CN106497550A - 3 hydroxyl, 2 naphthoic acid/1 perfluoroetane sulfonic acid/LYH complexs and its synthetic method - Google Patents
3 hydroxyl, 2 naphthoic acid/1 perfluoroetane sulfonic acid/LYH complexs and its synthetic method Download PDFInfo
- Publication number
- CN106497550A CN106497550A CN201610921966.8A CN201610921966A CN106497550A CN 106497550 A CN106497550 A CN 106497550A CN 201610921966 A CN201610921966 A CN 201610921966A CN 106497550 A CN106497550 A CN 106497550A
- Authority
- CN
- China
- Prior art keywords
- lyh
- hydroxy
- naphthoic
- complex
- sodium
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7701—Chalogenides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
Abstract
The embodiment of the invention discloses a kind of 2 naphthoic acid/1 perfluoroetane sulfonic acid of 3 hydroxyl/LYH complexs and its synthetic method, 3 hydroxyl, the 2 naphthoic acid/1 perfluoroetane sulfonic acid/LYH complexs, constitute with below formula：Y(OH)2.5(C11H7O3)x(C8H17O3S)y·zH2O, wherein, X=0.07 0.13, y=0.36 0.37, z=1 2.By NO in this programme3LYH is combined with 3 hydroxyl, 2 naphthoic acid (i.e. 3 hydroxyl, 2 naphthoic acid radical ion) and 1 perfluoroetane sulfonic acid radical ion of deprotonation, obtain 3 hydroxyl, 2 naphthoic acid/1 perfluoroetane sulfonic acid/LYH complexs, the fluorescent emission intensity of the complex apparently higher than 3 hydroxyl, 2 naphthoic acid sodium salt, therefore, it is possible to reduce detecting test limit during 32 naphthoic acid of hydroxyl using fluorescent spectrometry.
Description
Technical field
The present invention is related to organic synthesis field, more particularly to 3- hydroxy-2-naphthoic acids/1- perfluoroetane sulfonic acids/LYH complexs
And its synthetic method.
Background technology
(structural formula is 3- hydroxy-2-naphthoic acids) be dyestuff and organic pigment important intermediate, extensively
General be applied to the fields such as dyeing industry, for example be used for synthesize azoic coupling component AS and other various azoic coupling components etc..Made with 3- hydroxy-2-naphthoic acids
During dyestuff and organic pigment are produced for intermediate, the industrial wastewater containing 3- hydroxy-2-naphthoic acids can be produced, for preventing
3- hydroxy-2-naphthoic acids pollution environment in industrial wastewater, needs the harmless treatment such as carry out reclaiming, degrade to which.And at place
Before reason, then need to detect content of the 3- hydroxy-2-naphthoic acids in waste water.
Owing to thering is fluorescence emitting characteristics after 3-hydroxy-2-naphthoic acid generation sodium salt, therefore can adopt fluorescent spectrometry Detect its content.But the fluorescent emission intensity of 3-hydroxy-2-naphthoic acids is relatively low, cause test limit of a relatively high.
Therefore, the fluorescent emission intensity of 3- hydroxy-2-naphthoic acid sodium salts how is further improved, becomes art technology
Personnel's problem demanding prompt solution.
Content of the invention
The embodiment of the invention discloses a kind of 3- hydroxy-2-naphthoic acids/1- perfluoroetane sulfonic acids/LYH complexs and its synthesis side
Method, the fluorescent emission intensity for solving the problems, such as 3- hydroxy-2-naphthoic acid sodium salts are relatively low.Technical scheme is as follows：
The embodiment of the present invention provide firstly a kind of 3- hydroxy-2-naphthoic acids/1- perfluoroetane sulfonic acids/LYH complexs, with
Lower chemical formula composition：
Y(OH)2.5(C11H7O3)x(C8H17O3S)y·zH2O,
Wherein, X=0.07-0.13, y=0.36-0.37, z=1-2.
Preferably, the Fluorescence Characteristic of the complex includes：When the complex is scattered in colloidal suspensions,
The complex launches blue light.
Preferably, the Fluorescence Characteristic of the complex includes：The complex and 3- hydroxy-2-naphthoic acid sodium salt phases
Than 3 times or so for the latter's fluorescent emission intensity of the former fluorescent emission intensity.
