CN100584893C - A kind of azo-dyes congo layered hydrotalcite and preparation method thereof - Google Patents
A kind of azo-dyes congo layered hydrotalcite and preparation method thereof Download PDFInfo
- Publication number
- CN100584893C CN100584893C CN200810113104A CN200810113104A CN100584893C CN 100584893 C CN100584893 C CN 100584893C CN 200810113104 A CN200810113104 A CN 200810113104A CN 200810113104 A CN200810113104 A CN 200810113104A CN 100584893 C CN100584893 C CN 100584893C
- Authority
- CN
- China
- Prior art keywords
- hydrotalcite
- congo red
- azoic dyestuff
- intercalation
- congo
- 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
Abstract
A kind of azo-dyes congo layered hydrotalcite and preparation method thereof.Its chemical formula is: [(M
2+)
1-x(M
3+)
x(OH)
2]
X+(C
32H
22N
6O
6S
2 2-)
bMH
2O.At first adopting nucleation/crystallization isolation method to prepare interlayer anion is NO
3 -Perhaps Cl
-The hydrotalcite precursor, then the Congo red negatively charged ion of azoic dyestuff is replaced interlayer anion through the hydro-thermal ion exchange method and enters hydrotalcite layers, constitute the anionic supramolecule stratified material of the Congo red anion intercalation hydrotalcite of azoic dyestuff.The preparation method is: adopt nucleation/crystallization isolation method to prepare the hydrotalcite precursor earlier, carry out the hydro-thermal ion exchange reaction with Congo red solution then in reactor, obtain the hydrotalcite composite material of the Congo red dianion intercalation of azoic dyestuff.Advantage is: the azoic dyestuff negatively charged ion that ionic radius is bigger is successfully introduced hydrotalcite layers, and the photo and thermal stability of intercalation product has all had significant raising.
Description
Technical field
The invention belongs to the azoic dyestuff technical field, it is characterized in that providing a kind of azoic dyestuff Congo red (C
32H
22N
6Na
2O
6S
2) intercalated houghite and preparation method thereof.
Background technology
Azoic dyestuff is a kind of dyestuff that has one or more azo bond in the molecule, this class dyestuff be with arylamine in acidic medium, make amino generation diazotization reaction on the arylamine with Sodium Nitrite, form with suitable arylamine or phenols generation coupling reaction then.In synthetic dyestuff, azoic dyestuff is the maximum dye of kind quantity, accounts for 60% of whole world dye species, comprised acidity, alkalescence, ice dyeing, directly, dispersion, activity, media, solvent dye and pigment dyestuff etc.; Azoic dyestuff also is most widely used a kind of dyestuff simultaneously.But, because the azo group that has easy participation oxidation and reduction reaction in the azoic dyestuff molecule, the reaction of azo bond fracture takes place under ambient conditionss such as illumination, high temperature easily, destroy the conjugated system in the molecular structure of dye, thereby cause chromophoric group to decompose, influence the dyefastness of dyestuff on fiber.
Congo red (Congo Red, be called for short CR) is one of synthetic azoic dyestuff the earliest, contains two azo bond in its molecule.The Congo red printing dye that both can be used as also can be used as acid base indicator; Nearest achievement in research shows, the Congo red dyestuff that also can be used as in the medical experiment can stop some abnormal proteins of brain to gather, control " huntington's chorea ".By to Congo red research and application, it is found that the Congo red shortcoming that relatively poor, the easy decolouring of photo and thermal stability is faded that also exists when the printing dye, therefore we find a kind of method to improve its photo and thermal stability at expectation, to expand Congo red Application Areas.
