554448B (en) * | 2018-05-17 | 2021-05-18 | 扬州工业职业技术学院 | Catalyst for catalyzing glycerol to prepare glycerol phosphate and preparation method thereof |
| CN111153802A (en) * | 2018-11-08 | 2020-05-15 | 中国石油化工股份有限公司 | Green nitration method based on strong acid proton type ionic liquid catalysis |
| CN113801272B (en) * | 2021-09-14 | 2024-03-15 | 中国科学院化学研究所 | Self-healing 3D printable ionic gel and preparation and application thereof |
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| CN101007760A (en) * | 2007-01-17 | 2007-08-01 | 广东工业大学 | Unsaturated acid esterification method |
| CN101209973A (en) * | 2006-12-26 | 2008-07-02 | 中国科学院兰州化学物理研究所 | Bronsted acidic ion liquid using polyamine as cation and preparation method thereof |
| CN102060715A (en) * | 2010-12-22 | 2011-05-18 | 南京大学 | Double quaternary ammonium carboxylate functional ionic liquid and preparation method thereof |
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