CN104327101A - Control synthesis and application of aryl organic multidentate ligand-cucurbituril porous framework polymer - Google Patents
Control synthesis and application of aryl organic multidentate ligand-cucurbituril porous framework polymer Download PDFInfo
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- CN104327101A CN104327101A CN201410538187.0A CN201410538187A CN104327101A CN 104327101 A CN104327101 A CN 104327101A CN 201410538187 A CN201410538187 A CN 201410538187A CN 104327101 A CN104327101 A CN 104327101A
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- Prior art keywords
- btb
- polymkeric substance
- aromatic base
- porous framework
- base organic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic System without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
Abstract
The invention relates to control synthesis and application of an aryl organic multidentate ligand-cucurbituril porous framework polymer, and belongs to a multidimensional multi-cavity cucurbituril organic polymer and a synthetic method and application. The aryl organic multidentate ligand-cucurbituril porous framework polymer is BTB<3->-Q[6]-NH4<+> and BTB<3->-Q[6]-Cs<+>. Firstly, BTB<3->-Q[6]-Cs<+> is synthesized under a certain condition, then BTB<3->-Q[6]-Cs<+> is dissolved in diluted hydrochloric acid for obtaining BTB<3->-Q[6]-NH4<+>, and in an ammonia solution with a certain concentration and in the presence of Cs<+>, BTB<3->-Q[6]-NH4<+> is converted into BTB<3->-Q[6]-Cs<+>, so that separation and enrichment of Cs<+> are realized. The synthetic method is performed at normal temperature under normal pressure, and has the characteristics of simple and rapid operation, high efficiency, high yield and the like.
Description
Technical field
Introduction of the present invention belongs to and has multidimensional porous cave melon cyclic group organic framework polymer and synthetic method and application.Be exactly specifically unordered melon ring (Cucurbit [
n] urils, Q [
6] s) molecule in the solution, containing aromatic base organic polydentate part and Q [
6] under the C-H π of outer wall and π π sintering action, ordered arrangement and form Supramolecular self assembly monomer, this Supramolecular self assembly monomer again by metal ion and the direct coordination of melon central port ketonic oxygen, thus forms melon cyclic group multidimensional porous cave supermolecule polymer.This supermolecule polymer selectivity can catch basic metal Cs
+ion.
Background technology
Caesium (Cs) element, since this life of German famous chemist in 1860 and physicist Kiel dagger-axe husband are found with spectroscopic analysis methods first time from German Dole's base nurse mineral water, has received the common concern of countries in the world scientist.The most important physical properties of caesium is photovoltaic effect, and it is under atomic weak illumination effect, just can ejected electron.Utilize this photoelectric property can realize a series of automatic control.Caesium is in mist or have absorption ultrared ability night, can be made into the infrared radiation light source on opticinstrument, also can be made into infrared telescope, for military reconnaissance, frontier defense patrol, warship night flight etc.Caesium is also very sensitive to radioactive rays, can be made into radioactive rays and experience resolving device, be applied to aerospace detection uranium ore; Caesium warning horn can also be made, once there be radioactive substance to overflow, will give the alarm, provide against any misfortune.Caesium metal and compound thereof and alloy are applied to from military affairs to civilian industry due to the performance of its uniqueness, from top science technology to every field such as daily lives.But the content of the rare alkaline metal caesium that occurring in nature exists is very low, and normal and other alkali metal symbiosis.Therefore along with the fast development of new high-tech industry, heavy rare alkaline metal caesium and compound thereof are applied in the various materials such as optical fiber, electronics, luminescence, soldering flux and energetic material more and more widely, and first these bases and application work need solution is the high efficiency separation of caesium.In addition, the process of nuclear industry high activity liquid waste is problem extremely concerned in environmental science and radiological chemistry.The radionuclide contained in waste liquid
137cs has long transformation period (T
1/2=30.17), be gamma-ray main source, huge hidden danger is also existed to environment.Will
137cs removes or reclaims, then not only can obtain the radionuclide with extensive use
137cs also greatly can reduce the processing costs of waste liquid simultaneously, brings huge economic benefit and social benefit.
