CN106243363B - It is complete that the hexa-atomic melon ring of cyclopenta-rare earth is replaced to form supermolecule polymer and preparation method thereof - Google Patents
It is complete that the hexa-atomic melon ring of cyclopenta-rare earth is replaced to form supermolecule polymer and preparation method thereof Download PDFInfo
- Publication number
- CN106243363B CN106243363B CN201610614630.7A CN201610614630A CN106243363B CN 106243363 B CN106243363 B CN 106243363B CN 201610614630 A CN201610614630 A CN 201610614630A CN 106243363 B CN106243363 B CN 106243363B
- Authority
- CN
- China
- Prior art keywords
- rare earth
- cyclopenta
- hexa
- melon ring
- atomic melon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a kind of full substitution hexa-atomic melon ring of cyclopenta-rare earths to form supermolecule polymer and preparation method thereof.The present invention utilizes inorganic matter zinc chloride (ZnCl2) or caddy (CdCl2) inducing action, make that the hexa-atomic melon ring of cyclopenta is replaced directly to be coordinated with serial rare-earth metal ion entirely, a series of full Supramolecular self assembly body polymer for replacing the hexa-atomic melon ring-rare earth metal of cyclopenta are synthesized, replace the hexa-atomic melon ring of cyclopenta different from light rare earth metal ion (La, Ce, Pr, Nd, Sm, Eu) and heavy rare earth metal (Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) the formation time of Supramolecular self assembly polymer using complete, can be used for the separation of weight rare earth ion.
Description
Technical field
Field of material technology of the present invention, the especially a kind of full substitution hexa-atomic melon ring of cyclopenta-rare earth form supermolecule polymerization
Object and preparation method thereof.
Background technique
Rare earth element communication information, petroleum catalysis, colored display, in terms of the angle that can not be substituted of performer
Color has the title of industrial " vitamin ".U.S. Department of Defense and Japan Defense Agency (JDA) are first as strategy 16 kinds in 17 kinds of elements of rare earth
Element, in so-called 35 kinds strategic elements, rare earth has accounted for half.Using cascade extraction technology, Mr. Xu Guangxian is first in the world
The secondary countercurrent extraction theory for proposing to be suitable for rare earth extraction separation establishes complete Rare Earth Separation optimization process design method,
Realize " step amplification " of design parameter to actual production.Above-mentioned achievement is widely used to China's rare-earth industry, is China
Technology of Separating Rare Earth level and production capacity leap to first place in the world and have made important contribution.It is used in present Rare Earth Production
Separation method be mainly using the difference in rare earth compound solubility to be separated and purified.Melon ring (Cucurbit
[n] urils, Q [n]) it is a kind of big ring cage compound linked up by n glycosides urea unit and 2n methylene bridge.Due to melon
This circle carbonylic oxygen atom " is inlayed " in two ports of ring, have with metallic ion coordination formed complex ability, in recent years by
As organic ligand, received more and more attention in the research field that metal-organic supermolecular polymer is constructed.And ring penta
Base melon ring is a kind of potential substituted cucurbituril being just reported recently.The tetrachloro acid group of discovery cadmium and zinc is also shown recently
Similar " honeycomb effect " induces hexa-atomic melon ring (Q [6]) to be directly coordinated with serial rare-earth metal ion, has synthesized a series of six
First melon ring-rare earth metal tubulose supermolecule polymer.Precipitate light rare earth ion (La, Ce, Pr, Nd) rapidly.Thus
Applied " a kind of hexa-atomic melon ring of utilization synthesis-rare earth metal linear polymer separation weight rare earth method (application number:
201210457330.4) ", but in the patent, light rare earth ion (La, Ce, Pr, Nd) is because precipitating can not form supermolecule and gather
Close object.
In general, rare earth ion and the full substitution hexa-atomic melon ring of cyclopenta are difficult directly in neutral, slightly acidic water solution
It is coordinated and constructs to form supermolecule polymer.But when the water that zinc chloride or caddy introducing rare earth ion and melon ring coexist
In solution, inducing action can be played, rare earth ion and the hexa-atomic melon ring of cyclopenta is enable directly to be coordinated to form oversubscription rapidly
Sub- self-assembling polymers.
