CN100569865C - A kind of Photothermic stabilization type acidic intermedium dark yellow GG intercalation pigment and preparation method thereof - Google Patents
A kind of Photothermic stabilization type acidic intermedium dark yellow GG intercalation pigment and preparation method thereof Download PDFInfo
- Publication number
- CN100569865C CN100569865C CNB2007101770460A CN200710177046A CN100569865C CN 100569865 C CN100569865 C CN 100569865C CN B2007101770460 A CNB2007101770460 A CN B2007101770460A CN 200710177046 A CN200710177046 A CN 200710177046A CN 100569865 C CN100569865 C CN 100569865C
- Authority
- CN
- China
- Prior art keywords
- hsab
- hydrotalcite
- acid
- ldhs
- preparation
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention provides a kind of Photothermic stabilization type acidic intermedium dark yellow GG supramolecular structure intercalation pigment and preparation method thereof.The present invention utilizes the intercalation of hydrotalcite, is NO with the interlayer anion
3 -Hydrotalcite [M
2+ 1-xM
3+ x(OH)
2] (NO
3 -)
xMH
2O adopts ion exchange method that the negatively charged ion of Acid Chrome Deep Yellow GG (being abbreviated as HSAB) is inserted into hydrotalcite layers, obtains intercalated houghite LDHs-HSAB.LDHs-HSAB compares with Acid Chrome Deep Yellow GG, and its photostabilization and thermotolerance all are greatly improved.Therefore replace Acid Chrome Deep Yellow GG to be used for polymer composite with LDHs-HSAB and can slow down the degree of fading and the speed that it in use causes because of illumination.
Description
Affiliated field
The present invention relates to a kind of Photothermic stabilization type acidic intermedium dark yellow GG intercalation pigment and preparation method thereof.
Background technology
Acid Chrome Deep Yellow GG (2-hydroxy-5-(4-sulfophenyl azo)-benzoate disodium is abbreviated as HSAB) is a kind of deep yellow dyestuff, is widely used in fields such as textile dyeing and macromolecule polymeric material be painted.Though HSAB color developing and light stability are better, its thermostability is relatively poor, fades easily in matrix material processing and use, thereby has limited its range of application, has reduced application performance.Therefore fast light, the resistance toheat that improve Acid Chrome Deep Yellow GG have crucial meaning.
Hydrotalcite (Layered Double Hydroxides, be abbreviated as LDHs) be a kind of anionic type laminated material, because but it has the performance of intercalation assembling, thereby utilize this performance some function species can be inserted into hydrotalcite layers, the supermolecular intercalation structure material that preparation has specific function.
Document Mohd Zobir bin Hussein, Zulkarnain Zainal, Asmah Hj.Yahaya, Azira bintiAbd.Aziz, Materials science and Engineering B88,2002,98-102. with the aqueous solution of matching stain naphthol blue black 10B with contain Mg
2+And Al
3+Aqueous solution, adjust the pH=10 of reaction system, obtaining interlayer is the anionic intercalated houghite of naphthol blue black 10B, this intercalation method is a coprecipitation method.Can the purpose of its research just obtains a kind of inorganic-organic nanocomposite, do not investigate product and use as a kind of novel pigment.
Document Umberto Costanino, Natascia Coletti, and Morena Nocchetti, Langmuir, 1999, among the 15:4454-4460, adopt the urea thermal synthesis method to obtain hydrotalcite [Zn earlier
0.67Al
0.33(OH)
2] [CO
3]
0.1650.4H
2O obtains hydrotalcite Zn with itself and NaCl and HCl reaction again
0.67Al
0.33(OH)
2Cl
0.330.4H
2O is again with Zn
0.67Al
0.33(OH)
2Cl
0.330.4H
2O is a precursor, and tropeolin-D (MO) is object, and assembling obtains intercalated houghite [Zn
0.67Al
0.33(OH)
2] [MO
0.31Cl
0.02] 0.85H
2O, they have investigated the fluorescence of product.Its shortcoming is a precursor preparation method complexity.
Summary of the invention
(be abbreviated as: LDHs-HSAB), another object of the present invention provides the preparation method of this intercalation pigment LDHs-HSAB to the purpose of this invention is to provide a kind of Photothermic stabilization type acidic intermedium dark yellow GG intercalation pigment.