The embodiment of the present invention additionally provides the synthesis of above-mentioned 3- hydroxy-2-naphthoic acids/1- perfluoroetane sulfonic acids/LYH complexs
Method, it is characterised in that comprise the following steps：
A) with sodium hydroxide or potassium hydroxide as base reagent, by sodium 1-octanesulfonate, base reagent and 3- hydroxy-2-naphthoic acids
It is dissolved in the water, obtains mixed solution, the wherein mol ratio of 3- hydroxy-2-naphthoic acids and base reagent is 1：(1-2)；3- hydroxyls-
The mol ratio of 2- naphthoic acids and sodium 1-octanesulfonate is 1：(3-5)；
B) by NO3After-LYH is dispersed in water, the mixed solution is added, hydro-thermal reaction 12-24 is little at 70-100 DEG C
Shi Hou, carries out post processing to product, wherein, the molal quantity sum of 3- hydroxy-2-naphthoic acids and sodium 1-octanesulfonate and NO3-LYH
The ratio of molal quantity is (1.5-6)：1, preferably (2-4)：1.
Preferably, in step a), the mol ratio of sodium 1-octanesulfonate, base reagent and 3- hydroxy-2-naphthoic acids is 3：1：
1.
Preferably, in step b), the molal quantity sum of 3- hydroxy-2-naphthoic acids and sodium 1-octanesulfonate and NO3-LYH
The ratio of molal quantity is 3：1.
Preferably, in obtained mixed solution in step a), the concentration of sodium 1-octanesulfonate is 0.08-0.2mmol/
mL.
Preferably, in step b), by NO3When-LYH is dispersed in water, NO3The concentration of-LYH is 0.002-
0.006mmol/mL.
Preferably, the post processing includes：Filter, wash, dry.
It can be seen that, anion exchange method is adopted in this programme, by hydro-thermal reaction by NO3- the 3- hydroxyls of LYH and deprotonation-
2- naphthoic acids (i.e. 3- hydroxy-2-naphthoic acids radical ion) and 1- perfluoroetane sulfonic acids radical ion are combined, and fix 3- hydroxy-2-naphthoic acids
Between LYH laminates, 3- hydroxy-2-naphthoic acids/1- perfluoroetane sulfonic acids/LYH complexs are obtained, the fluorescent emission intensity of the complex is bright
Aobvious is higher than 3- hydroxy-2-naphthoic acid sodium salts, therefore, it is possible to reduce detecting inspection during 3- hydroxy-2-naphthoic acids using fluorescent spectrometry
Survey limit.
In addition, the present invention is fixed on 3- hydroxy-2-naphthoic acids between LYH laminates, it is possible to use LYH laminates to 3- hydroxyls-
2- naphthoic acids are protected, it is possible to further the guarantor being applied in the synthesis of 3- hydroxy-2-naphthoic acids derivant to Organic substance
Shield.
And, complex provided by the present invention launch wavelength under different physics states is different, with 3- hydroxy-2-naphthoic acids
The luminous of sodium salt is compared, the obvious blue shift of launch wavelength, therefore can regulate and control glow color by intercalation, as Multicolor light-emitting device.
Description of the drawings
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
Accompanying drawing to be used needed for having technology description is briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can be with
Other accompanying drawings are obtained according to these accompanying drawings.