Summary of the invention
The object of the present invention is to provide a kind of complete hexa-atomic melon ring of substitution cyclopenta-rare earth formed supermolecule polymer and
Preparation method, a kind of crystalline solid is high molecular simultaneously preparing for it, realizes the initial gross separation of two kinds of rare earth ions, with
It overcomes the shortage of prior art.
The present invention is implemented as follows: replacing the hexa-atomic melon ring of cyclopenta-rare earth to form supermolecule polymer, its structure entirely
General formula are as follows:
{Ln(H2O)n(C54H60N24O12)}2[ZnCl4](H3O)X(H2O)
Ln represents rare earth metal in formula, and wherein n=5 or 6；X is crystalline water molecules quantity, 11≤X≤20.
The full preparation method for replacing the hexa-atomic melon ring of cyclopenta-rare earth to form supermolecule polymer, using zinc chloride as inorganic
Inducer will replace the hexa-atomic melon ring of cyclopenta and rare earth metal salt to carry out entirely under solutions of weak acidity of the concentration less than 2mol/L
Reaction forms the full substitution hexa-atomic melon ring-rare earth supermolecule polymer of cyclopenta.
Specifically comprise the following steps:
1) the hexa-atomic melon ring dilute hydrochloric acid of cyclopenta, phosphoric acid or sulfuric acid is replaced to be completely dissolved to obtain solution A by complete；
2) by rare earth metal salt and zinc chloride, 2~8:6 is mixed in molar ratio, is completely dissolved two kinds of substances with water,
Obtain solution B；
3) solution A is mixed with B, the hexa-atomic melon ring dilute hydrochloric acid of full substitution cyclopenta, rare earth gold in mixed solution
The molar ratio for belonging to salt and zinc chloride is 1:2~8:6；
4) mixed solution obtained to step 3) carries out standing 18~50 hours, obtains the full substitution hexa-atomic melon ring-of cyclopenta
Rare earth supermolecule polymer.
Can it is obtainable it is complete replace the hexa-atomic melon ring-rare earth supermolecule polymer of cyclopenta chemical formula it is as follows:
{La(H2O)6(C54H60N24O12)}2[ZnCl4]Cl 2(H3O)14(H2O)
{Ce(H2O)6(C54H60N24O12)}2[ZnCl4]Cl 2(H3O)12(H2O)
{Pr(H2O)5(C54H60N24O12)}2[ZnCl4](H3O)16(H2O)
{Nd(H2O)5(C54H60N24O12)}2[ZnCl4](H3O)14(H2O)
{Eu(H2O)5(C54H60N24O12)}2[ZnCl4](H3O)18(H2O)
{Gd(H2O)5(C54H60N24O12)}2[ZnCl4](H3O)11(H2O)
{Dy(H2O)5(C54H60N24O12)}2[ZnCl4](H3O)12(H2O)
Light rare earth samarium and the full substitution hexa-atomic melon ring of cyclopenta do not form supermolecule polymer, but form individually
" molecular capsule " structure.Its structural formula are as follows:
{Sm(H2O)6(C54H60N24O12)}2[ZnCl4](H3O)20(H2O)。
By adopting the above-described technical solution, compared with prior art, the present invention utilizes inorganic matter zinc chloride (ZnCl2) or
Caddy (CdCl2) inducing action, make that the hexa-atomic melon ring of cyclopenta is replaced directly to be coordinated with serial rare-earth metal ion entirely, synthesize
A series of full Supramolecular self assembly body polymer for replacing cyclopenta hexa-atomic melon ring-rare earth metals, and during the preparation process, benefit
With it is complete replace the hexa-atomic melon ring of cyclopenta and light rare earth metal ion (La, Ce, Pr, Nd, Sm, Eu) and heavy rare earth metal (Gd, Tb,
Dy, Ho, Er, Tm, Yb, Lu) form Supramolecular self assembly polymer time it is different, can be used for the separation of weight rare earth ion.
The invention is simple and feasible, low in cost, and using effect is good.