The present invention is NO with the interlayer anion
3 -Houghite be precursor, adopt ion exchange method to make the negatively charged ion of Acid Chrome Deep Yellow GG replace the NO of hydrotalcite layers
3 -Ion, generating interlayer anion is the anionic intercalated houghite of Acid Chrome Deep Yellow GG (LDHs-HSAB).
The chemical general formula of the Photothermic stabilization type acidic intermedium dark yellow GG intercalation pigment LDHs-HSAB of the present invention's preparation is:
[M
2+ 1-xM
3+ x(OH)
2](HSAB)
x/2·mH
2O
0.2＜x/ (1-x)＜0.5 wherein, m is an interlayer crystal water molecule number; M
2+Be divalent-metal ion Mg
2+, Zn
2+, Ni
2+, Fe
2+Or Cu
2+In any one, preferably Mg
2+Or Zn
2+M
3+Be trivalent metal ion Al
3+, Co
3+, Ti
3+, Fe
3+Or Cr
3+In any one, preferably Al
3+By changing M
2+With M
3+Mol ratio can regulate the anionic amount of Acid Chrome Deep Yellow GG of inserting hydrotalcite layers, can obtain a series of different LDHs-HSAB that form.LDHs-HSAB can be used as pigment and is used for macromolecule polymeric material, because the provide protection of hydrotalcite laminate, this pigment has than the better light of Acid Chrome Deep Yellow GG, thermal stability.
The preparation process of LDHs-HSAB is as follows:
A. be NO with interlayer anion
3 -The hydrotalcite precursor join in organic solvent ethylene glycol, ethylene glycol butyl ether or the diethyl carbitol, the room temperature lower magnetic force stirs, the hydrotalcite suspension that is mixed with concentration and is 0.05～0.1M is standby;
Interlayer anion is NO
3 -The hydrotalcite structure formula should satisfy: [M
2+ 1-xM
3+ x(OH)
2] (NO
3 -)
xMH
2O, 0.2＜x/ (1-x)＜0.5 wherein, m is an interlayer crystal water molecule number; M
2+Be divalent-metal ion Mg
2+, Zn
2+, Ni
2+, Cd
2+, Fe
2+Or Cu
2+In any one, preferably Mg
2+Or Zn
2+M
3+Be trivalent metal ion Al
3+, Co
3+, Ti
3+, Fe
3+Or Cr
3+In any one, preferably Al
3+
B. HSAB is dissolved in the deionized water, dripping dilute nitric acid solution separates out to no longer including precipitation, precipitate and separate, washing and oven dry are promptly got acid HSAB acid, acid HSAB acid is dissolved in the organic solvent identical with steps A, make its concentration be controlled at 0.075～0.2M; And be adjusted to pH=6～9 with dilute NaOH solution;
C. with the HSAB solution of step B preparation and the hydrotalcite suspension of steps A preparation; mol ratio sour according to HSAB and hydrotalcite is 1.5～4 ratio thorough mixing; and be adjusted to pH=8～11 with dilute NaOH solution; under 90～120 ℃ and nitrogen protection, reacted 12～72 hours; filter, wash colourless to washing lotion; 70～150 ℃ of dryings 6～24 hours, obtain the anion intercalated hydrotalcite LDHs-HSAB of Acid Chrome Deep Yellow GG.
The LDHs-HSAB that obtains is carried out XRD, FT-IR, UV-Vis and TG-DTA etc. characterize demonstration, the Acid Chrome Deep Yellow GG negatively charged ion has been assembled into stratified material LDHs interlayer.
Be placed on intercalation pigment LDHs-HSAB, HSAB powder in the baking oven respectively, respectively at temperature is that 100,150,200,250 and 300 ℃ of maintenances were taken out after 30 minutes, with the UV-Vis spectrophotometer its thermotolerance is analyzed, the results are shown in Figure 1, LDHs-HSAB has higher thermostability than Acid Chrome Deep Yellow GG as can be known.
HSAB and LDHs-HSAB place simultaneously power be shine 5,10,15,20,25,30,35,40,45 and 50 minutes respectively under 1000 watts the ultraviolet lamp after, measure its aberration Δ E size with color measurement instrument, the results are shown in Figure 2, show that by Fig. 2 the light stability of intercalation pigment LDHs-HSAB is higher than Acid Chrome Deep Yellow GG.