Melon ring (Cucurbit [n] urils or Q [
n] s) be the novel caged macrocylc compound of one in macrocylc compound family.To be classes replace by n glycosides urea or alkyl the large ring cage compound with both ends open that glycosides urea unit and 2n methylene bridge link up for they, melon ring (Q [
n]) chemical formula be (
c 6 h 6 n 4 o 2 ) n , structural formula schematically as follows:
It has interior hydrophobic outer hydrophilic cavity structure.Melon ring hydrophobic cavity, not only can inclusion amine ion, Cl
-deng, in addition can also optionally inclusion NO
3 -; And can CH be trapped
4, C
2h
4, N
2, O
2, CO
2deng gas molecule.In addition, " inlay " due to melon ring two ports and a circle carbonylic oxygen atom, can interact with many kinds of metal ions, and can identify some metal ion.
Based on melon ring constructional feature and develop its Study on Functional target for guiding, the present invention not only optimizes the synthetic method previously applied for a patent, and develops synthesized melon cyclic group multidimensional in this patent, the multi-level application of supermolecule polymer in metal ion identification.The application of this patent " the control Synthesis and application of aromatic base organic polydentate part-melon ring porous framework polymkeric substance " is therefore proposed.
Summary of the invention
The object of the invention is to the synergy utilizing aromatic base organic polydentate part and metal ion, the a series of melon cyclic group multidimensional porous cave supermolecule polymer with different structure feature and character of design and synthesis, study the synthetic method that it is new, the hydrothermal synthesis method of original high-temperature pressurizing is reduced to the simple synthesis of normal temperature and pressure conditions.And utilize this special polymkeric substance with metal-melon ring organic framework to study its application feature in metal ion seizure.
The present inventor, research and design aromatic base organic polydentate part-melon ring porous framework polymkeric substance and synthetic method thereof, and apply for national patent, application number 2014101400444, the present invention is the further research and development at above-mentioned patent application Research foundation, devise the method for the Fast back-projection algorithm aromatic base organic polydentate part-melon ring porous framework polymkeric substance under new normal temperature and pressure conditions, and find that such polymkeric substance efficiently can catch Cs
+ion, and Cs can be discharged under diluted acid condition
+, and framework can be kept constant, thus circulation catches Cs
+ion.
The present invention be with melon ring (Q [
6]) and aromatic base organic polydentate part and metal-salt be raw material, react in aqueous, synthesize constructed by melon ring, aromatic base organic polydentate part and metal ion there is multidimensional porous cave supermolecule polymer.
Above-mentioned melon cyclic group multidimensional porous cave metal organic frame polymkeric substance comprises two-dimension netted melon cyclic group metal organic frame polymkeric substance and 3 D stereo melon cyclic group metal organic frame polymkeric substance.
Aromatic base organic polydentate part of the present invention controls multidimensional porous cave melon cyclic group metal organic frame polymkeric substance and the synthetic method of synthesis, follows these steps to carry out:
(1) by aromatic base organic polydentate part, Q [6] and metal-salt C
3cl in molar ratio 1: 1.5 ~ 3: 4.5 ~ 6 batchings weighs respectively;
(2) by Q [
6] and metal-salt add water and strong stirring dissolve;
(3) added water by aromatic base organic polydentate part, strong stirring dissolves, and adds the strong aqua of half volume of water;
(4) under whipped state, step (3) solution adds rapidly in the mixing solutions of step (2);
(5) by after mixed solution strong stirring 12 h ~ 24 h of (4), stop stirring;
(6) by the turbid solution centrifugal gained white solid powder drying at room temperature of (5), be resulting polymers BTB
3--Q [6]-Cs
+;
(7) by step (6) gained BTB
3--Q [6]-Cs
+; Be dissolved in 0.001M HCl, generate BTB
3--Q [6]-NH
4 +, white powder, centrifugation, drying at room temperature, obtains BTB
3--Q [6]-NH
4 +;
(8) by step (7) gained BTB
3--Q [6]-NH
4 +; Be placed in certain density ammonia solution, at Cs
+under existence condition, BTB can be converted into again
3--Q [6]-Cs
+; Through centrifugation dry BTB
3--Q [6]-Cs
+white powder.
The melon ring (Q [6]) of above-mentioned indication (structural formula as shown in the formula); Above-mentioned an alkali metal salt is cesium chloride or cesium carbonate; Above-mentioned aromatic base organic polydentate part is 4,4', 4''-benzene-1,3,5-, tri--phenylformic acid (H
3bTB) (structural formula as shown in the formula).
