CN106243363A - The full cyclopenta hexa-atomic melon ring rare earth that replaces forms supermolecule polymer and preparation method thereof - Google Patents

The full cyclopenta hexa-atomic melon ring rare earth that replaces forms supermolecule polymer and preparation method thereof Download PDF

Info

Publication number
CN106243363A
CN106243363A CN201610614630.7A CN201610614630A CN106243363A CN 106243363 A CN106243363 A CN 106243363A CN 201610614630 A CN201610614630 A CN 201610614630A CN 106243363 A CN106243363 A CN 106243363A
Authority
CN
China
Prior art keywords
rare earth
hexa
cyclopenta
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.)
Granted
Application number
CN201610614630.7A
Other languages
Chinese (zh)
Other versions
CN106243363B (en
Inventor
马培华
魏连通
周开志
屈云霞
陶朱
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guizhou University
Original Assignee
Guizhou University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Guizhou University filed Critical Guizhou University
Priority to CN201610614630.7A priority Critical patent/CN106243363B/en
Publication of CN106243363A publication Critical patent/CN106243363A/en
Application granted granted Critical
Publication of CN106243363B publication Critical patent/CN106243363B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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

Abstract

The invention discloses a kind of full cyclopenta hexa-atomic melon ring rare earth that replaces and form supermolecule polymer and preparation method thereof.The present invention utilizes inorganic matter zinc chloride (ZnCl2) or Caddy (Cleary) (CdCl2) inducing action, make entirely to replace cyclopenta hexa-atomic melon ring to be directly coordinated with serial rare-earth metal ion, synthesize the Supramolecular self assembly body polymer of a series of full replacement cyclopenta hexa-atomic melon ring rare earth metal, utilize full replacement cyclopenta hexa-atomic melon ring different from the time that 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, can be used for the separation of weight rare earth ion.