The bimetal complex hydroxide claims hydrotalcite (Layered Double Hydroxides again, be abbreviated as LDHs) be a kind of novel multifunctional stratified material, its chemical stability is good, has stronger heat resistanceheat resistant performance, but and LDHs laminate metal ion modulation, interlayer anion has interchangeability, and multiple functional negatively charged ion all can be introduced interlayer by ion exchange method, obtains various functional composite materials.Therefore, can attempt Congo red anion intercalated its interlayer that enters of azoic dyestuff is utilized the space confinement effect of hydrotalcite laminate and the interaction between the Subjective and Objective, improve the Congo red photo and thermal stability of azoic dyestuff with hydrotalcite as template.
Summary of the invention
The object of the present invention is to provide a kind of azo-dyes congo layered hydrotalcite and preparation method thereof, obtain azoic dyestuff/hydrotalcite composite material that a kind of photo and thermal stability improves, with solve at present Congo red as printing dye in the restriction aspect the dyefastness.
Azo dye intercalation hydrotalcite of the present invention; can be by the space confinement effect of interlayer and the host-guest interaction between interlayer azoic dyestuff negatively charged ion and the laminate; conjugated system chromophoric group in the protection azoic dyestuff molecule, thereby the photo and thermal stability of raising azoic dyestuff.
The chemical formula of this azo dye intercalation hydrotalcite is: [(M
2+)
1-x(M
3+)
x(OH)
2]
X+(C
32H
22N
6O
6S
2 2-)
bMH
2O; M
2+Be divalent metal, M
3+Be trivalent metal cation.Described divalent metal is Mg
2+, Zn
2+, Ni
2+Any, trivalent metal cation is Al
3+, Fe
3+Any.X is M
3+/ (M
2++ M
3+) molar ratio, span is 0.2≤x≤0.33.M is the quantity of crystal water, and span is 0≤m≤2; B is x/2.At first adopting nucleation/crystallization isolation method to prepare interlayer anion is NO
3 -Perhaps Cl
-The hydrotalcite precursor, then the Congo red negatively charged ion of azoic dyestuff is replaced interlayer anion through the hydro-thermal ion exchange method and enters hydrotalcite layers, obtain the anionic supramolecule stratified material of the Congo red anion intercalation hydrotalcite of azoic dyestuff.This material can make full use of the space confinement effect of its interlayer and the interaction between the Subjective and Objective, improves the photo and thermal stability of azoic dyestuff.The decomposition temperature of interlayer object 500 ℃ before by intercalation are brought up to 521 ℃, and thermostability improves.
The preparation process of azo-dyes congo layered hydrotalcite of the present invention is as follows:
A. adopt nucleation/crystallization isolation method, preparation laminate divalence, trivalent metal cation mol ratio are M
2+/ M
3+=2.0～4.0, interlayer anion is NO
3 -Perhaps Cl
-The hydrotalcite precursor, and the hydrotalcite precursor added take off CO
2Deionized water in, fully concussion is stirred in ultrasonic generator, makes slurries;
B. CO is taken off in the Congo red adding of azoic dyestuff
2Deionized water in, fully stir and make its dissolving, obtain containing the Congo red anionic solution of azoic dyestuff;
C. Congo red according to azoic dyestuff, hydrotalcite precursor mol ratio is 1.2～5.0, the hydrotalcite slurries of step a preparation, the Congo red anion solutions of azoic dyestuff of step b preparation are placed reactor jointly, carry out ion exchange reaction 2～16h under 100～150 ℃, product is with taking off CO
2Deionized water thorough washing centrifugation 3～4 times, can obtain azo-dyes congo layered hydrotalcite behind 40～60 ℃ of oven dryings.
With above-mentioned prepared material:
Prove that by XRD, FT-IR, elemental analysis azoic dyestuff is Congo red in the success of hydrotalcite layers intercalation.The matrix material interlamellar spacing of XRD data presentation behind azo dye intercalation increases, and its unit cell parameters a value remains unchanged in the intercalation front and back, has complete laminate structure; TG-DTA characterizes the thermostability that shows this matrix material certain raising; Ultraviolet light and aging experiment shows that this matrix material light stability has had and significantly improves.