。
The ammonia solution concentration of step (8) indication is V
strong aqua︰ V
water=1: 4 ~ 6.
Step (8) and step (7) can be carried out repeatedly.
Utilize the control synthetic product BTB of the aromatic base organic polydentate part-melon ring porous framework polymkeric substance of gained of the present invention
3--Q [6]-Cs
+cs is discharged in dilute acid soln
+form BTB
3--Q [6]-NH
4 +, BTB
3--Q [6]-NH
4 +containing Cs
+cs is caught in solution
+generate BTB
3--Q [6]-Cs
+, so repeatedly carry out, caesium can be separated from Ar ion mixing solution, and reach the effect of enrichment caesium.
Melon cyclic group multidimensional porous cave supermolecule polymer synthesized in the present invention adopts the means such as PXRD powdery diffractometry and EDS to carry out structural characterization.Polymkeric substance synthesized in the present invention is characterized by PXRD powdery diffractometry and the present inventor applies for a patent in " aromatic base organic polydentate part-melon ring porous framework polymkeric substance and synthetic method thereof ", the crystalline structure simulation PXRD peak type of described title complex is completely the same, shows that polymkeric substance described in patent of the present invention is subject polymer.
Take a certain amount of above-mentioned polymkeric substance in the present invention, be placed in respectively containing Cs
+in ionic metal solution and mixed alkali metal solution, stirred for several hour, characterize through means such as PXRD powdery diffractometry and EDS, structure shows that this polymkeric substance is to Cs
+ion has well identification and capturing ability.Be immersed in stirred for several hour in dilute acid soln again, filter, the means such as throw out EDS characterized, structure shows that this polymkeric substance can discharge Cs in dilute acid soln
+ion, and characterize this polymkeric substance after dilute acid soln soaks through PXRD powdery diffractometry, still keep original framework.Show that this base polymer can to selectivity to Cs
+ion-catching, and can Reusability.
The present invention is compared with background technology application number 2014101400444, it is the further research and development at above-mentioned patent application Research foundation, devise the method for the Fast back-projection algorithm aromatic base organic polydentate part-melon ring porous framework polymkeric substance under new normal temperature and pressure conditions, and find this polymer B TB
3--Q [6]-NH
4 +cs can be caught
+ion, and Cs can be discharged under diluted acid condition
+, and framework can be kept constant, thus circulation catches Cs
+ion, reaches Cs
+the separation and consentration of ion.
The synthetic method advantage that patent of the present invention uses is to have simple to operate, and fast, efficient and productive rate high, for the performance development of this type of melon cyclic group multidimensional porous cave supermolecule polymer and practical application are laid a good foundation.
Accompanying drawing explanation
The crystalline structure figure that Fig. 1 aromatic base organic polydentate part controls the multidimensional porous cave melon cyclic group organic framework of synthesis illustrates: the hexa-atomic melon ring that (a) is unordered; B () adds BTB
3-modular construction in the melon cyclic group multidimensional porous cave supermolecule polymer formed with Q [6]; BTB in (c) this element structure
3-with BTB
3-interaction relationship illustrates; BTB in (d and e) this element structure
3-illustrate with Q [6] interphase interaction relation.
The PXRD spectrogram of the multidimensional porous cave supermolecule polymer crystalline structure matching of Fig. 2 this patent embodiment 1 method synthesis and PXRD spectrogram thereof.
The PXRD spectrogram of the multidimensional porous cave supermolecule polymer crystalline structure matching of Fig. 3 this patent embodiment 2 method synthesis and PXRD spectrogram thereof.
Fig. 4 aromatic base organic polydentate part controls the multidimensional porous cave supermolecule polymer release Cs of synthesis
+(left figure) and release Cs before ion
+after ion, the EDS of (right figure) characterizes.
The PXRD spectrogram (upper figure) of the multidimensional porous cave supermolecule polymer crystalline structure matching of Fig. 5 this patent embodiment 1 method synthesis; The multidimensional porous cave supermolecule polymer of this patent embodiment 2 method synthesis discharges Cs through acid soak
+(middle figure) and the PXRD spectrogram (figure below) without acid soak after ion.
The multidimensional porous cave supermolecule polymer circulation of Fig. 6 this patent embodiment 1 method synthesis catches Cs
+pXRD before and after ion characterizes.(A represents that the multidimensional porous cave supermolecule polymer that embodiment 1 method is synthesized catches first time Cs
+before ion; B represents that the multidimensional porous cave supermolecule polymer first time that embodiment 1 method is synthesized catches Cs
+after ion, form the multidimensional porous cave supermolecule polymer of embodiment 2 method synthesis; A-1 represents that B discharges Cs in rare molten acid solution
+after multidimensional porous cave supermolecule polymer, B-1 represents that A-1 catches Cs again
+multidimensional porous cave supermolecule polymer, so recycle).
The multidimensional porous cave supermolecule polymer circulation of Fig. 7 this patent embodiment 1 method synthesis catches Cs
+eDS before and after ion characterizes.(A represents that the multidimensional porous cave supermolecule polymer that embodiment 1 method is synthesized catches first time Cs
+before ion; B represents that the multidimensional porous cave supermolecule polymer first time that embodiment 1 method is synthesized catches Cs
+after ion, form the multidimensional porous cave supermolecule polymer of embodiment 2 method synthesis; A-1 represents that B discharges Cs in rare molten acid solution
+after multidimensional porous cave supermolecule polymer, B-1 represents that A-1 catches Cs again
+multidimensional porous cave supermolecule polymer, so recycle.）
specific implementation method
Embodiment 1: aromatic base organic polydentate part control synthesis multidimensional porous cave melon cyclic group metal organic frame polymkeric substance (
a) synthesis implementation method.Take hexa-atomic melon ring (Q [6]) 0.35 g (0.3 mmol) and H respectively
3bTB 0.044 g (0.1 mmol).Q [6] is placed in the beaker of 100 mL containing 50 mL distilled water, shakes 10 minutes, make Q [6] Granular composite even, add magneton and stir.Again by H
3bTB is placed in the beaker of 50 mL containing 10mL distilled water, adds magneton and stirs, and under agitation, injects 5mL concentrated ammonia solution.After stirring 10 min, be poured in Q [6] turbid solution, stir 48 h.Stop stirring, centrifugally obtaining white powder, is subject polymer.Productive rate at 50 ~ 60%(based on Q [6]) (accompanying drawing 1 please be see, 2).
Embodiment 2: aromatic base organic polydentate part control synthesis multidimensional porous cave melon cyclic group metal organic frame polymkeric substance (
b) synthesis implementation method.Take hexa-atomic melon ring (Q [6]) 0.35 g (0.3 mmol) respectively, CsCl 0.2 g (1.2 mmol), H
3bTB 0.044 g (0.1 mmol).Q [6] and CsCl is placed in the round-bottomed flask of 250 mL containing 90mL distilled water, shakes 10 minutes, make Q [6] Granular composite even, add magneton and stir.Again by H
3bTB is placed in the beaker of 50 mL containing 10 mL distilled water, adds magneton and stirs, under agitation, inject 5 mL concentrated ammonia solutions.After stirring 10 min, be poured in Q [6] turbid solution, oil bath heats up 60 DEG C, magnetic agitation 4 h.Stop stirring, centrifugally obtaining white powder, is subject polymer.Productive rate please see accompanying drawing 3 at 60 ~ 70%().
Embodiment 3: get subject polymer (BTB in 100 mg embodiments 2
3--Q [6]-Cs
+).Be placed in 5mL 0.001M HCl solution, stir after 4h centrifugal, drying at room temperature, subject polymer in embodiment 1
a-1(accompanying drawing 4-7 please be see).
Embodiment 4: get subject polymer in 80 mg embodiments 3
a-1.To be placed in solution 5mL (V strong aqua: water=1:5) solution and to add 30 mg CsCl, centrifugal after stirring 1h, drying at room temperature, subject polymer in embodiment 2
b-1(accompanying drawing 4-7 please be see).
Claims (5)
1. a control synthetic method for aromatic base organic polydentate part-melon ring porous framework polymkeric substance, described aromatic base organic polydentate part-melon ring porous framework polymkeric substance is BTB
3--Q [6]-NH
4 +, its structural formula is { (NH
4 +)
6(H
2o)
6(Q [6])
32(BTB) x H
2o } and BTB
3--Q [6]-Cs
+, its structural formula is { Cs
6(H
2o)
6(Q [6])
32(BTB) x H
2o }, it is characterized in that BTB
3--Q [6]-NH
4 +and BTB
3--Q [6]-Cs
+synthetic method be:
(1) by H
3bTB, Q [6], cesium salt in molar ratio 1: 1.5 ~ 3: 4.5 ~ 6 batchings weigh respectively;
(2) by Q [6] water dissolution;
(3) by H
3bTB water dissolution, injects the strong aqua of half volume of water;
(4) under whipped state, step (3) solution adds rapidly in the solution of step (2);
(5) by step (4) solution strong stirring 12 ~ 24h, stop stirring;
(6) by centrifugal for the turbid solution of step (5) gained white powder, drying at room temperature obtains BTB
3--Q [6]-Cs
+;
(7) by step (6) gained BTB
3--Q [6]-Cs
+; Be dissolved in 0.001M HCl, generate BTB
3--Q [6]-NH
4 +, white powder, centrifugation, drying at room temperature, obtains BTB
3--Q [6]-NH
4 +;
(8) by step (7) gained BTB
3--Q [6]-NH
4 +; Be placed in certain density ammonia solution, at Cs
+under existence condition, BTB can be converted into again
3--Q [6]-Cs
+; Through centrifugation dry BTB
3--Q [6]-Cs
+white powder.
2. the control synthetic method of a kind of aromatic base organic polydentate part according to claim 1-melon ring porous framework polymkeric substance, it is characterized in that described aromatic base organic polydentate part is 4,4', 4''-benzene-1,3,5-, tri--phenylformic acid, structural formula is:
.
3. the control synthetic method of a kind of aromatic base organic polydentate part according to claim 1-melon ring porous framework polymkeric substance, is characterized in that the ammonia solution concentration of step (8) indication is V
strong aqua︰ V
water=1: 4 ~ 6.
4. the control synthetic method of a kind of aromatic base organic polydentate part according to claim 1-melon ring porous framework polymkeric substance, is characterized in that step (8) and step (7) can be carried out repeatedly.
5. the application of the control synthetic method of a kind of aromatic base organic polydentate part as claimed in claim 1-melon ring porous framework polymkeric substance, is characterized in that the control synthetic product BTB of the aromatic base organic polydentate part-melon ring porous framework polymkeric substance utilizing gained of the present invention
3--Q [6]-Cs
+cs is discharged in dilute acid soln
+form BTB
3--Q [6]-NH
4 +, BTB
3--Q [6]-NH
4 +containing Cs
+cs is caught in solution
+generate BTB
3--Q [6]-Cs
+, so repeatedly carry out, caesium can be separated from Ar ion mixing solution, and reach the effect of enrichment caesium.
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|---|---|---|---|
| CN201410538187.0A CN104327101A (en) | 2014-10-14 | 2014-10-14 | Control synthesis and application of aryl organic multidentate ligand-cucurbituril porous framework polymer |
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|---|---|---|---|
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ID=52401918
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880292A (en) * | 2010-06-21 | 2010-11-10 | 贵州大学 | Cucurbit[n]uril metal-organic framework polymer in multilayer porous reticular structure and synthesis method thereof |
| CN104017003A (en) * | 2014-04-09 | 2014-09-03 | 南京大学 | Aromatic organic multidentate ligand- cucurbituril porous frame polymer and synthesis method thereof |
-
2014
- 2014-10-14 CN CN201410538187.0A patent/CN104327101A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880292A (en) * | 2010-06-21 | 2010-11-10 | 贵州大学 | Cucurbit[n]uril metal-organic framework polymer in multilayer porous reticular structure and synthesis method thereof |
| CN104017003A (en) * | 2014-04-09 | 2014-09-03 | 南京大学 | Aromatic organic multidentate ligand- cucurbituril porous frame polymer and synthesis method thereof |
Non-Patent Citations (3)
| Title |
|---|
| YOUNG JIN JEON ET AL.: ""Artificial Ion Channel Formed by Cucurbit[n]uril Derivatives with a Carbonyl Group Fringed Portal Reminiscent of the Selectivity Filter of K+ Channels"", 《J. AM. CHEM. SOC.》 * |
| 张桂玲 等: ""以瓜环为主体的金属离子配合物研究新进展"", 《化工技术与开发》 * |
| 陈凯: ""瓜环基—有机酸超分子自组装体的设计及可控制备"", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
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