Detailed description of the invention
Fig. 1 is the full crystal structure figure for replacing the hexa-atomic melon ring of cyclopenta；
Fig. 2 is rare earth ion and the full complex for replacing the hexa-atomic melon ring of cyclopenta to be formed；
Wherein: a indicates La3+The complex formed with CyP6Q [6]；B indicates rare earth ion Ce3+With CyP6Q [6] shape
At complex；The one-dimensional supermolecule polymer that the complex that c and rare earth ion and CyP6Q [6] are formed is formed；D is dilute
The accumulation graph for the complex that earthmetal cations and CyP6Q [6] are formed；
Fig. 3 is rare earth ion and the full complex for replacing the hexa-atomic melon ring of cyclopenta to be formed；
Wherein: a indicates Sm3+The complex formed with CyP6Q [6]；B indicates Sm3+The complex formed with CyP6Q [6]
Accumulation graph；
Fig. 4 lists the powder diagram of the complex of 3 rare earth ions (Gd, Sm, Eu) and CyP6Q [6] formation；
Fig. 5 is the IR spectrum of CyP6Q [6] and CyP6Q [6]/Ln system；
Fig. 6 is the differential thermal (DTA) and thermogravimetric (TG) analysis map of CyP6Q [6]/Ln system crystal；
Fig. 7 is the electron spectroscopy analysis result of product；
Wherein, a is the Pr of molar ratio 1:13+And Lu3+The electron spectroscopy analysis result of crystal is obtained in mixed solution；B is
The La of molar ratio 1:13+And Tm3+The electron spectroscopy analysis result of crystal is obtained in mixed solution；C is the Ce of molar ratio 1:13+With
Ho3+The electron spectroscopy analysis result of crystal is obtained in mixed solution；A is the La of molar ratio 1:13+、Ce3+、Pr3+、Nd3+And Lu3+、
Er3+、Tm3+、Yb3+The electron spectroscopy analysis result of crystal is obtained in mixed solution.
Specific embodiment
The present invention is described in further detail with reference to the accompanying drawing, but not as any limitation of the invention
The embodiment of the present invention 1: the full preparation method for replacing the hexa-atomic melon ring of cyclopenta-rare earth to form supermolecule polymer,
Specifically comprise the following steps:
1) it is completely dissolved the full substitution hexa-atomic melon ring of cyclopenta of self-control to obtain solution A with dilute hydrochloric acid；
2) by rare earth metal salt (rare earth metal includes La and Ho) and zinc chloride, 4:6 is mixed in molar ratio, uses water
Two kinds of substances are completely dissolved, solution B is obtained；
3) solution A is mixed with B, the hexa-atomic melon ring dilute hydrochloric acid of full substitution cyclopenta, rare earth gold in mixed solution
The molar ratio for belonging to salt and zinc chloride is 1:4:6；
4) mixed solution obtained to step 3) carries out standing 24 hours, obtains the full substitution hexa-atomic melon ring-rare earth of cyclopenta
Supermolecule polymer.
{La(H2O)6(C54H60N24O12)}2[ZnCl4]Cl 2(H3O)14(H2O)
The embodiment of the present invention 2: the full preparation method for replacing the hexa-atomic melon ring of cyclopenta-rare earth to form supermolecule polymer,
Specifically comprise the following steps:
1) it is completely dissolved the full substitution hexa-atomic melon ring of cyclopenta of self-control to obtain solution A with dilute hydrochloric acid；
2) by rare earth metal salt (rare earth metal includes La and Lu) and zinc chloride, 2:6 is mixed in molar ratio, uses water
Two kinds of substances are completely dissolved, solution B is obtained；
3) solution A is mixed with B, the hexa-atomic melon ring dilute hydrochloric acid of full substitution cyclopenta, rare earth gold in mixed solution
The molar ratio for belonging to salt and zinc chloride is 1:2:6；
4) mixed solution obtained to step 3) carries out standing 18 hours, obtains the full substitution hexa-atomic melon ring-rare earth of cyclopenta
Supermolecule polymer.
{La(H2O)6(C54H60N24O12)}2[ZnCl4]Cl 2(H3O)14(H2O)
The embodiment of the present invention 3: the full preparation method for replacing the hexa-atomic melon ring of cyclopenta-rare earth to form supermolecule polymer,
Specifically comprise the following steps:
1) it is completely dissolved the full substitution hexa-atomic melon ring of cyclopenta of self-control to obtain solution A with dilute hydrochloric acid；
2) by rare earth metal salt (rare earth metal includes La and Tm) and zinc chloride, 2:6 is mixed in molar ratio, uses water
Two kinds of substances are completely dissolved, solution B is obtained；
3) solution A is mixed with B, the hexa-atomic melon ring dilute hydrochloric acid of full substitution cyclopenta, rare earth gold in mixed solution
The molar ratio for belonging to salt and zinc chloride is 1:8:6；
4) mixed solution obtained to step 3) carries out standing 50 hours, obtains the full substitution hexa-atomic melon ring-rare earth of cyclopenta
Supermolecule polymer.