This intercalation pigment LDHs-HSAB can be used in the macromolecule polymeric material, HSAB/PE (a) and LDHs-HSAB/PE (b) have been measured respectively at aberration after the different photoaging time and the aberration after aging half an hour under the differing temps, the results are shown in Figure 3, Fig. 4, by Fig. 3,4 as can be seen LDHs-HSAB have better photo and thermal stability than HSAB.
Remarkable advantage: the prepared intercalated houghite LDH-HSAB of the present invention can be used as pigment and uses, and the light of this novel pigment, thermostability are compared with Acid Chrome Deep Yellow GG and are had a more substantial increase, and therefore replace Acid Chrome Deep Yellow GG to be used for polymer composite with LDHs-HSAB and can slow down its fade degree and speed.The precursor preparation method that is adopted is easy, after the Acid Chrome Deep Yellow GG acidifying, selects appropriate organic solvent can make the smooth intercalation of Acid Chrome Deep Yellow GG negatively charged ion in hydrotalcite.This LDHs-HSAB pigment also can replace Acid Chrome Deep Yellow GG to be used for polymer composite.
Description of drawings:
Fig. 1 is HSAB (a), HSAB and the ZnAl-NO of embodiment 1
3The UV-Vis curve of-LDHs physical mixture (b) and the different aging temperatures of LDHs-HSAB (c).
Fig. 2 is the aberration after HSAB (a) and LDHs-HSAB (b) different photoaging time of embodiment 1.
Fig. 3 is the aberration after HSAB/PE (a) and LDHs-HSAB/PE (b) different photoaging time of embodiment 1.
Fig. 4 is HSAB/PE (a) and LDHs-HSAB/PE (b) aberration after aging half an hour under differing temps of embodiment 1.
Embodiment:
Embodiment 1:
Steps A: take by weighing 28.80g (0.72mol) NaOH adding 300ml and take off CO
2Deionized water in proportionaling alkali-forming solution; Other takes by weighing 71.39g (0.24mol) Zn (NO
3)
26H
2O and 45.02g (0.12mol) Al (NO
3)
39H
2O is dissolved in 300ml and takes off CO
2Deionized water in be made into mixing salt solution.Two kinds of solution are added in the rotation liquid film reactor fast nucleation simultaneously with identical flow velocity, and crystallization 6h under reflux temperature then, is washed to the pH value less than 8 at centrifuging, obtains ZnAl-NO
3-LDHs filter cake takes by weighing 2.30g (0.005mol) ZnAl-NO
3-LDHs filter cake, fully decentralized system becomes slurries in 50ml ethylene glycol.
Step B: HSAB is dissolved in the deionized water, drips dilute nitric acid solution and separate out to no longer including precipitation.With precipitate and separate, washing, dry Acid Chrome Deep Yellow GG acid, be 2 ratio according to the mol ratio of Acid Chrome Deep Yellow GG acid and hydrotalcite precursor, Acid Chrome Deep Yellow GG acid is dissolved in the 100ml ethylene glycol, be adjusted to pH=7 with the NaOH solution of 0.1M.
Step C: with the Acid Chrome Deep Yellow GG solution of step B preparation and the hydrotalcite suspension thorough mixing of steps A preparation; and be adjusted to pH=10 with the NaOH solution of 0.1M; in temperature is reaction 16 hours under 90 ℃ and the nitrogen protection; filter, wash colourless to washing lotion; 100 ℃ of dryings 24 hours, obtain the anion intercalated hydrotalcite LDHs-HSAB of Acid Chrome Deep Yellow GG.
The LDHs-HSAB that obtains is carried out XRD, FT-IR, UV-Vis and TG-DTA etc. characterize demonstration, the Acid Chrome Deep Yellow GG negatively charged ion has been assembled into stratified material LDHs interlayer; Results of elemental analyses shows that its chemical structural formula is Zn
0.67Al
0.33(OH)
2(HSAB)
0.1650.56H
2O.By (seeing Fig. 1-4) as can be known after the test of this intercalation pigment being carried out light, thermal stability, it is fast light, resistance toheat is all than the height of Acid Chrome Deep Yellow GG.
Embodiment 2:
Steps A: the ZnAl-NO that takes by weighing embodiment 1 preparation
3-LDHs filter cake 2.30g (0.005mol), fully decentralized system becomes slurries in 50ml ethylene glycol.
Step B: with embodiment 1.
Step C: with the Acid Chrome Deep Yellow GG solution of step B preparation and the hydrotalcite suspension thorough mixing of steps A preparation; and be adjusted to pH=9 with the NaOH solution of 0.1M; reaction is 16 hours under 90 ℃ and nitrogen protection; filter, wash colourless to washing lotion; 100 ℃ of dryings 24 hours, obtain the anion intercalated hydrotalcite LDHs-HSAB of Acid Chrome Deep Yellow GG.Results of elemental analyses shows that its chemical structural formula is Zn
0.66Al
0.34(OH)
2(HSAB)
0.170.52H
2O, this intercalation pigment photo and thermal stability of photo and thermal stability test shows are all than the height of Acid Chrome Deep Yellow GG.
Embodiment 3:
Steps A: with embodiment 2.
Step B: with embodiment 1, difference is that the mol ratio of Acid Chrome Deep Yellow GG acid and hydrotalcite precursor is 1.5.
Step C: with the Acid Chrome Deep Yellow GG solution of step B preparation and the hydrotalcite suspension thorough mixing of steps A preparation; and be adjusted to pH=10 with the NaOH solution of 0.1M; reaction is 12 hours under 95 ℃ and nitrogen protection; filter, wash colourless to washing lotion; at 100 ℃ of dry 24h, obtain the anion intercalated hydrotalcite LDHs-HSAB of Acid Chrome Deep Yellow GG.Results of elemental analyses shows that its chemical structural formula is Zn
0.67Al
0.33(OH)
2(HSAB)
0.1650.49H
2O, this intercalation pigment photo and thermal stability of photo and thermal stability test shows are all than the height of Acid Chrome Deep Yellow GG.
Embodiment 4:
Steps A: take by weighing 28.80g (0.72mol) NaOH adding 300ml and take off CO
2Deionized water in proportionaling alkali-forming solution; Other takes by weighing 61.536g (0.24mol) Mg (NO
3)
26H
2O and 45.02g (0.12mol) Al (NO
3)
39H
2O is dissolved in 300ml and takes off CO
2Deionized water in be made into mixing salt solution.Two kinds of solution are added in the rotation liquid film reactor fast nucleation simultaneously with identical flow velocity, and crystallization 6h under reflux temperature then, is washed to the pH value less than 8 at centrifuging, obtains MgAl-NO
3-LDHs filter cake takes by weighing 4.8g (0.005mol) MgAl-NO
3-LDHs filter cake, fully decentralized system becomes slurries in 50ml ethylene glycol.
Step B: with embodiment 1.
Step C: with the Acid Chrome Deep Yellow GG solution of step B preparation and the hydrotalcite suspension thorough mixing of steps A preparation; and be adjusted to pH=9 with the NaOH solution of 0.1M; reaction is 24 hours under 90 ℃ and nitrogen protection; filter, wash colourless to washing lotion; 100 ℃ of dryings 24 hours, obtain the anion intercalated hydrotalcite LDHs-HSAB of Acid Chrome Deep Yellow GG.
The LDHs-HSAB that obtains is carried out XRD, FT-IR, UV-Vis and TG-DTA etc. characterize demonstration, the Acid Chrome Deep Yellow GG negatively charged ion has been assembled into stratified material LDHs interlayer; Results of elemental analyses shows that its chemical structural formula is Mg
0.67Al
0.33(OH)
2(HSAB)
0.1650.48H
2O.By after the test of this intercalation pigment being carried out light, thermal stability as can be known, it is fast light, resistance toheat is all than the height of Acid Chrome Deep Yellow GG.
Embodiment 5:
Steps A: the MgAl-NO that takes by weighing embodiment 4 preparations
3-LDHs filter cake 4.8g (0.005mol), fully decentralized system becomes slurries in 50ml ethylene glycol.
Step B: with embodiment 1, difference is that the mol ratio of Acid Chrome Deep Yellow GG is sour and hydrotalcite precursor is 2.5.