The technology of nucleation of the present invention/crystallization isolation method takes by weighing the soluble salt that contains the laminate metal ion for being 2 according to laminate divalence, trivalent metal cation mol ratio, is dissolved in and takes off CO
2Deionized water in obtain mixed salt solution; According to hydroxide ion, metallic cation mol ratio is 1.9, and the weighing sodium hydroxide solid is dissolved in and takes off CO
2Deionized water in obtain alkaline solution; Metal salt solution is injected full back-mixing rotation liquid film reactor with alkaline solution with identical speed mix, violent circulation was stirred 2 minutes, placed reactor at 100 ℃ of following crystallization certain hours in slurries, and product is with taking off CO
2Deionized water thorough washing centrifugation 3～4 times; Behind 60 ℃ of dry 24h, obtain the required hydrotalcite precursor of intercalation.
The invention has the advantages that: by the hydro-thermal ion exchange method, the introducing hydrotalcite layers of the azoic dyestuff negatively charged ion success that ionic radius is bigger; Utilize the space confinement effect of hydrotalcite stratified material and the interaction between the Subjective and Objective, the chromophoric group between protective layer in the Congo red negatively charged ion realizes that hydrotalcite is fast light to azoic dyestuff, the raising of heat-resistant stability.
Description of drawings
Fig. 1 is the hydrotalcite precursor that obtains under the specific embodiment of the invention condition and the XRD spectra of intercalation product; X-coordinate is 2 θ, unit: degree; Ordinate zou is an intensity.Wherein, a is ZnAl-NO
3-LDHs; B is ZnAl-CR-LDHs.
Fig. 2 is the intercalation product that obtains under the specific embodiment of the invention condition and the pure Congo red variation of value of chromatism under the ultra violet lamp different time; X-coordinate is the time, unit: minute; Ordinate zou is aberration Δ E.Wherein, a is CR; B is ZnAl-CR-LDHs.
Embodiment:
[embodiment 1]
Steps A: take by weighing 71.39g Zn (NO
3)
26H
2O and 45.02g Al (NO
3)
39H
2O is dissolved in 200ml and takes off CO
2Deionized water in be mixed with mixing salt solution, other gets 27.36gNaOH and is dissolved in 200ml and takes off CO
2Deionized water in be mixed with alkaline solution.The solution for preparing is become mixing rapidly in the nuclear reactor at full back-mixing rotation liquid film, and violent circulation was stirred after 2 minutes, placed reactor at 100 ℃ of following crystallization 14h in the gained slurries.With taking off CO
2Deionized water thorough washing crystallization product to pH＜8.0; Keep a large amount of fresh filter cakes in order to ion-exchange usefulness, only take out small amount of sample and characterize behind the dry 24h down, obtain ZnAl-NO at 60 ℃
3-LDHs precursor, its Zn
2+/ Al
3+=2.
Step B:, hydrotalcite precursor mol ratio Congo red according to azoic dyestuff is 2, takes by weighing the Congo red 40ml of being dissolved in of 3.48g earlier and takes off CO
2Deionized water in; Taking by weighing filter cake that 4.06g makes by steps A again is dissolved in 60ml and takes off CO
2Deionized water in, concussion makes it abundant dispersion in ultrasonic generator; Two kinds of solution are placed reactor, at 120 ℃ of following ion-exchange 12h; Product spends CO
2Deionized water wash centrifugation 3～4 times, will be deposited in 60 ℃ of dry 24h down, can obtain Congo red anion intercalated stratified composite.
Step C: get Congo red respectively and the intercalation product, in mould, be pressed into the uniform thin slice of thickness, under the 500W ultraviolet lamp, shine 5,10,15,20,25min, measure value of chromatism Δ E with colour examining colour-difference-metre, color rendering difference DELTA E is to the change curve of UV-irradiation time.