{La(H2O)6(C54H60N24O12)}2[ZnCl4]Cl 2(H3O)14(H2O)
Separation detection structure after embodiment 1-3 reaction is as shown in table 1.
1 La of the table separating effect with three kinds of rare earth metals respectively
-- it indicates that the element is not added in experiment
It joined metal in example 1 as above, but the metal contained in crystallization is La, do not contain Ho.
The present embodiment only illustrates with the hexa-atomic melon ring-rare earth supermolecule polymer of the full substitution cyclopenta of La as an example,
Principle when separating other types is identical.
Claims (2)
1. a kind of full substitution hexa-atomic melon ring of cyclopenta-rare earth forms supermolecule polymer, it is characterised in that: its general structure
Are as follows:
{Ln(H2O)n(C54H60N24O12)}2[ZnCl4](H3O)X(H2O)
Ln represents rare earth metal in formula, and wherein n=5 or 6；X is crystalline water molecules quantity, 11≤X≤20.
2. a kind of full preparation side for replacing the hexa-atomic melon ring of cyclopenta-rare earth to form supermolecule polymer as described in claim 1
Method, it is characterised in that: using zinc chloride as inorganic inducing agent, under solutions of weak acidity of the concentration less than 2mol/L, will replace entirely
The hexa-atomic melon ring of cyclopenta carries out reacting the full substitution hexa-atomic melon ring-rare earth supermolecule polymer of cyclopenta of formation with rare earth metal salt；
Specifically comprise the following steps:
1) the hexa-atomic melon ring of cyclopenta is replaced to be completely dissolved to obtain solution A with dilute hydrochloric acid by complete；
2) by rare earth metal salt and zinc chloride, 2~8:6 is mixed in molar ratio, is completely dissolved two kinds of substances with water, is obtained
Solution B；
3) solution A is mixed with B, the hexa-atomic melon ring dilute hydrochloric acid of full substitution cyclopenta, rare earth metal salt in mixed solution
And the molar ratio of zinc chloride is 1:2~8:6；
4) mixed solution obtained to step 3) carries out standing 18~50 hours, obtains the full substitution hexa-atomic melon ring-rare earth of cyclopenta
Supermolecule polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610614630.7A CN106243363B (en) | 2016-07-31 | 2016-07-31 | It is complete that the hexa-atomic melon ring of cyclopenta-rare earth is replaced to form supermolecule polymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610614630.7A CN106243363B (en) | 2016-07-31 | 2016-07-31 | It is complete that the hexa-atomic melon ring of cyclopenta-rare earth is replaced to form supermolecule polymer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106243363A CN106243363A (en) | 2016-12-21 |
| CN106243363B true CN106243363B (en) | 2019-07-05 |
Family
ID=57606177
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610614630.7A Active CN106243363B (en) | 2016-07-31 | 2016-07-31 | It is complete that the hexa-atomic melon ring of cyclopenta-rare earth is replaced to form supermolecule polymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106243363B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107446568A (en) * | 2017-07-12 | 2017-12-08 | 贵州大学 | A kind of fluorescent material |
| CN109916874B (en) * | 2019-04-16 | 2021-07-13 | 贵州大学 | Preparation method of fluorescent material for formaldehyde gas detection |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102936259A (en) * | 2012-11-15 | 2013-02-20 | 贵州大学 | Method for synthesizing cucurbit [6] uril, Q[6]-rear earth linear polymer and separating light rear earth from heavy rear earth |
| CN103965229A (en) * | 2014-04-17 | 2014-08-06 | 贵州大学 | Ortho four methyl six cucurbituril-terrae rare supermolecule polymer and synthetic method and application thereof |
| CN104262371A (en) * | 2014-10-10 | 2015-01-07 | 贵州大学 | IQ[6]-rare earth complex, as well as synthesis and application thereof |
-
2016
- 2016-07-31 CN CN201610614630.7A patent/CN106243363B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102936259A (en) * | 2012-11-15 | 2013-02-20 | 贵州大学 | Method for synthesizing cucurbit [6] uril, Q[6]-rear earth linear polymer and separating light rear earth from heavy rear earth |