Step C: with the Acid Chrome Deep Yellow GG solution of step B preparation and the hydrotalcite suspension thorough mixing of steps A preparation; and be adjusted to pH=9.5 with the NaOH solution of 0.1M; reaction is 12 hours under 95 ℃ and nitrogen protection; filter, wash colourless to washing lotion; 100 ℃ of dryings 24 hours, obtain the anion intercalated hydrotalcite LDHs-HSAB of Acid Chrome Deep Yellow GG.
Results of elemental analyses shows that its chemical structural formula is Mg
0.66Al
0.34(OH)
2(HSAB)
0.170.52H
2O, this intercalation pigment photo and thermal stability of photo and thermal stability test shows are all than the height of Acid Chrome Deep Yellow GG.
Claims (3)
1. a Photothermic stabilization type acidic intermedium dark yellow GG intercalation pigment is abbreviated as LDHs-HSAB, and its chemical general formula is:
[M
2+ 1-xM
3+ x(OH)
2](HSAB)
x/2·mH
2O
0.2＜x/ (1-x)＜0.5 wherein, m is an interlayer crystal water molecule number; M
2+Be divalent-metal ion Mg
2+, Zn
2+, Ni
2+, Fe
2+Or Gu
2+In any one; M
3+Be trivalent metal ion Al
3+, Co
3+, Ti
3+, Fe
3+Or Cr
3+In any one.
2. Photothermic stabilization type acidic intermedium dark yellow GG intercalation pigment according to claim 1 is characterized in that M
2+Be Mg
2+Or Zn
2+, M
3+Be Al
3+
3. the preparation method of a Photothermic stabilization type acidic intermedium dark yellow GG intercalation pigment as claimed in claim 1, concrete preparation process is as follows:
A. be NO with interlayer anion
3 -The hydrotalcite precursor join in organic solvent ethylene glycol, ethylene glycol butyl ether or the diethyl carbitol, the room temperature lower magnetic force stirs, the hydrotalcite suspension that is mixed with concentration and is 0.05～0.1M is standby;
Described interlayer anion is NO
3 -Hydrotalcite, its structural formula should satisfy: [M
2+ 1-xM
3+ x(OH)
2] (NO
3 -)
x -MH
2O, 0.2＜x/ (1-x)＜0.5 wherein, m is an interlayer crystal water molecule number; M
2+Be divalent-metal ion Mg
2+, Zn
2+, Ni
2+, Cd
2+, Fe
2+Or Cu
2+In any one, M
3+Be trivalent metal ion Al
3+, Co
3+, Ti
3+, Fe
3+Or Cr
3+In any one;
B. with Acid Chrome Deep Yellow GG, be abbreviated as HSAB, be dissolved in the deionized water, dripping dilute nitric acid solution separates out to no longer including precipitation, precipitate and separate, washing and oven dry are promptly got acid HSAB acid, acid HSAB acid is dissolved in the organic solvent identical with steps A, makes its concentration be controlled at 0.075～0.2M; And be adjusted to pH=6～9 with dilute NaOH solution;
C. with the HSAB solution of step B preparation and the hydrotalcite suspension of steps A preparation; mol ratio sour according to HSAB and hydrotalcite is 1.5～4 ratio thorough mixing; and be adjusted to pH=8～11 with dilute NaOH solution; under 90～120 ℃ and nitrogen protection, reacted 12～72 hours; filter, wash colourless to washing lotion; 70～150 ℃ of dryings 6～24 hours, obtain the anion intercalated hydrotalcite LDHs-HSAB of Acid Chrome Deep Yellow GG.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101770460A CN100569865C (en) | 2007-11-09 | 2007-11-09 | A kind of Photothermic stabilization type acidic intermedium dark yellow GG intercalation pigment and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101770460A CN100569865C (en) | 2007-11-09 | 2007-11-09 | A kind of Photothermic stabilization type acidic intermedium dark yellow GG intercalation pigment and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101186760A CN101186760A (en) | 2008-05-28 |
| CN100569865C true CN100569865C (en) | 2009-12-16 |
Family
ID=39479389
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007101770460A Expired - Fee Related CN100569865C (en) | 2007-11-09 | 2007-11-09 | A kind of Photothermic stabilization type acidic intermedium dark yellow GG intercalation pigment and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100569865C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101982509A (en) * | 2010-10-08 | 2011-03-02 | 北京化工大学 | Acid yellow 17 intercalation pigment with light stability, thermal stability and supramolecular structure and preparation method thereof |
