CN105130950A - Bisamide-substituted novel calixcrown ether compound as well as synthesis method and application thereof - Google Patents
Bisamide-substituted novel calixcrown ether compound as well as synthesis method and application thereof Download PDFInfo
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Abstract
The invention relates to a bisamide-substituted novel calixcrown ether compound. The general chemical formula of the bisamide-substituted novel calixcrown ether compound is 11,23-di(acylamino)-25,27-di(2-propoxy)-calix[4]arene-crown-6; a synthesis method comprises the following steps: firstly, synthesizing an intermediate of 11,23-di(amino)-25,27-di(2-propoxy)-calix[4]arene-crown-6, and condensing the intermediate and acyl chloride so as to obtain the bisamide-substituted novel calixcrown ether compound. According to the synthesized 11,23-di(acylamino)-25,27-di(2-propoxy)-calix[4]arene-crown-6, the hydrophobicity of an extraction agent is increased by increasing the length of carbon chains of acylamino, the extraction distribution ratio of the calixcrown ether compound, in which acylamino is introduced, to caesium is increased by five times or above at least under the same extraction condition, the extraction performance is improved, the grade of an extraction device in the extraction process is reduced, the separation cost is reduced and the bisamide-substituted novel calixcrown ether compound has a high potential of being applied to removal of caesium ions in radioactive wastewater.
Description
Technical field
The invention belongs to organic extractant technical field, the Calix aromatic hydrocarbons crown compound replaced in particular to a kind of bisamide and synthetic method thereof and application, this Calix aromatic hydrocarbons crown compound is 11,23-bis-(amide group)-25,27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6.
Background technology
Caesium-137 is one of long lifetime sliver nucleic produced in fuel fission process, is mainly present in the high activity liquid waste of spent fuel aftertreatment generation, has high heat release rate and highly active feature.If it is separated from high activity liquid waste, not only contribute to the radioactive intensity reducing high activity liquid waste, and the volume of vitrification can be reduced, thus significantly reduce the cost of disposal of high activity liquid waste.Therefore, the isolation technique of development caesium-137 is the demands meeting advanced fuel circulation strategy, is also the prerequisite realizing nuclear energy Sustainable development.
At present the precipitator method, ion exchange method, membrane separation process and solvent extration are mainly contained for the method being separated caesium under strong acid condition.And wherein solvent extration has the advantages such as selectivity is high, good separating effect, equipment are simple, easy to operate due to it, be considered to the separation being hopeful most to be applied to caesium in high activity liquid waste.
Calixarene crown ether has very strong complexing action to alkali and alkaline earth metal ions, has been widely used in solvent extraction, liquid film separation and ion specific electrode at present.The power of itself and metal complexation depends on the three-dimensional arrangement of the number of Sauerstoffatom and the length of Crown Ether Bridged and calixarene.Wherein 1,3-diisopropoxy cup [4] aromatic hydrocarbons-hat-6 replacing conformation is proved to be and has very strong coordination ability with cesium ion.In complexation process, cesium ion is not only had an effect with the Sauerstoffatom of 6 on crown ether cycle, also with the aromatic ring π-electron generation conjugation on calixarene.1,3 replace 25,27-bis-(2-propoxy-)-cup [4] of conformation although aromatic hydrocarbons-hat-6 has good extraction ability to caesium in acid condition, and the partition ratio of caesium is lower, and it is fat-soluble bad, the partition ratio in the conventional thinner such as chloroform, dimethylbenzene is not high.By changing the chemical environment of aromatic nucleus in calixarene, not only can overcome the problems referred to above, being also expected to improve the distribution ratio of cup [4] aromatic hydrocarbons-hat-6 for caesium.
Summary of the invention
Not enough for prior art, the invention provides the Calix aromatic hydrocarbons crown compound that a kind of bisamide replaces, comprise its synthetic method and application.
The Calix aromatic hydrocarbons crown compound that bisamide replaces, its chemical general formula is 11,23-bis-(amide group)-25,27-bis-(2-propoxy-)-cup [4]-hat-6, and its general structure is as follows:
Wherein R is (CH
2)
ncH
3, n=0-7.