Fig. 1 is the NO of the synthesis of the embodiment of the present invention 13- LYH and embodiment 2-in-1 into 3- hydroxy-2-naphthoic acids/1- octanes
The XRD figure of sulfonic acid/LYH complexs；Wherein, in Fig. 1, (a) is NO3The XRD figure of-LYH, in Fig. 1, (b) is 3- hydroxyl -2- naphthalene first
The XRD figure of acid/1- perfluoroetane sulfonic acids/LYH complexs；
Fig. 2 is 3- hydroxy-2-naphthoic acids, sodium 1-octanesulfonate, the NO of the synthesis of embodiment 13- LYH and embodiment 2-in-1 into
The infrared spectrogram of 3- hydroxy-2-naphthoic acids/1- perfluoroetane sulfonic acids/LYH complexs；Wherein, (a), (b), (c) and (d) point in Fig. 2
Wei not 3- hydroxy-2-naphthoic acids, sodium 1-octanesulfonate, NO3The FT-IR figures of-LYH and complex；
Fig. 3 be 3- hydroxy-2-naphthoic acids sodium salt and the embodiment of the present invention 2-in-1 into 3- hydroxy-2-naphthoic acids/1- octane sulphurs
The fluorescence spectra of acid/LYH complexs, wherein, fluorescence of (a) 3- hydroxy-2-naphthoic acid sodium salts in formamide solution in Fig. 3
Spectrogram, fluorescence spectra when (b) is scattered in Methanamide colloidal suspensions for complex in Fig. 3；
Fig. 4 is 3- hydroxy-2-naphthoic acids/1- octane sulphurs that 3- hydroxy-2-naphthoic acids sodium salt and the embodiment of the present invention 3 synthesize
The fluorescence spectra of acid/LYH complexs, wherein, fluorescence of (a) 3- hydroxy-2-naphthoic acid sodium salts in formamide solution in Fig. 4
Spectrogram, fluorescence spectra when (b) is scattered in Methanamide colloidal suspensions for complex in Fig. 4；
Fig. 5 is 3- hydroxy-2-naphthoic acids/1- octane sulphurs that 3- hydroxy-2-naphthoic acids sodium salt and the embodiment of the present invention 4 synthesize
The fluorescence spectra of acid/LYH complexs, wherein, fluorescence of (a) 3- hydroxy-2-naphthoic acid sodium salts in formamide solution in Fig. 5
Spectrogram, fluorescence spectra when (b) is scattered in Methanamide colloidal suspensions for complex in Fig. 5.
Specific embodiment
Present invention firstly provides a kind of 3- hydroxy-2-naphthoic acids/1- perfluoroetane sulfonic acids/LYH complexs, with following chemistry
Formula is constituted：
Y(OH)2.5(C11H7O3)x(C8H17O3S)y·zH2O,
Wherein, X=0.07-0.13, y=0.36-0.37, z=1-2, it is preferable that z=1.1-1.7.
The complex that the present invention is provided has following Fluorescence Characteristic：
When the complex is scattered in colloidal suspensions, launch blue light.Described colloidal suspensions are referred to will be compound
Body is scattered in formation colloidal suspensions in the preferred Methanamide of solvent.The complex is compared with 3- hydroxy-2-naphthoic acid sodium salts, front
More than 3 times for the latter's fluorescent emission intensity of the fluorescent emission intensity of person.
Present invention also offers the synthetic method of above-mentioned complex, may comprise steps of：
A) with sodium hydroxide or potassium hydroxide as base reagent, by sodium 1-octanesulfonate, base reagent and 3- hydroxy-2-naphthoic acids
It is dissolved in the water, obtains mixed solution, wherein, the mol ratio of 3- hydroxy-2-naphthoic acids and base reagent is 1：(1-2)；3- hydroxyls-
The mol ratio of 2- naphthoic acids and sodium 1-octanesulfonate is 1：(3-5)；
As LYH laminates are positively charged, interlayer is tradable anion, is easily combined with anionic compound, therefore,
Need, by 3- hydroxy-2-naphthoic acid deprotonations, to form anionic compound, allow it to insert LYH interlayers.Specifically,
Sodium hydroxide or potassium hydroxide can be used as base reagent so as to react with 3- hydroxy-2-naphthoic acids, so that 3- hydroxyl -2-
Naphthoic acid deprotonation, obtains 3- hydroxy-2-naphthoic acids sodium salt or potassium salt.In practical application, sodium 1-octanesulfonate, alkali are tried
After agent and 3- hydroxy-2-naphthoic acids are added in water, can by ultrasonic power make sodium 1-octanesulfonate, base reagent and 3- hydroxyls-
2- naphthoic acids dissolve, and obtain the mixed solution that clarifies.In the specific implementation process of step a), sodium 1-octanesulfonate, base reagent
3 are preferably with the mol ratio of 3- hydroxy-2-naphthoic acids：1：1, in obtained mixed solution, the concentration of sodium 1-octanesulfonate
For being preferably 0.08-0.2mmol/mL.
B) by NO3After-LYH is dispersed in water, the mixed solution is added, hydro-thermal reaction 12-24 is little at 70-100 DEG C
Shi Hou, carries out post processing to product, wherein, the molal quantity sum of 3- hydroxy-2-naphthoic acids and sodium 1-octanesulfonate and NO3-LYH
The ratio of molal quantity is (1.5-6)：1, preferably (2-4)：1.By hydro-thermal reaction, the 3- hydroxyls of sodium 1-octanesulfonate and deprotonation are made
Base -2- naphthoic acids and NO3NO between-LYH laminates3 -Exchange, insert LYH interlayers.