By XRD figure as can be known, Congo red negatively charged ion is after hydro-thermal ion-exchange enters the LDHs interlayer, and its laminate spacing increases to 2.64nm by the 0.89nm of precursor, proves Congo red anion intercalated success; Near 2 θ were 61 °, two kinds of LDHs had the obvious diffraction peak, and corresponding unit cell parameters a is approximately 0.30nm, illustrates that the laminate electric density of Congo red anion intercalated front and back LDHs does not change, and the LDHs laminate obtains more complete maintenance.The FT-IR spectrogram shows that the intercalation product is at 1044cm
-1, 1113cm
-1, 1173cm
-1Congo red characteristic peak occurs at the place, also proved Congo red anion intercalated success.By thermogravimetric analysis as can be known, the heat decomposition temperature of interlayer object 500 ℃ before by intercalation are brought up to 521 ℃ in the matrix material, illustrate that its thermostability improves.By the variation of value of chromatism as can be known, pure Congo red behind UV-irradiation 5min value of chromatism be 1.25, along with the prolongation of irradiation time, value of chromatism has bigger increase; And that the value of chromatism of matrix material is about is pure Congo red about 30%, changes the amplitude that increases in time also less than pure Congo red, illustrates that its light stability has had significant raising.
[embodiment 2]
Steps A: take by weighing 46.15g Mg (NO
3)
26H
2O and 33.76g Al (NO
3)
39H
2O is dissolved in 150ml and takes off CO
2Deionized water in be mixed with mixing salt solution, other gets 21.60gNaOH and is dissolved in 150ml and takes off CO
2Deionized water in be mixed with alkaline solution.The solution for preparing is become mixing rapidly in the nuclear reactor at full back-mixing rotation liquid film, and violent circulation was stirred after 2 minutes, placed reactor at 100 ℃ of following crystallization 4h in the gained slurries.With taking off CO
2Deionized water thorough washing crystallization product to pH＜8.0; Keep a large amount of fresh filter cakes in order to ion-exchange usefulness, only take out small amount of sample and characterize behind the dry 24h down, obtain MgAl-NO at 60 ℃
3-LDHs precursor, its Mg
2+/ Al
3+=2.
Step B:, hydrotalcite precursor mol ratio Congo red according to azoic dyestuff is 2, takes by weighing the Congo red 40ml of being dissolved in of 3.48g earlier and takes off CO
2Deionized water in; Taking by weighing filter cake that 5.12g makes by steps A again is dissolved in 60ml and takes off CO
2Deionized water in, concussion makes it abundant dispersion in ultrasonic generator; Two kinds of solution are placed reactor, at 120 ℃ of following ion-exchange 12h; Product is with taking off CO
2Deionized water wash centrifugation 3～4 times, will be deposited in 60 ℃ of dry 24h down, can obtain Congo red anion intercalated stratified composite.
Step C: take step C method in the similar embodiment 1, respectively Congo red and intercalation product are shone different time under ultraviolet lamp, carry out the light stability test, obtain the light stability curve.
By XRD figure as can be known, Congo red negatively charged ion is after ion-exchange enters the LDHs interlayer, and its laminate spacing has the 0.87nm of precursor to increase to 2.62nm, proves Congo red anion intercalated success; Near 2 θ were 61 °, two kinds of LDHs had the obvious diffraction peak, and corresponding unit cell parameters a is approximately 0.30nm, illustrates that the laminate electric density of Congo red anion intercalated front and back LDHs does not change, and the LDHs laminate obtains more complete maintenance.The FT-IR spectrogram shows that the intercalation product is at 1044cm
-1, 1113cm
-1, 1173cm
-1Congo red characteristic peak occurs at the place, also proved Congo red anion intercalated success.By thermogravimetric analysis as can be known, the heat decomposition temperature of interlayer object 500 ℃ before by intercalation are brought up to 512 ℃ in the matrix material, illustrate that its thermostability improves.By the variation of value of chromatism as can be known, pure Congo red behind UV-irradiation 5min value of chromatism be 1.81, and along with the prolongation of irradiation time, value of chromatism has bigger increase; And that the value of chromatism of matrix material is about is pure Congo red about 40%, illustrates that its light stability has had significant raising.