Description

The full cyclopenta hexa-atomic melon ring-rare earth that replaces forms supermolecule polymer and preparation thereof Method
Technical field
Field of material technology of the present invention, especially a kind of full cyclopenta hexa-atomic melon ring-rare earth that replaces forms supermolecule polymerization Thing and preparation method thereof.
Background technology
The angle that rare earth element can not be substituted the aspect performer such as communication information, oil catalysis, colored display, hydrogen storage material Color, has the title of industry " 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 of strategic elements, rare earth has accounted for half.Utilizing cascade extraction technology, Mr. Xu Guangxian is the most first Secondary proposition is applicable to the countercurrent extraction theory that rare earth extraction separates, and establishes complete Rare Earth Separation and optimizes process design method, Achieve the design parameter " step is amplified " to actual production.Above-mentioned achievement is widely used to China's rare-earth industry, for China Technology of Separating Rare Earth level and production capacity leap to first place in the world and have made important contribution.Now Rare Earth Production uses Separation method carry out separating and purify mainly by the difference on rare earth compound dissolubility.
Melon ring (Cucurbit [n] urils, Q [n]) is the macro ring that a class is linked up by n glycosides urea unit and 2n methylene bridge Cage compound.Owing to two ports of melon ring " inlay " this circle carbonylic oxygen atom, have and coordinate with metallic ion coordination formation The ability of thing, is used as organic ligand in recent years, is come by more in the research field that metal-organic supermolecular polymer is constructed The most concerns.And cyclopenta melon ring is the potential substituted cucurbituril of the one being the most just in the news.Find cadmium and zinc recently Tetrachloro acid group also show similar " Nidus Vespae effect ", induce hexa-atomic melon ring (Q [6]) directly to join with serial rare-earth metal ion Position, has synthesized a series of hexa-atomic melon ring-rare earth metal tubulose supermolecule polymer.Particularly make light rare earth ion (La, Ce, Pr, Nd) precipitate rapidly.Apply for that for this " a kind of utilization synthesizes hexa-atomic melon ring-rare earth metal linear polymer separation weight rare earth Method (application number: 201210457330.4) ", but in this patent, light rare earth ion (La, Ce, Pr, Nd) is because precipitation cannot Form supermolecule polymer.
Generally, rare earth ion is difficult to directly in neutrality, slightly acidic water solution with the full cyclopenta hexa-atomic melon ring that replaces It is coordinated and constructs formation supermolecule polymer.But when zinc chloride or Caddy (Cleary) are introduced the water that rare earth ion coexists with melon ring In solution, it can play inducing action, makes rare earth ion and cyclopenta hexa-atomic melon ring can the most directly be coordinated formation oversubscription Sub-self-assembling polymers.
Summary of the invention
It is an object of the invention to: provide a kind of complete replace cyclopenta hexa-atomic melon ring-rare earth formed supermolecule polymer and Its preparation method, it prepare a class crystalline solid high molecular while, it is achieved by the initial gross separation of two kinds of rare earth ions, with Overcome prior art not enough.
The present invention is achieved in that the full cyclopenta hexa-atomic melon ring-rare earth that replaces forms supermolecule polymer, its structure Formula is:
{Ln(H2O)n(C54H60N24O12)}2[ZnCl4](H3O)X(H2O)
In formula, Ln represents rare earth metal, and wherein n=5 or 6；X is crystalline water molecules quantity, 11 X 20.
The full cyclopenta hexa-atomic melon ring-rare earth that replaces forms the preparation method of supermolecule polymer, using zinc chloride as inorganic Derivant, under the concentration solutions of weak acidity less than 2mol/L, is carried out entirely replacing cyclopenta hexa-atomic melon ring with rare earth metal salt Reaction forms full replacement cyclopenta hexa-atomic melon ring-rare earth supermolecule polymer.
Specifically include following steps:
1) it is completely dissolved obtains solution A by entirely replacing cyclopenta hexa-atomic melon ring dilute hydrochloric acid, phosphoric acid or sulphuric acid；
2) rare earth metal salt and zinc chloride 2～8:6 are mixed in molar ratio, with water, two kinds of materials are completely dissolved, Obtain solution B；
3) solution A is mixed with B, the full replacement cyclopenta hexa-atomic melon ring dilute hydrochloric acid in mixed solution, rare earth gold The mol ratio belonging to salt and zinc chloride is 1:2～8:6；
4) treat step 3) mixed solution that obtains carries out standing 18～50 hours, it is thus achieved that complete replace cyclopenta hexa-atomic melon ring- Rare earth supermolecule polymer.
Can the chemical formula of obtainable full replacement cyclopenta hexa-atomic melon ring-rare earth supermolecule polymer 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 does not form supermolecule polymer with the full cyclopenta hexa-atomic melon ring that replaces, but defines individually " molecular capsule " structure.Its structural formula is:
{Sm(H2O)6(C54H60N24O12)}2[ZnCl4](H3O)20(H2O)。
Owing to have employed technique scheme, compared with prior art, the present invention utilizes inorganic matter zinc chloride (ZnCl2) or Caddy (Cleary) (CdCl2) inducing action, make entirely to replace cyclopenta hexa-atomic melon ring and be directly coordinated with serial rare-earth metal ion, synthesis The Supramolecular self assembly body polymer of a series of full replacement cyclopenta hexa-atomic melon ring-rare earth metal, and in preparation process, profit With complete replace cyclopenta hexa-atomic melon ring 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 different, can be used for the separation of weight rare earth ion. The present invention is simple, with low cost, and using effect is good.
Accompanying drawing explanation
Fig. 1 is the crystal structure figure entirely replacing cyclopenta hexa-atomic melon ring；
Fig. 2 is that rare earth ion replaces, with complete, the coordination compound that cyclopenta hexa-atomic melon ring is formed；
Wherein: a represents La3+The coordination compound formed with CyP6Q [6]；B represents rare earth ion Ce3+With CyP6Q [6] shape The coordination compound become；The one-dimensional supermolecule polymer of the coordination compound formation that c is formed with CyP6Q [6] with rare earth ion；D is dilute The accumulation graph of the coordination compound that earthmetal cations and CyP6Q [6] are formed；
Fig. 3 is that rare earth ion replaces, with complete, the coordination compound that cyclopenta hexa-atomic melon ring is formed；
Wherein: a represents Sm3+The coordination compound formed with CyP6Q [6]；B represents Sm3+The coordination compound formed with CyP6Q [6] Accumulation graph；
Fig. 4 lists the powder diagram of the coordination compound that 3 rare earth ions (Gd, Sm, Eu) are formed with CyP6Q [6]；
Fig. 5 is the IR spectrum of CyP6Q [6] and CyP6Q [6]/Ln system；
Fig. 6 is differential thermal (DTA) and thermogravimetric (TG) the analysis collection of illustrative plates of the system crystal of CyP6Q [6]/Ln；
Fig. 7 is the electron spectroscopy analysis result of product；
Wherein, a is the Pr of mol ratio 1:13+And Lu3+Mixed solution obtains the electron spectroscopy analysis result of crystal；B is The La of mol ratio 1:13+And Tm3+Mixed solution obtains the electron spectroscopy analysis result of crystal；C is the Ce of mol ratio 1:13+With Ho3+Mixed solution obtains the electron spectroscopy analysis result of crystal；A is the La of mol ratio 1:13+、Ce3+、Pr3+、Nd3+And Lu3+、 Er3+、Tm3+、Yb3+Mixed solution obtains the electron spectroscopy analysis result of crystal.
Detailed description of the invention
The present invention is described in further detail below in conjunction with the accompanying drawings, but not as any limitation of the invention
Embodiments of the invention 1: the full cyclopenta hexa-atomic melon ring-rare earth that replaces forms the preparation method of supermolecule polymer, Specifically include following steps:
1) self-control entirely replaces cyclopenta hexa-atomic melon ring dilute hydrochloric acid be completely dissolved and obtain solution A；
2) rare earth metal salt (rare earth metal includes La and Ho) and zinc chloride 4:6 in molar ratio are mixed, use water Two kinds of materials are completely dissolved, obtain solution B；
3) solution A is mixed with B, the full replacement cyclopenta hexa-atomic melon ring dilute hydrochloric acid in mixed solution, rare earth gold The mol ratio belonging to salt and zinc chloride is 1:4:6；
4) step 3 is treated) mixed solution that obtains carries out standing 24 hours, it is thus achieved that complete replace cyclopenta hexa-atomic melon ring-rare earth Supermolecule polymer.
{La(H2O)6(C54H60N24O12)}2[ZnCl4]Cl 2(H3O)14(H2O)
Embodiments of the invention 2: the full cyclopenta hexa-atomic melon ring-rare earth that replaces forms the preparation method of supermolecule polymer, Specifically include following steps:
1) self-control entirely replaces cyclopenta hexa-atomic melon ring dilute hydrochloric acid be completely dissolved and obtain solution A；
2) rare earth metal salt (rare earth metal includes La and Lu) and zinc chloride 2:6 in molar ratio are mixed, use water Two kinds of materials are completely dissolved, obtain solution B；
3) solution A is mixed with B, the full replacement cyclopenta hexa-atomic melon ring dilute hydrochloric acid in mixed solution, rare earth gold The mol ratio belonging to salt and zinc chloride is 1:2:6；
4) step 3 is treated) mixed solution that obtains carries out standing 18 hours, it is thus achieved that complete replace cyclopenta hexa-atomic melon ring-rare earth Supermolecule polymer.
{La(H2O)6(C54H60N24O12)}2[ZnCl4]Cl 2(H3O)14(H2O)
Embodiments of the invention 3: the full cyclopenta hexa-atomic melon ring-rare earth that replaces forms the preparation method of supermolecule polymer, Specifically include following steps:
1) self-control entirely replaces cyclopenta hexa-atomic melon ring dilute hydrochloric acid be completely dissolved and obtain solution A；
2) rare earth metal salt (rare earth metal includes La and Tm) and zinc chloride 2:6 in molar ratio are mixed, use water Two kinds of materials are completely dissolved, obtain solution B；
3) solution A is mixed with B, the full replacement cyclopenta hexa-atomic melon ring dilute hydrochloric acid in mixed solution, rare earth gold The mol ratio belonging to salt and zinc chloride is 1:8:6；
4) step 3 is treated) mixed solution that obtains carries out standing 50 hours, it is thus achieved that complete replace cyclopenta hexa-atomic melon ring-rare earth Supermolecule polymer.
{La(H2O)6(C54H60N24O12)}2[ZnCl4]Cl 2(H3O)14(H2O)
Embodiment 1-3 reacted separation detection structure is as shown in table 1.
The separating effect of table 1 respectively with three kinds of rare earth metals of La
--represent in experiment and do not add this element
Example 1 as above adds metal, but the metal contained in crystallization is La, does not contains Ho.
The present embodiment only illustrates as an example with the full cyclopenta hexa-atomic melon ring-rare earth supermolecule polymer that replaces of La, Principle when separating other kinds is identical.

Claims (3)

1. full replacement cyclopenta hexa-atomic melon ring-rare earth forms supermolecule polymer, it is characterised in that: its general structure For:
{Ln(H2O)n(C54H60N24O12)}2[ZnCl4](H3O)X(H2O)
In formula, Ln represents rare earth metal, and wherein n=5 or 6；X is crystalline water molecules quantity, 11 X 20.
2. the full cyclopenta hexa-atomic melon ring-rare earth that replaces as claimed in claim 1 forms the preparation side of supermolecule polymer Method, it is characterised in that: using zinc chloride as inorganic inducing agent, under the concentration solutions of weak acidity less than 2mol/L, will entirely replace Cyclopenta hexa-atomic melon ring and rare earth metal salt carry out reaction and form full replacement cyclopenta hexa-atomic melon ring-rare earth supermolecule polymer.
Preparation method the most according to claim 2, it is characterised in that: specifically include following steps:
1) it is completely dissolved obtains solution A by entirely replacing cyclopenta hexa-atomic melon ring dilute hydrochloric acid, phosphoric acid or sulphuric acid；
2) rare earth metal salt and zinc chloride 2～8:6 are mixed in molar ratio, with water, two kinds of materials are completely dissolved, obtain Solution B；
3) solution A is mixed with B, full replacement cyclopenta hexa-atomic melon ring dilute hydrochloric acid, the rare earth metal salt in mixed solution And the mol ratio of zinc chloride is 1:2～8:6；
4) step 3 is treated) mixed solution that obtains carries out standing 18～50 hours, it is thus achieved that complete replace cyclopenta hexa-atomic melon ring-rare earth Supermolecule polymer.
CN201610614630.7A 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 Active CN106243363B (en)

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 true CN106243363A (en) 2016-12-21
CN106243363B 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)

Cited By (2)

* Cited by examiner, † Cited by third party
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
CN109916874A (en) * 2019-04-16 2019-06-21 贵州大学 A kind of formaldehyde gas detection preparation method of fluorescent material

Citations (3)

* Cited by examiner, † Cited by third party
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
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

Cited By (3)

* Cited by examiner, † Cited by third party
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
CN109916874A (en) * 2019-04-16 2019-06-21 贵州大学 A kind of formaldehyde gas detection preparation method of fluorescent material
CN109916874B (en) * 2019-04-16 2021-07-13 贵州大学 Preparation method of fluorescent material for formaldehyde gas detection

Also Published As

Publication number Publication date
CN106243363B (en) 2019-07-05

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
CN106854175B (en) Terpyridyl zinc benzoate complex and preparation condition
Wang et al. Step-by-step and competitive assembly of two Dy (III) single-molecule magnets with their performance tuned by Schiff base ligands
Lee et al. Synthesis and Photoluminescence Properties of Eu3+‐Doped Silica@ Coordination Polymer Core–Shell Structures and Their Calcinated Silica@ Gd2O3: Eu and Hollow Gd2O3: Eu Microsphere Products
CN104230969B (en) Symmetrical tetramethyl cucurbituril and rare earth coordination compound and addition compound, synthetic method and application
CN106243363A (en) The full cyclopenta hexa-atomic melon ring rare earth that replaces forms supermolecule polymer and preparation method thereof
CN103965229B (en) Ortho position Tetramethyl melon ring-rare earth supermolecule polymer and synthetic method and application
CN103951687B (en) Ortho position Tetramethyl melon ring rare earth adduct and synthetic method and application
CN103467531A (en) H3PMo12O40-(HO)10Q[5]-light rare earth metal heterocomplex and synthesis and application
CN101412908B (en) Synthesis and use of rare earth Eu or Y and Eu mixing complex type photoluminescent material
Huang et al. Study on macromolecular metal complexes: synthesis, characterization, and fluorescence properties of stoichiometric complexes for rare earth coordinated with poly (acrylic acid)
Sun et al. Lanthanide complex-functionalized polyhedral oligomeric silsesquioxane with multicolor emission covered from 450 nm to 1700 nm
CN104262371A (en) IQ[6]-rare earth complex, as well as synthesis and application thereof
CN103265568A (en) Cucurbit [8]urils-rare earth metal supramolecular polymer as well as synthetic method and application thereof
CN102584686A (en) Water soluble terpyridyl fluorescent compound and preparation method thereof
CN103992340B (en) The hexa-atomic melon ring-rare earth adduct of monosubstituted hexamethyl and synthetic method and application
Wu et al. A novel bi-layered samarium complex with an unprecedented coordination mode of orotic acid [Sm2 (HL) 2 (ox)(H2O) 2] n· 2.5 nH2O (H3L= orotic acid, ox2−= oxalate2−): Synthesis, crystal structure and physical properties
CN101786989B (en) 4,4-di(4,4,5,5-tetramethyl imidazoline-3-oxidation-1-oxy radical) phenyl ether and preparation method thereof
CN103224509A (en) Fluoboride fluorescent derivative, and preparation method and application thereof
Zhou et al. Synthesis and spectroscopic study of a terbium (III) 2, 6-pyridinedicarboxylate complex
CN103224536B (en) Plumbous silver-colored iodine quaternary compound of rare earth of a kind of organic hybrid and preparation method thereof
Hassan et al. Synthesis and characterization of benzohydroxamic acid metal complexes and their cytotoxicity study
CN102936258A (en) Cucurbit [7] uril-rare earth tubular polymer induced by tetrachloro zinc acidic group and synthetic method thereof
CN101759711A (en) Synthesization and structure of inorganic-organic coordination polymer containing praseodymium
Ma et al. Synthesis, structures and properties of ternary rare earth complexes with m-methoxybenzoic acid and 1, 10-phenanthroline

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