In the specific implementation process of step b), the molal quantity sum of 3- hydroxy-2-naphthoic acids and sodium 1-octanesulfonate with
NO3The ratio of-LYH molal quantitys is preferably 3：1.In practical application, in step b), NO3The water yield used when-LYH is dispersed in water
Can be determined according to practical situation and the reaction kit for being used, it is preferable that by NO3When-LYH is dispersed in water, NO3-LYH
Concentration be 0.002-0.006mmol/mL.It should be noted that in this application, described NO3It is cloudy that-LYH refers to interlayer
Ion is NO3 -Stratiform yttrium hydroxide (LYH), can by existing synthetic method be obtained, it is also possible to commercially.
After hydro-thermal reaction terminates, need post processing to be carried out to product, can include：It is filtered, washed and dried process.Specifically
, after hydro-thermal reaction terminates, first product at reduced pressure can be filtered, then carry out carrying out washing treatment to filtered solid with water, one
As repeat 3-4 time after, at 30-50 DEG C, vacuum drying treatment 20-30 hour is obtained 3- hydroxy-2-naphthoic acids/1- octanes
Sulfonic acid/LYH complexs.
It should be noted that above-mentioned hydro-thermal reaction, washing and dried are experimental technique commonly used in the art, upper
State experimental apparatus used in processing procedure and equipment, concrete operation method can be selected according to practical situation by those skilled in the art
Select, here is not described in detail and specifically limits.Synthesis in 3- hydroxy-2-naphthoic acids/1- perfluoroetane sulfonic acids/LYH complexs
Medicine used and reagent in journey, in the case of without specified otherwise, can be synthesized by prior art or commercially
Purchase.
Explanation is needed further exist for, water used in this application is preferably deionized water.
Accompanying drawing in below in conjunction with the embodiment of the present invention, to the embodiment of the present invention in technical scheme carry out clear, complete
Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiment.It is based on
Embodiment in the present invention, it is every other that those of ordinary skill in the art are obtained under the premise of creative work is not made
Embodiment, belongs to the scope of protection of the invention.
Embodiment 1NO3The synthesis and structure of-LYH is characterized
Synthesized using sluggish precipitation, specific as follows：By 0.3383g (1mmol) Y (NO3)3·6H2O,1.10g
(13mmol)NaNO3, 0.14g (1mmol) hexamethylenetetramine (HMT) be dissolved in 80mL aerofluxuss water, go in reactor and logical N2
5 minutes, then 90 DEG C of hydro-thermal reactions 12 hours；After reaction terminates, the product that sucking filtration is obtained is washed with deionized after product again
Sucking filtration is carried out, 3 times repeatedly, is vacuum dried 24 hours, is obtained white powder NO3-LYH 0.177g.With Y (NO3)3·6H2O is
Benchmark, yield are 96.2%.
Elemental analyser (the model produced using German Elementar companies：Vario EL) measure the embodiment of the present invention 1
The NO of middle synthesis3The C of-LYH, H, N content；The plasma inductive produced using Spectro Analypical Instruments GmbH is former
Sub- emission spectrometer (ICP) (model：SPECTROARCOSEOP) NO synthesized in the embodiment of the present invention 1 is measured3The Y of-LYH contains
Amount, so that calculate the NO synthesized in the embodiment of the present invention 13The chemical composition of-LYH is Y (OH)2.5(NO3)0.5·1.2H2O, phase
Close data as shown in table 1.
Table 1NO3The elementary analysiss of-LYH and icp analysis data
Adopt3- LYH three times, synthesized go out NO3- LYH is applied to each enforcement below
Example.
The synthesis and structure of 2 complex of embodiment is characterized
By the 3- hydroxy-2-naphthoic acids of 0.0607g (0.3225mmol), the sodium hydroxide of 0.0129g (0.3225mmol)
It is added in the deionized water of 8ml with the sodium 1-octanesulfonate of 0.2267g (0.9675mmol), ultrasound makes 3- hydroxyl -2- naphthalene first
The dissolving of acid, sodium hydroxide and sodium 1-octanesulfonate, obtains the mixing containing 3- hydroxy-2-naphthoic acids sodium and sodium 1-octanesulfonate molten
Liquid；
NO by 0.07912g (0.43mmol)3- LYH is scattered in 130ml deionized waters, adds mixed solution, mixing
It is transferred in reactor after uniform, hydro-thermal reaction 24 hours at 70 DEG C.After reaction terminates, reduce pressure sucking filtration, and then product is used
Deionized water carries out carrying out washing treatment, 3 times repeatedly, then at 40 DEG C be vacuum dried 24 hours, obtain 3- hydroxy-2-naphthoic acids/
1- perfluoroetane sulfonic acids/LYH complex 0.1011g, with NO3On the basis of-LYH, yield is 91.4%.