| CN102618074B (en) * | 2012-02-24 | 2014-12-03 | 山东大学 | Thermal stabilization type ponceau 2R intercalation hydrotalcite dye and preparation method thereof |
| CN103450704B (en) * | 2013-08-01 | 2016-03-16 | 安徽省安邦矿物有限公司 | The synthetic method of a kind of attapulgite/dihydroxyphenyl propane hybrid pigment |
| CN106693945B (en) * | 2016-11-29 | 2019-10-18 | 北京化工大学 | Delamination hydrotalcite nano piece based composite catalyst and preparation method thereof |
-
2007
- 2007-11-09 CN CNB2007101770460A patent/CN100569865C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 超分子插层结构光热稳定型颜料的制备及其性能研究. 张伟锋.中国优秀博硕士学位论文全文数据库（硕士） 工程科技Ⅰ辑，第1期. 2005 |
| 超分子插层结构光热稳定型颜料的制备及其性能研究. 张伟锋.中国优秀博硕士学位论文全文数据库（硕士） 工程科技Ⅰ辑，第1期. 2005 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101186760A (en) | 2008-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Durupthy et al. | Influence of pH and ionic strength on vanadium (V) oxides formation. From V 2 O 5· n H 2 O gels to crystalline NaV 3 O 8· 1.5 H 2 O | |
| CN108998007B (en) | Preparation method of rare earth metal organic framework material | |
| CN103965654B (en) | A kind of supermolecular intercalation structure of resistance to light type pigment and preparation method thereof | |
| CN100569865C (en) | A kind of Photothermic stabilization type acidic intermedium dark yellow GG intercalation pigment and preparation method thereof | |
| CN106040291B (en) | A kind of preparation method and applications of core-shell material catalyst | |
| CN109970990B (en) | Terbium coordination polymer and preparation method and application thereof | |
| CN110218333B (en) | Pyridine methylene phosphonic acid nickel coordination polymer and preparation method and application thereof | |
| CN101982509A (en) | Acid yellow 17 intercalation pigment with light stability, thermal stability and supramolecular structure and preparation method thereof | |
| Wang et al. | Four coordination polymers based on 5-(3, 5-dicarboxybenzyloxy) isophthalic acid: Synthesis, structures, photocatalytic properties, fluorescence sensing and magnetic properties | |
| CN102732055A (en) | Multi-component chromogenic anion co-intercalation supramolecular structure pigment and preparation method thereof | |
| CN106831830B (en) | A kind of supermolecule cage complex and its preparation method and application | |
| Lin et al. | An ultrastable {SiNb18O54}-based hybrid polyoxoniobate framework for selective removal of crystal violet from aqueous solution and proton-conduction | |
| CN103421030B (en) | As the binary aromatic acid cerium complexes and preparation method thereof of cadmium ion fluorescent probe | |
| CN103359791B (en) | A kind of vanadic acid-chrome molybdenum acid mixed cluster polyacid compound structure and preparation method | |
| Chai et al. | Syntheses, structures of three Ln-MOFs (Ln= La, Ce, Dy), fluorescent sensing Fe3+ and MnO4− of La-MOF film, and magnetic properties of Dy-MOF | |
| CN107501565B (en) | Rare earth metal-organic framework material Ho-MOF and preparation method and application thereof | |
| CN108914207A (en) | A kind of metal organic framework crystal functional material and its preparation method and application | |
| CN110551291B (en) | Porous interpenetrating zinc-organic supramolecular polymer and preparation method and application thereof | |
| Li et al. | A multifunctional Eu-MOF with multi-color and proton conduction switching and its anti-counterfeiting applications | |
| CN103588809B (en) | Preparation method of two types of metal-organic frame materials containing Pb ions | |
| CN104789206B (en) | A kind of low-temp reversible thermochromic material and its production and use | |
| Majid et al. | Synthesis, characterization and coordinating behaviour of aminoalcohol complexes with transition metals | |
| CN101240164B (en) | Method for synthesizing sensitive photochromic WO3 nano powder by formaldehyde inducement | |
| CN109054036A (en) | Sandwich type manganese coordination polymer, preparation method and its application in cation detection of blue-green fluorescent | |
| CN111116929B (en) | Nickel coordination polymer material with wide-temperature-zone reversible thermochromic property and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20091216 Termination date: 20121109 |