Claims (3)
1. an azo-dyes congo layered hydrotalcite is characterized in that, chemical formula is: [(M
2+)
1-x(M
3+)
x(OH)
2]
X+(C
32H
22N
6O
6S
2 2-)
bMH
2O; M
2+Be divalent metal, M
3+Be trivalent metal cation, x is M
3+/ (M
2++ M
3+) molar ratio, its span is 0.2≤x≤0.33, m is the quantity of crystal water, its span is 0≤m≤2, b is x/2; Adopting nucleation/crystallization isolation method to prepare interlayer anion is NO
3 -Perhaps Cl
-The hydrotalcite precursor; By the Congo red the moon of the hydro-thermal ion exchange method azoic dyestuff that ionic radius is bigger, the ionic replacement interlayer anion enters hydrotalcite layers, constitutes the anionic supramolecule stratified material of the Congo red anion intercalation hydrotalcite of azoic dyestuff; This material can make full use of the space confinement effect of its interlayer and the interaction between the Subjective and Objective, improves the photo and thermal stability of azoic dyestuff;
Described divalent metal is Mg
2+, Zn
2+In any, trivalent metal cation is Al
3+
2, a kind of method for preparing the described azo-dyes congo layered hydrotalcite of claim 1 is characterized in that, preparation process is:
A. adopting nucleation/crystallization isolation method to prepare interlayer anion is NO
3 -Perhaps Cl
-, laminate divalence, trivalent metal cation mol ratio M
2+/ M
3+=2.0～4.0 hydrotalcite precursor;
B. Congo red the joining of azoic dyestuff taken off CO
2Deionized water in, stir and to make its dissolving, thereby obtain containing the Congo red anionic solution of azoic dyestuff;
C. Congo red according to azoic dyestuff, hydrotalcite precursor mol ratio is 1.2～5.0, and both solution are placed reactor, carries out hydro-thermal ion exchange reaction 2～16h at 100～150 ℃, and product is with taking off CO
2Deionized water thorough washing centrifugation 3～4 times; Behind 40～60 ℃ of dry 24h, obtain the azo dye intercalation hydrotalcite, chemical formula is: [(M
2+)
1-x(M
3+)
x(OH)
2]
X+(C
32H
22N
6O
6S
2 2-)
bMH
2O.
3, method according to claim 2 is characterized in that, the technology of nucleation/crystallization isolation method is: according to laminate divalence, trivalent metal cation mol ratio is 2, takes by weighing the soluble salt that contains the laminate metal ion, is dissolved in and takes off CO
2Deionized water in obtain mixed salt solution; According to hydroxide ion, metallic cation mol ratio is 1.9, and the weighing sodium hydroxide solid is dissolved in and takes off CO
2Deionized water in obtain alkaline solution; Metal salt solution is injected full back-mixing rotation liquid film reactor with alkaline solution with identical speed mix, violent circulation was stirred 2 minutes, placed reactor at 100 ℃ of following crystallization certain hours in slurries, and product is with taking off CO
2Deionized water thorough washing centrifugation 3～4 times; Behind 60 ℃ of dry 24h, obtain the required hydrotalcite precursor of intercalation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810113104A CN100584893C (en) | 2008-05-28 | 2008-05-28 | A kind of azo-dyes congo layered hydrotalcite and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810113104A CN100584893C (en) | 2008-05-28 | 2008-05-28 | A kind of azo-dyes congo layered hydrotalcite and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101280119A CN101280119A (en) | 2008-10-08 |
| CN100584893C true CN100584893C (en) | 2010-01-27 |
Family
ID=40012797
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810113104A Expired - Fee Related CN100584893C (en) | 2008-05-28 | 2008-05-28 | A kind of azo-dyes congo layered hydrotalcite and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100584893C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775277B (en) * | 2009-12-31 | 2012-07-11 | 北京化工大学 | Photosensitive composite film and preparation method thereof |
| CN101864293B (en) * | 2010-06-02 | 2013-01-16 | 北京化工大学 | Sulfonated cyanine dyes/hydrotalcite composite film and preparation method thereof |
| CN103319913A (en) * | 2013-06-18 | 2013-09-25 | 安科智慧城市技术（中国）有限公司 | Preparation method of dye intercalation hydrotalcite-like nanometer composite material |
| CN112300404B (en) * | 2020-11-02 | 2022-06-28 | 北京化工大学 | Preparation method of active supramolecular polymer based on layered double-hydroxide bionic confinement driving |
| CN115873008A (en) * | 2023-03-01 | 2023-03-31 | 中化学科学技术研究有限公司 | Method for purifying isosorbide and purified isosorbide |
-
2008
- 2008-05-28 CN CN200810113104A patent/CN100584893C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101280119A (en) | 2008-10-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100584893C (en) | A kind of azo-dyes congo layered hydrotalcite and preparation method thereof | |
| CN105732728B (en) | Metal organic framework complex nanometer sheet, preparation method and its usage | |
| CN105749903B (en) | MgZnCr-TiO2Houghite visible light catalyst and its preparation method and application | |
| CN106910874B (en) | A kind of surface cladding Li2TiO3With the high-nickel material and preparation method of surface layer doping Ti | |
| CN103771544B (en) | Preparation method of hollow cobaltosic oxide microsphere | |
| CN105778906A (en) | Method for synthesizing metallic element in-situ doped fluorescence carbon dots deriving from chitosan biomass | |
| CN103627214A (en) | Temperature-resistant iron oxide yellow pigment with flame retardant function and preparation method thereof | |
| CN108393073A (en) | A kind of preparation method of general magnetic adsorbent and application | |
| CN108609599A (en) | The preparation method of nickel hydroxide nano piece self assembly nickel phosphates cobalt club shaped structure composite material | |
| CN101982509A (en) | Acid yellow 17 intercalation pigment with light stability, thermal stability and supramolecular structure and preparation method thereof | |
| CN106040291A (en) | Preparation method and application for nuclearshell material catalyst | |
| CN100363431C (en) | Conductive polymer-intercalated hydrotalcite and method for preparing same | |
| CN102618074B (en) | Thermal stabilization type ponceau 2R intercalation hydrotalcite dye and preparation method thereof | |
| CN102240540A (en) | Flaky gallium-containing nano photocatalyst and use thereof in light degradation of organic pollutants | |
| CN110217825B (en) | Preparation method of high-nuclear manganese metal cluster | |
| Kalapsazova et al. | Oxygen-storage materials to stabilize the oxygen redox activity of three-layered sodium transition metal oxides | |
| WO2020052656A1 (en) | Lake pigment preparation method, lake pigment and application thereof | |
| CN104017557A (en) | Preparation method and application of diphenylamine sulfonate intercalated hydrotalcite material | |
| CN102107880A (en) | Method for preparing zeolite 4A | |
| CN106423178B (en) | A kind of Er ions cobalt acid zinc photochemical catalyst raw powder's production technology and application | |
| CN104556728A (en) | Method for preparing aluminum-doped nickel oxide electrochromic film by virtue of hydrotalcite precursor pyrolysis | |
| CN100569865C (en) | A kind of Photothermic stabilization type acidic intermedium dark yellow GG intercalation pigment and preparation method thereof | |
| CN102491416A (en) | Method for preparing Eu2Zr207 nanometer powder | |
| Rezvani et al. | Intercalation of Mordant orange 1 into ZnAl-layered double hydroxide and its dual-color photoluminescence emission | |
| CN1601785A (en) | Method of prepn, of positive electrode laminated cell lithium manganate of lithium ion |
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: 20100127 Termination date: 20100528 |