Elementary analysiss：
3- hydroxyl -2- naphthalene the first gone out synthesized by the present embodiment is determined using instrument same as Example 1 and test condition
The content of C, H, N and Y of acid/1- perfluoroetane sulfonic acids/LYH complexs, so that calculate the complex synthesized in the embodiment of the present invention
Chemical composition be Y (OH)2.5(C11H7O3)0.13(C8H17O3S)0.37·1.67H2O, related data are as shown in table 2.
2 embodiment of table 2-in-1 into complex elementary analysiss and icp analysis data
X-ray diffraction (X-ray diffraction, XRD) is analyzed
Using Philips X'Pert diffractometers, in CuK α targets, wavelength X=0.15418nm, scanatron pressure, pipe flow difference
For 40mA, 40kV, step-length is 0.2 °, and sweep time is 10 steps/second, and it is 4.5-70 ° to scan big angle range, and little angle range is 0.8-
Under conditions of 6 °, the NO synthesized in embodiment 1 is measured3- LYH and embodiment 2-in-1 into complex XRD figure as shown in Figure 1.
In Fig. 1, (a) is as can be seen that NO3Occur the series of features such as 0.89nm, 0.45nm, 0.29nm in the XRD figure of-LYH
Diffraction maximum, illustrates NO3- LYH is layer structure.Interlamellar spacing is 0.89nm；Diffraction peak shape is sharp, illustrates that degree of crystallinity is very high.
In Fig. 1 (b) as can be seen that embodiment 2-in-1 into complex keep NO3The layer structure of-LYH, 2.02,
1.01,0.67,0.51,0.40 and at 0.34nm, there is Series diffractive peak, form the complex that interlamellar spacing is 2.02nm.Interlamellar spacing
Increase, illustrates that the 3- hydroxy-2-naphthoic acids and 1- perfluoroetane sulfonic acid roots of deprotonation are successively inserted into LYH interlayers, and forming interlamellar spacing is
The complex of 2.02nm, XRD peak shapes are sharp, illustrate that the degree of crystallinity of products obtained therefrom is preferable.
Infrared spectrum (FT-IR) is analyzed
Fourier transform infrared spectrometer (the FT-IR) (model produced using Nicolet companies of the U.S.：Nicolet360)
The NO synthesized by 3- hydroxy-2-naphthoic acids, sodium 1-octanesulfonate, embodiment 13- LYH and embodiment 2-in-1 into complex carry out
Infrared Characterization (using KBr pressed disc methods, is scanned under room temperature, test scope is 4000-400cm-1), FT-IR figures are as shown in Figure 2.
In Fig. 2, (a), (b), (c) and (d) is respectively 3- hydroxy-2-naphthoic acids, sodium 1-octanesulfonate, NO3- LYH and compound
The FT-IR figures of body.
(a) in Fig. 2 is schemed for the FT-IR of 3- hydroxy-2-naphthoic acids, 3284cm in figure-1Stretching vibration for-OH absorbs,
1665cm-1And 1467cm-1The symmetrical stretching vibration of respectively-COOH absorbs and antisymmetric stretching vibration absorbs, 1218cm-1For
C-O stretching vibrations absorb, 1516cm-1For naphthalene nucleus carbon skeleton absorption of vibrations；FT-IRs of (b) in Fig. 2 for sodium 1-octanesulfonate
Figure, 2920cm in figure-1、2851cm-1For-CH2Antisymmetry and symmetrical stretching vibration absorb.1200cm-1、1065cm-1Pungent for 1-
SO in alkyl sulfonic acid sodium3 -Characteristic absorption；(c) in Fig. 2 is NO3The FT-IR figures of-LYH, 1384cm in figure-1For NO3 -Feature
Absorb, 637cm-1For Y-O flexible/bending vibration absorbs.(d) in Fig. 2 is schemed for the FT-IR of complex, 2920cm in figure-1、
2856cm-1For-CH2Antisymmetry and symmetrical stretching vibration absorb, 1165cm-1、1049cm-1For SO3 -Characteristic absorption, explanation
The presence of sodium 1-octanesulfonate；1526cm-1And 1401cm-1Respectively-COO-Symmetrical flexible and antisymmetric stretching vibration absorbs, and says
The insertion of the 3- hydroxy-2-naphthoic acids of bright deprotonation, 606cm-1And 467cm-1For Y-O flexible/bending vibration absorbs.Above letter
Breath proves that embodiment 2 successfully synthesizes 3- hydroxy-2-naphthoic acids/1- perfluoroetane sulfonic acids/LYH complexs.