The preparation method of the Calix aromatic hydrocarbons crown compound that a kind of bisamide described above replaces, mainly comprises the following steps:
1) synthesis of 11,23-bis-(nitro)-25,27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6
Be 1:(200 ~ 400 by mol ratio) 25, 27-bis-(isopropoxy) cup [4] aromatic hydrocarbons-hat-6 and diacetyl oxide join in reaction vessel, be cooled to 5 ~-15 DEG C, stir 0.5 ~ 1h, then be (50 ~ 100) by volume ratio: (40 ~ 100): the diacetyl oxide of 1, the mixed solution of acetic acid and concentrated nitric acid is slowly added drop-wise in above-mentioned system, dropping terminates rear continuation stirring 2 ~ 5h, rise to room temperature, stir 12 ~ 24h at ambient temperature, then be poured in mixture of ice and water, be stirred to solid all to separate out, suction filtration, dry, obtain thick product, be (2 ~ 4) by volume ratio: the methyl alcohol of 1 and the mixed solvent of ether carry out recrystallization, obtain pale yellow powder solid, be 11, 23-bis-(nitro)-25, 27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6,
2) synthesis of 11,23-bis-(amino)-25,27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6
Be 1:(1200 ~ 1600 by mol ratio) 11, 23-bis-(nitro)-25, 27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6 and ethanol join in reaction vessel, logical nitrogen is protected, and add palladium-carbon catalyst and hydrazine hydrate, wherein palladium-carbon catalyst and 11, 23-bis-(nitro)-25, the mass ratio of 27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6 is 1:(10 ~ 20), 11, 23-bis-(nitro)-25, 27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6 is 1:(100 ~ 200 with the mol ratio of hydrazine hydrate), after dropping terminates, logical nitrogen is protected, be heated to 80 DEG C, backflow 0.5 ~ 5h, after reaction terminates, be cooled to room temperature, suction filtration removes solid catalyst, filtrate is through vacuum rotary steam, the thick product obtained obtains white plates crystal again after recrystallization, be product 11, 23-bis-(amino)-25, 27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6,
3) synthesis of 11,23-bis-(amide group)-25,27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6
Be 1:(200 ~ 500 by mol ratio) 11, 23-bis-(amino)-25, 27-bis-(2-propoxy-)-cup [4 aromatic hydrocarbons]-hat-6 and dichloromethane solution join in reaction vessel, logical nitrogen is protected, and mixed solution is cooled to 5 ~-5 DEG C, then add acyl chlorides (CH respectively
3(CH
2)
nc (=O) Cl, and triethylamine n=0-7), wherein added acyl chlorides, triethylamine and 11, 23-bis-(amino)-25, the mol ratio of 27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6 is (2 ~ 5): (2 ~ 4): 1, after dropping terminates, rise to room temperature, stir, reflux 1 ~ 3h, after reaction terminates, reaction solution is directly reduced pressure and is spin-dried for, the thick product organic solvent obtained dissolves, and wash with distilled water, collect organic phase, dry, suction filtration, get filtrate being spin-dried for, add a small amount of organic solvent dissolution, drip in sherwood oil and obtain white precipitate, namely filtration drying obtains product 11, 23-bis-(amide group) 25, 27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6.
Wherein, step 3) described in organic solvent be methylene dichloride, trichloromethane or tetracol phenixin.
Step 3) described in the Dryly use anhydrous sodium sulphate of organic phase, silica gel, activated alumina or molecular sieve.
The application of the Calix aromatic hydrocarbons crown compound that a kind of bisamide described above replaces in extraction caesium.
Described being applied as extracts caesium from containing the caesium aqueous solution.
Described containing concentration of nitric acid C in the caesium aqueous solution
hNO3=0 ~ 6mol/L.
The Calix aromatic hydrocarbons crown ether that bisamide replaces uses thinner dilution as extraction agent, thinner be selected from trichloromethane, methylene dichloride and ethyl acetate one or more.
The temperature of extractive reaction is 25 DEG C.
Beneficial effect of the present invention is: the present invention, by three-step reaction, has synthesized cup [4] aromatic hydrocarbons-hat-6 derivative that amide group replaces, for the structure of Calix aromatic hydrocarbons crown ether extraction agent provides a kind of new thinking with synthesis.It is lower that method of the present invention controls temperature of reaction, avoids the generation of more by product in reaction process, and whole building-up process reaction efficiency is high simultaneously, and purifying process is simple, is separated the purity >95% that can ensure product without the need to post.In addition, 11 of the present invention's synthesis, 23-bis-(amide group) 25,27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6 not only can increase the hydrophobicity of extraction agent by the length increasing amide group carbochain, and the amide group introduced can promote that calixarene crown ether is in acid condition for the extraction of caesium to a certain extent.With obtain 11,23-bis-(propionamido-) 25,27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6 is example, its in trichloromethane to the extraction of caesium, compared to do not carry out modifying 25,27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6, under same extraction conditions, distribution ratio at least improves more than 5 times, and the lifting of extraction ability, decrease the progression of centrifugal extractor in extraction process, reduce separation costs, be expected to be applied to the removal of cesium ion in radioactive wastewater.
Accompanying drawing explanation
Fig. 1 is that the distribution ratio D of a kind of Calix aromatic hydrocarbons crown ether 11,23-bis-(propionamido-)-25,27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6 pairs of caesiums of the present invention is with concentration of nitric acid C
hNO3the graphic representation of change.
Embodiment
Below with the amide group (CH of different carbon chain lengths
3(CH
2)
nc (=O) NH-, wherein n=0-7) replace 11,23-bis-(amide group) 25,27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6 synthesize example, in conjunction with specific embodiments the present invention is described.
Embodiment one 11,23-bis-(propionamido-)-25,27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6
1) 11,23-bis-(nitro)-25, the synthesis of 27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6: 25,27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6 replacing conformation by 1 of 4.26g, 3 is dissolved in 150mL diacetyl oxide, be cooled to-10 DEG C, stir 30min, the mixed solution of 100mL diacetyl oxide, 100mL acetic acid, 1mL concentrated nitric acid composition is slowly added drop-wise to above-mentioned system, drip off after terminating and continue to stir 3h, rise to room temperature, stir 12h.Reaction solution is poured in the mixture of ice and water of 500mL, being stirred to solid separates out complete, suction filtration, drying, the thick product volume ratio obtained is the methyl alcohol of 5:2, ether mixed solvent carries out recrystallization, obtains pale yellow powder solid, be 11,23-bis-(nitro)-25,27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6, productive rate=93%;
2) 11, 23-bis-(amino)-25, the synthesis of 27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6: get the said products 0.8g and join in 80mL ethanol, logical nitrogen, add 0.05g palladium-carbon catalyst, then the hydrazine hydrate that 10mL massfraction is 80% is added, be heated to 80 DEG C, heating is stopped after backflow 3h, be cooled to room temperature, suction filtration removes catalyzer, get filtrate decompression and revolve steaming, the thick product ethanol obtained carries out recrystallization, obtain white plates crystal, be product 11, 23-bis-(amino)-25, 27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6, productive rate=87%,
3) 11,23-bis-(propionamido-) 25, the synthesis of 27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6: the white plates crystal 0.740g obtained is joined in 20mL methylene dichloride and dissolves, logical nitrogen, is cooled to 0 DEG C, add 0.20g propionyl chloride, drip 0.25g triethylamine, after dripping off end, rise to room temperature, stir, reflux 2h.After reaction terminates, reaction solution is directly reduced pressure and is spin-dried for, dissolve with methylene dichloride, and with distilled water wash three times, collect organic phase, carry out drying by anhydrous sodium sulphate, suction filtration, get filtrate being spin-dried for, add a small amount of methylene dichloride and dissolve, drip in sherwood oil and obtain white precipitate, namely filtration drying obtains product 11,23-bis-(propionamido-) 25,27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6, productive rate is 81%.
By extraction agent 11,23-bis-(propionamido-) 25,27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6 is dissolved in trichloromethane, be mixed with the organic solution that concentration is 0.01mol/L, be 0.3g/L containing cesium ion concentration in the caesium aqueous solution, concentration of nitric acid is respectively 0.1mol/L, 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L.Get isopyknic aqueous phase and organic phase respectively in the centrifuge tube of 10mL, under barometric point, vibrate 60min in the constant temperature water bath of 25 DEG C, centrifugal layering, and detect aqueous phase cesium ion concentration, under drawing different concentration of nitric acid, the percentage extraction of caesium is all more than 90%; Calculate the cesium ion concentration of organic phase with minusing, and then try to achieve partition ratio according to the concentration ratio of cesium ion in two-phase.As shown in figure 1 and table 1, C
hNO3during=3mol/L, partition ratio reaches as high as 67, C
hNO3during=5mol/L, partition ratio still reaches 22.9.
Extraction data under the different concentration of nitric acid of table 1
Embodiment 2 11,23-bis-(propionamido-)-25,27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6
The method of synthesis white plates crystal 11,23-bis-(amino)-25,27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6 is with embodiment 1.
The white plates crystal 0.740g obtained is joined 20mL methylene dichloride dissolve, logical nitrogen, is cooled to-5 DEG C, adds 0.25g propionyl chloride, drips 0.3g triethylamine, after dripping off end, and reflux 3h.After reaction terminates, reaction solution is directly reduced pressure and is spin-dried for, dissolve with methylene dichloride, and with distilled water wash three times, merge organic phase, carry out drying with sodium sulfate, suction filtration, get filtrate being spin-dried for, add a small amount of methylene dichloride to dissolve, drip in sherwood oil and obtain white precipitate, namely filtration drying obtains product 11,23-bis-(propionamido-) 25,27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6.
Embodiment 3 11,23-bis-(amide-based small) 25,27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6
1) 11,23-bis-(nitro)-25, the synthesis of 27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6: 25,27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6 replacing conformation by 1 of 4.26g, 3 is dissolved in 150mL diacetyl oxide, be cooled to-15 DEG C, stir 30min, the mixed solution of 100mL diacetyl oxide, 100mL acetic acid, 1mL concentrated nitric acid composition is slowly added drop-wise to above-mentioned system, drip off after terminating and continue to stir 3h, rise to room temperature, stir 12h.Reaction solution is poured in the mixture of ice and water of 500mL, be stirred to solid and separate out complete, suction filtration, dry, the thick product volume ratio obtained is the methyl alcohol of 5:2, ether mixed solvent carries out recrystallization, obtain faint yellow solid.
2) 11,23-bis-(amino)-25, the synthesis of 27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6: get the said products 0.8g and join in 80mL ethanol, logical nitrogen, add 0.05g palladium-carbon catalyst, then 8mL hydrazine hydrate is added, be heated to 80 DEG C, stop heating after backflow 1h, suction filtration removes catalyzer, get filtrate decompression and revolve steaming, the thick product ethanol obtained carries out recrystallization, obtains white plates crystal, is product 11,23-bis-(amino)-25,27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6.
3) 11,23-bis-(amide-based small) 25, the synthesis of 27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6: the white plates crystal 0.740g obtained is joined 30mL methylene dichloride and dissolves, logical nitrogen, be cooled to 0 DEG C, add 0.25g butyryl chloride, drip 0.25g triethylamine, after dripping off end, reflux 2h.After reaction terminates, reaction solution is directly reduced pressure and is spin-dried for, dissolve with methylene dichloride, and with distilled water wash three times, merge organic phase, carry out drying by anhydrous sodium sulphate, suction filtration, get filtrate being spin-dried for, add a small amount of methylene dichloride and dissolve, drip in sherwood oil and obtain white precipitate, namely filtration drying obtains product 11,23-bis-(amide-based small) 25,27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6, productive rate=80%.
Embodiment 4 11,23-bis-(decoyl amido) 25,27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6
The method of synthesis white plates crystal 11,23-bis-(amino)-25,27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6 is with embodiment 3.
The white plates crystal 0.740g obtained is joined 30mL methylene dichloride dissolve, logical nitrogen, is cooled to-5 DEG C, adds 0.5g capryl(yl)chloride, drips 0.3g triethylamine, after dripping off end, and reflux 3h.After reaction terminates, reaction solution is directly reduced pressure and is spin-dried for, dissolve with methylene dichloride, and with distilled water wash three times, merge organic phase, carry out drying by anhydrous sodium sulphate, suction filtration, get filtrate being spin-dried for, add a small amount of methylene dichloride and dissolve, drip in sherwood oil and obtain white precipitate, namely filtration drying obtains product 11,23-bis-(decoyl amido) 25,27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6, productive rate=84%.
Claims (9)
1. a Calix aromatic hydrocarbons crown compound for bisamide replacement, it is characterized in that, its chemical general formula is 11,23-bis-(amide group)-25,27-bis-(2-propoxy-)-cup [4]-hat-6, and its general structure is as follows:
Wherein R is (CH
2)
ncH
3, n=0-7.
2. the preparation method of the Calix aromatic hydrocarbons crown compound of a kind of bisamide replacement as claimed in claim 1, is characterized in that, mainly comprise the following steps:
1) synthesis of 11,23-bis-(nitro)-25,27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6
Be 1:(200 ~ 400 by mol ratio) 25, 27-bis-(isopropoxy) cup [4] aromatic hydrocarbons-hat-6 and diacetyl oxide join in reaction vessel, be cooled to 5 ~-15 DEG C, stir 0.5 ~ 1h, then be (50 ~ 100) by volume ratio: (40 ~ 100): the diacetyl oxide of 1, the mixed solution of acetic acid and concentrated nitric acid is slowly added drop-wise in above-mentioned system, dropping terminates rear continuation stirring 2 ~ 5h, rise to room temperature, stir 12 ~ 24h at ambient temperature, then be poured in mixture of ice and water, be stirred to solid all to separate out, suction filtration, dry, obtain thick product, be (2 ~ 4) by volume ratio: the methyl alcohol of 1 and the mixed solvent of ether carry out recrystallization, obtain pale yellow powder solid, be 11, 23-bis-(nitro)-25, 27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6,
2) synthesis of 11,23-bis-(amino)-25,27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6
Be 1:(1200 ~ 1600 by mol ratio) 11, 23-bis-(nitro)-25, 27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6 and ethanol join in reaction vessel, logical nitrogen is protected, and add palladium-carbon catalyst and hydrazine hydrate, wherein palladium-carbon catalyst and 11, 23-bis-(nitro)-25, the mass ratio of 27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6 is 1:(10 ~ 20), 11, 23-bis-(nitro)-25, 27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6 is 1:(100 ~ 200 with the mol ratio of hydrazine hydrate), after dropping terminates, logical nitrogen is protected, be heated to 80 DEG C, backflow 0.5 ~ 5h, after reaction terminates, be cooled to room temperature, suction filtration removes solid catalyst, filtrate is through vacuum rotary steam, the thick product obtained obtains white plates crystal again after recrystallization, be product 11, 23-bis-(amino)-25, 27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6,
3) synthesis of 11,23-bis-(amide group)-25,27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6
Be 1:(200 ~ 500 by mol ratio) 11, 23-bis-(amino)-25, 27-bis-(2-propoxy-)-cup [4 aromatic hydrocarbons]-hat-6 and dichloromethane solution join in reaction vessel, logical nitrogen is protected, and mixed solution is cooled to 5 ~-5 DEG C, then add acyl chlorides (CH respectively
3(CH
2)
nc (=O) Cl, and triethylamine n=0-7), wherein added acyl chlorides, triethylamine and 11, 23-bis-(amino)-25, the mol ratio of 27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6 is (2 ~ 5): (2 ~ 4): 1, after dropping terminates, rise to room temperature, stir, reflux 1 ~ 3h, after reaction terminates, reaction solution is directly reduced pressure and is spin-dried for, the thick product organic solvent obtained dissolves, and wash with distilled water, collect organic phase, dry, suction filtration, get filtrate being spin-dried for, add a small amount of organic solvent dissolution, drip in sherwood oil and obtain white precipitate, namely filtration drying obtains product 11, 23-bis-(amide group) 25, 27-bis-(2-propoxy-)-cup [4] aromatic hydrocarbons-hat-6.
3. preparation method as claimed in claim 2, is characterized in that, step 3) described in organic solvent be methylene dichloride, trichloromethane or tetracol phenixin.
4. preparation method as claimed in claim 2, is characterized in that, step 3) described in the Dryly use anhydrous sodium sulphate of organic phase, silica gel, activated alumina or molecular sieve.
5. the Calix aromatic hydrocarbons crown compound that a kind of bisamide replaces as claimed in claim 1 is extracting the application in caesium.
6. apply as claimed in claim 5, it is characterized in that, this is applied as and extracts caesium from containing the caesium aqueous solution.
7. apply as claimed in claim 6, it is characterized in that, containing concentration of nitric acid C in the caesium aqueous solution
hNO3=0 ~ 6mol/L.
8. apply as claimed in claim 5, it is characterized in that, the Calix aromatic hydrocarbons crown ether that described bisamide replaces uses thinner dilution as extraction agent, described thinner be selected from trichloromethane, methylene dichloride and ethyl acetate one or more.
9. apply as claimed in claim 5, it is characterized in that, the temperature of extractive reaction is 25 DEG C.
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| CN108091411A (en) * | 2018-01-19 | 2018-05-29 | 东华理工大学 | A kind of method for separating caesium and rubidium simultaneously using carbon-based calixarenes crown ether hybrid material |
| CN109248660A (en) * | 2018-11-23 | 2019-01-22 | 东华理工大学 | A kind of adsorbent and the preparation method and application thereof |
| CN110180504A (en) * | 2019-06-04 | 2019-08-30 | 东华理工大学 | Carbon-based asymmetric double crown supermolecule hybrid material of one kind and its preparation method and application |
| CN111285880A (en) * | 2019-08-28 | 2020-06-16 | 中南大学 | Preparation and application of switch compound containing bisprown ether |
| CN112574166A (en) * | 2020-12-26 | 2021-03-30 | 贵州民族大学 | Synthesis method of crown ether sulfonyl hydrazide compound |
| CN113614072A (en) * | 2019-03-15 | 2021-11-05 | 创新药物筛选有限公司 | Calixago compounds and uses thereof |
| CN116730973A (en) * | 2023-08-15 | 2023-09-12 | 兰州大学 | 4-tert-butyl benzyloxy substituted calixarene crown ether compound as well as preparation method and application thereof |
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| CN108091411A (en) * | 2018-01-19 | 2018-05-29 | 东华理工大学 | A kind of method for separating caesium and rubidium simultaneously using carbon-based calixarenes crown ether hybrid material |
| CN108091411B (en) * | 2018-01-19 | 2020-02-21 | 东华理工大学 | Method for simultaneously separating cesium and rubidium by using carbon-based calixarene crown ether hybrid material |
| CN109248660A (en) * | 2018-11-23 | 2019-01-22 | 东华理工大学 | A kind of adsorbent and the preparation method and application thereof |
| CN113614072A (en) * | 2019-03-15 | 2021-11-05 | 创新药物筛选有限公司 | Calixago compounds and uses thereof |
| CN110180504A (en) * | 2019-06-04 | 2019-08-30 | 东华理工大学 | Carbon-based asymmetric double crown supermolecule hybrid material of one kind and its preparation method and application |
| CN111285880A (en) * | 2019-08-28 | 2020-06-16 | 中南大学 | Preparation and application of switch compound containing bisprown ether |
| CN112574166A (en) * | 2020-12-26 | 2021-03-30 | 贵州民族大学 | Synthesis method of crown ether sulfonyl hydrazide compound |
| CN116730973A (en) * | 2023-08-15 | 2023-09-12 | 兰州大学 | 4-tert-butyl benzyloxy substituted calixarene crown ether compound as well as preparation method and application thereof |
| CN116730973B (en) * | 2023-08-15 | 2023-10-20 | 兰州大学 | 4-tert-butyl benzyloxy substituted calixarene crown ether compound as well as preparation method and application thereof |
| CN117756776A (en) * | 2023-12-20 | 2024-03-26 | 中国科学技术大学 | Sulfoamidated dibenzo 18 crown ether 6 extractant and preparation method thereof |
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