| CN103965229A (en) * | 2014-04-17 | 2014-08-06 | 贵州大学 | Ortho four methyl six cucurbituril-terrae rare supermolecule polymer and synthetic method and application thereof |
| CN104262371A (en) * | 2014-10-10 | 2015-01-07 | 贵州大学 | IQ[6]-rare earth complex, as well as synthesis and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106243363A (en) | 2016-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102936259B (en) | Synthesize the method for hexa-atomic melon ring-rare earth linear polymer and separation weight rare earth thereof | |
| An et al. | Synthesis, structure, white-light emission, and temperature recognition properties of Eu/Tb mixed coordination polymers | |
| Freund et al. | Thiophene based europium β-diketonate complexes: effect of the ligand structure on the emission quantum yield | |
| Li et al. | Trigonal pyramidal {AsO2 (OH)} bridging tetranuclear rare-earth encapsulated polyoxotungstate aggregates | |
| Feng et al. | Anion-induced self-assembly of luminescent and magnetic homoleptic cyclic tetranuclear Ln4 (Salen) 4 and Ln4 (Salen) 2 complexes (Ln= Nd, Yb, Er, or Gd) | |
| Leonzio et al. | Circularly polarized luminescence from an Eu (III) complex based on 2-thenoyltrifluoroacetyl-acetonate and a tetradentate chiral ligand | |
| CN106243363B (en) | It is complete that the hexa-atomic melon ring of cyclopenta-rare earth is replaced to form supermolecule polymer and preparation method thereof | |
| CN101402855B (en) | Polyarylether rare-earth complexes luminous material and preparing process thereof | |
| Li et al. | Energy transfer and photoluminescence properties of lanthanide-containing polyoxotitanate cages coordinated by salicylate ligands | |
| CN103965229B (en) | Ortho position Tetramethyl melon ring-rare earth supermolecule polymer and synthetic method and application | |
| CN104230969B (en) | Symmetrical tetramethyl cucurbituril and rare earth coordination compound and addition compound, synthetic method and application | |
| Xu et al. | Assembly, stabilities, and photophysical behaviors of highly efficient luminescent materials fabricated from a terbium complex doped silica/polymer hybrids | |
| CN103951687B (en) | Ortho position Tetramethyl melon ring rare earth adduct and synthetic method and application | |
| CN114133581B (en) | Mg-MOFs, preparation method thereof and application thereof in iron ion detection | |
| You et al. | Cage Bismuth Metal–Organic Framework Materials Based on a Flexible Triazine–Polycarboxylic Acid: Subgram Synthesis, Application for Sensing, and White Light Tuning | |
| Sun et al. | Lanthanide complex-functionalized polyhedral oligomeric silsesquioxane with multicolor emission covered from 450 nm to 1700 nm | |
| CN103467531A (en) | H3PMo12O40-(HO)10Q[5]-light rare earth metal heterocomplex and synthesis and application | |
| CN103265568B (en) | A kind of eight yuan of melon ring-rare earth metal supermolecule polymers and synthetic method and application | |
| CN104262371A (en) | IQ[6]-rare earth complex, as well as synthesis and application thereof | |
| Wang et al. | Magnetism and luminescence of a MOF with linear Mn3 nodes derived from an emissive terthiophene-based imidazole linker | |
| CN102584686A (en) | Water soluble terpyridyl fluorescent compound and preparation method thereof | |
| CN102060997A (en) | Cucurbit[5]uril-rare-earth metal supramolecular polymer synthesized through induction of organic molecule and synthesizing method thereof | |
| CN109912633B (en) | Eu-complex fluorescent probe and preparation method and application thereof | |
| Zhang et al. | Syntheses, structures, photoluminescent and magnetic properties of pyrazine-2, 3-dicarboxylate-based cadmium-lanthanide/lanthanide coordination polymers tuned by CdII | |
| CN108659023B (en) | Rare earth-potassium bimetallic complex with extremely high fluorescence quantum yield |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |