CN104592240A - Seven-membered cucurbituril bridged acrylic acid naphthol ester as well as preparation method and application thereof - Google Patents

Seven-membered cucurbituril bridged acrylic acid naphthol ester as well as preparation method and application thereof Download PDF

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Publication number
CN104592240A
CN104592240A CN201510002460.2A CN201510002460A CN104592240A CN 104592240 A CN104592240 A CN 104592240A CN 201510002460 A CN201510002460 A CN 201510002460A CN 104592240 A CN104592240 A CN 104592240A
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China
Prior art keywords
yuan
melon ring
ring bridging
vinylformic acid
bridging
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CN201510002460.2A
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Inventor
高瑞晗
肖勃
陈鹏
范颖
薛赛凤
陶朱
祝黔江
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Guizhou University
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Guizhou University
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Priority to CN201510002460.2A priority Critical patent/CN104592240A/en
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Abstract

The invention relates to seven-membered cucurbituril bridged acrylic acid naphthol ester as well as a preparation method and application thereof and belongs to the technical field of modified cucurbituril. The preparation method comprises the following step: with seven-membered cucurbituril bridged acrylic acid, thionyl chloride and naphthol as raw materials, synthesizing seven-membered cucurbituril bridged acrylic acid naphthol ester. According to seven-membered cucurbituril bridged acrylic acid naphthol ester as well as the preparation method and the application thereof disclosed by the invention, an esterification product of seven-membered cucurbituril is lowered in water solubility and can be applied as a solid adsorption material; by utilizing the host-guest interaction of the seven-membered cucurbituril and the synergistic effect of carboxyl hydrogen bond, adsorption and release of basic dyes are realized.

Description

A kind of seven yuan of melon ring bridging vinylformic acid naphthol esters and its preparation method and application
Technical field
The present invention is a kind of seven yuan of melon ring bridging vinylformic acid naphthol ester preparation methods and to dyestuff absorption reversibly and release, belongs to modification melon loop technique field.
Background technology
The fields such as the research of porous material comprises class micro-pore zeolite, mesoporous silicon oxide, metal oxide usually, the polymkeric substance of metal-organic framework compound (MOF) and macropore.Their research range relates to the numerous areas from structured material to energy technology, and in catalysis, absorption, is used widely in the aspects such as ion-exchange and Supramolecular self assembly body.Macroporous polymer utilizes the duct formed between polymer molecule to be adsorbed Cucumber by weak key action.
Melon ring (Cucurbit [ n] urils, Q [ n] s) there is the large ring cage compound linked up by n glycosides urea unit and 2n methylene bridge, two opening end edge " is inlayed " and a circle carbonylic oxygen atom, thus have the ability forming title complex with metal ion, the coordination of organic molecule functional group, pile up by hydrogen bond, π-π, direct coordination etc. acts on the melon cyclic group organic framework polymer constructed and formed and have various structures feature.Therefore, utilize the outer wall effect of melon ring to form melon cyclic group Supramolecular self assembly and become a kind of approach constructing the porous material with regular pore canal or void structure.The Kim of Korea S, once when not adding other component, synthesizes Q [6] based porous materials.And have certain absorption property to volatility organic molecule.
Inventor herein, by the research to one pot process melon ring bridging acrylate copolymer, has invented a kind of seven yuan of melon ring bridging acrylate copolymer, and patent applied for.Denomination of invention " a kind of seven yuan of melon ring bridging acrylate copolymer and preparation method and application ", application number: 201410394063.X.
Summary of the invention
The object of the invention is to a kind of seven yuan of melon ring bridging vinylformic acid naphthol ester compounds of synthesis, be raw material by seven yuan of melon ring bridging vinylformic acid, react with sulfur oxychloride, product after chloride and naphthol reaction, obtain the carboxylate of seven yuan of melon ring bridging vinylformic acid and naphthols, for the absorption of basic dyestuff and release.
The present invention is a kind of seven yuan of melon ring bridging vinylformic acid naphthol esters, is with seven yuan of melon ring bridging vinylformic acid and sulfur oxychloride SOCl 2reaction, obtain seven yuan of melon ring bridging acrylate chlorides, react with seven yuan of melon ring bridging acrylate chlorides and naphthols again, obtain seven yuan of melon ring bridging vinylformic acid naphthol esters, in seven yuan of melon ring bridging vinylformic acid, vinylformic acid and sulfur oxychloride mol ratio are 1:5-10, in seven yuan of melon ring bridging acrylate chlorides, acrylate chloride and naphthols mol ratio are 1:5-10, and seven yuan of melon ring bridging vinylformic acid naphthols esterification products are water insoluble, can adsorb or discharge basic dyestuff.
The method of a kind of seven yuan of melon ring bridging vinylformic acid naphthol esters of the present invention follows these steps to carry out:
(1) take a certain amount of seven yuan of melon ring bridging vinylformic acid, add in round-bottomed flask in Acrylic Acid Monomer and sulfur oxychloride with the ratio of mol ratio 1:5-10, reaction backflow 12h, obtains seven yuan of melon ring bridging acrylate chlorides;
(2) the said products is dried, seven yuan of melon ring bridging acrylate chlorides of drying and appropriate tosic acid are added in there-necked flask, take toluene as solvent, the ratio being 1:5-10 in the acrylate chloride in yuan melon ring bridging acrylate chloride product of seven in above-mentioned product and naphthols mol ratio is dissolved in toluene, slowly drip in solution, reaction backflow 12h;
(3) decompress filter, first with the NaOH solution dispersion 0.5h of pH=9, then by ether repetitive scrubbing precipitation, then dries, productive rate about 60%.
Because after chloride, reactive behavior is higher, the carboxylate of different stationary phase optionally can be synthesized according to the object of seven yuan of melon ring functions.Functionalization described in it has optical activity group, for the research of the aspects such as analyzing and testing, drug delivery, biological tracing as introduced; As modified in solid surface, be then likely used as special separating-purifying material, fixing equal .
The present invention is raw material by seven yuan of melon ring bridging vinylformic acid, reacts, the product after chloride and naphthol reaction, obtain the carboxylate of seven yuan of melon ring bridging vinylformic acid and naphthols with sulfur oxychloride.Synthetic method of the present invention is a kind of efficient quick, the synthetic method of high yield, high-adaptability obtains seven yuan of melon ring bridging vinylformic acid naphthol ester compounds.
The application of a kind of seven yuan of melon ring bridging vinylformic acid naphthol esters of the present invention is absorption for aqueous solution neutral and alkali dyestuff and release, seven yuan of melon ring bridging vinylformic acid naphthol esters to acridine orange, proflavine, thionine, toluylene red, basic yellow, the adsorptive capacity of thiazole orange is respectively 15.42, and 12.29,13.06,48.13,11.39,26.48mg/g;
Effect 1 of the present invention) synthetic method that uses has simple to operate, productive rate high.2) seven yuan of acrylic acid further functionalization of melon ring bridging, utilize the synergy of the host-guest interaction of melon ring and carboxyl hydrogen bond carry out absorption to dyestuff and can discharge in ethanol.
Accompanying drawing explanation
Fig. 1 seven yuan of melon ring bridging vinylformic acid naphthol ester synthesis schematic diagram
Fig. 2 seven yuan of melon ring bridging vinylformic acid naphthol ester infrared spectrums
Fig. 3 seven yuan of melon ring bridging vinylformic acid naphthol esters are to dye adsorption uv-absorbing spectrogram
Wherein (1) acridine orange (2) basic yellow (3) thionine (4) thiazole orange (5) proflavine (6) toluylene red in Fig. 3
Fig. 4 seven yuan of melon ring bridging vinylformic acid naphthol esters are to dye adsorption absorption spirogram.
Embodiment
(1) take 1g seven yuan of melon ring bridging vinylformic acid, measure 5mL sulfur oxychloride and add in 150mL round-bottomed flask, be heated to 80 DEG C of backflows, reaction 12h;
(2) after above-mentioned product utilization Rotary Evaporators is spin-dried for, by gained solid, 30mL toluene and 0.01g tosic acid add there-necked flask, are heated to 70 DEG C, are dissolved in by 1g naphthols in 10mL toluene, slowly drip in solution, backflow 12h;
(3) prepare the sodium hydroxide solution of pH=9, above-mentioned product at reduced pressure suction filtration, the precipitated solid obtained added after disperseing 0.5h in 50mL sodium hydroxide solution, decompress filter, obtains solid;
(4) above-mentioned solid is utilized washed with diethylether 4 times, put into baking oven dry, weigh, productive rate is approximately 60%;
(5) each for above-mentioned product 1mg is dropped into 5mL5 × 10 -5in the dye solution of mol/L, utilize measurement of ultraviolet-visible spectrophotometer seven yuan of melon ring bridging vinylformic acid naphthol esters to acridine orange, proflavine, thionine, toluylene red, basic yellow, the adsorptive capacity of thiazole orange is respectively 15.42, and 12.29,13.06,48.13,11.39,26.48mg/g;
(6) seven of above-mentioned absorbing dye yuan of melon ring bridging vinylformic acid naphthol esters are put into ethanolic soln, dyestuff discharges, and release rate is more than 90%.

Claims (4)

1. seven yuan of melon ring bridging vinylformic acid naphthol esters, is characterized in that with seven yuan of melon ring bridging vinylformic acid and sulfur oxychloride SOCl 2be obtained by reacting seven yuan of melon ring bridging acrylate chlorides, react with seven yuan of melon ring bridging acrylate chlorides and naphthols again, obtain seven yuan of melon ring bridging vinylformic acid naphthol esters, in seven yuan of melon ring bridging vinylformic acid, vinylformic acid and sulfur oxychloride mol ratio are 1:5-10, in seven yuan of melon ring bridging acrylate chlorides, acrylate chloride and naphthols mol ratio are 1:5-10, seven yuan of melon ring bridging vinylformic acid naphthols esterification products are water insoluble, can adsorb or discharge basic dyestuff.
2. a preparation method for seven yuan of melon ring bridging vinylformic acid naphthol esters, is characterized in that following these steps to carry out:
(1) a certain amount of seven yuan of melon ring bridging vinylformic acid are taken, by Acrylic Acid Monomer and SOCl 2add in round-bottomed flask with the ratio of mol ratio 1:5-10, reaction backflow 12h, obtains seven yuan of melon ring bridging acrylate chlorides;
(2) the said products is dried, seven yuan of melon ring bridging acrylate chlorides of drying and appropriate tosic acid are added in there-necked flask, take toluene as solvent, the ratio being 1:5-10 in the acrylate chloride in yuan melon ring bridging acrylate chloride product of seven in above-mentioned product and naphthols mol ratio is dissolved in toluene, slowly drip in solution, reaction backflow 12h;
(3) decompress filter, first with the NaOH solution dispersion 0.5h of pH=9, then by ether repetitive scrubbing precipitation, then dries, productive rate about 60%.
3. the preparation method of seven yuan of melon ring bridging vinylformic acid naphthol esters according to claim 2, is characterized in that: after chloride, reactive behavior is higher, optionally can synthesize the carboxylate of different stationary phase according to the object of seven yuan of melon ring functions.
4. a kind of application of seven yuan of melon ring bridging vinylformic acid naphthol esters is characterized in that as claimed in claim 1: for absorption and the release of aqueous solution neutral and alkali dyestuff.
CN201510002460.2A 2015-01-05 2015-01-05 Seven-membered cucurbituril bridged acrylic acid naphthol ester as well as preparation method and application thereof Pending CN104592240A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007102634A1 (en) * 2006-03-09 2007-09-13 Postech Academy-Industry Foundation Cucurbituril added cigarettes and manufacturing method thereof
CN101108851A (en) * 2007-07-11 2008-01-23 贵州大学 Melon ring and method of synthesizing substituted melon ring
CN104151459A (en) * 2014-08-12 2014-11-19 贵州大学 Quinary, senary or octonary cucurbituril bridged acrylic acid polymer and preparation method thereof
CN104193867A (en) * 2014-08-12 2014-12-10 贵州大学 Seven-membered cucurbit urils bridged acrylic polymer and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007102634A1 (en) * 2006-03-09 2007-09-13 Postech Academy-Industry Foundation Cucurbituril added cigarettes and manufacturing method thereof
CN101108851A (en) * 2007-07-11 2008-01-23 贵州大学 Melon ring and method of synthesizing substituted melon ring
CN104151459A (en) * 2014-08-12 2014-11-19 贵州大学 Quinary, senary or octonary cucurbituril bridged acrylic acid polymer and preparation method thereof
CN104193867A (en) * 2014-08-12 2014-12-10 贵州大学 Seven-membered cucurbit urils bridged acrylic polymer and preparation method and application thereof

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Application publication date: 20150506