Spectrofluorimetry
Spectrofluorophotometer (the model produced using Australian VARIAN companies：Cary Eclipse) to 3- hydroxyls
Base -2- naphthoic acids sodium salt and the embodiment of the present invention 2-in-1 into 3- hydroxy-2-naphthoic acids/1- perfluoroetane sulfonic acids/LYH complexs carry out
Fluorometric investigation, fluorescence spectrum are as shown in Figure 3；Wherein,
In Fig. 3, (a) is emission spectrum of the 3- hydroxy-2-naphthoic acid sodium salts in formamide solution (exciting slit in test
For 2.5nm, transmite slit is 2.5nm, excitation wavelength 390nm), wherein, 3- hydroxy-2-naphthoic acids sodium salt can pass through 3- hydroxyls
After the sodium hydroxide of base -2- naphthoic acids and same molar is dissolved in water, evaporation solvent separates out solid, then by solid filtration drying
And obtain, the 3- hydroxy-2-naphthoic acid sodium salt solids of 0.025g gained are dissolved in 10ml Methanamides carries out fluorescence spectrum test；Figure
In 3, (b) is emission spectrum (exciting slit 2.5nm, transmite slit 2.5nm that complex is scattered in Methanamide colloidal suspensions
Excitation wavelength 390nm), wherein, Methanamide colloidal suspensions are obtained by 0.025g complexs are dispersed in 10ml Methanamides；
Knowable to (a) in Fig. 3, the emission peak of 3- hydroxy-2-naphthoic acid sodium salts is located at 512nm, is green emission；From Fig. 3
In (b) understand, when complex is in Methanamide colloidal suspensions, emission peak is displaced to 480nm, belongs to blue emission, blue shift
32nm, and it was unexpectedly determined that knowable to synthesis Fig. 3, the emissive porwer of the complex synthesized by the present embodiment is much larger than 3- hydroxyls
The emissive porwer of base -2- naphthoic acid sodium salts, the former can reach 3 times of the latter or so.
The synthesis and structure of embodiment 3 complexs characterizes
By the NaOH of the 3-hydroxy-2-naphthoic acid of 0.0607g (0.3225mmol), 0.0194g (0.4838mmol) With the 1-perfluorooctane sulfonate of 0.3023g (1.29mmol) joins in the deionized water of 10ml, ultrasonic 3-hydroxyl-2-naphthalene first that makes Acid, NaOH and 1-perfluorooctane sulfonate dissolve, and the mixing that obtains containing 3-hydroxy-2-naphthoic acid sodium and 1-perfluorooctane sulfonate is molten Liquid;
By the NO of 0.0736g (0.40mmol)3-LYH is scattered in 130ml deionized water, add mixed solution, after mixing, be transferred in reactor, hydro-thermal reaction 14 hours at 90 DEG C. after reaction finishes, decompress filter, then carries out carrying out washing treatment to product by deionized water, 3 times repeatedly, then vacuum drying 24 hours at 40 DEG C, obtains 3-hydroxy-2-naphthoic acid/1-perfluoroetane sulfonic acid/LYH complex 0.0891g, with NO3-LYH is benchmark, and productive rate is 92.2%.
Elementary analysis:
Adopt the instrument identical with embodiment 1 and test condition to measure the content of C, H, N and the Y of 3-hydroxy-2-naphthoic acid/1-perfluoroetane sulfonic acid/LYH complex that the present embodiment synthesized goes out, thereby the chemical composition that calculates complex synthetic in the embodiment of the present invention is Y (OH)2.5(C11H7O3)0.11(C8H17O3S)0.36·1.12H2O.
Elementary analysis and the icp analysis data of the synthetic complex of table 3 embodiment 3
Spectrofluorimetry
Adopt the equipment identical with embodiment 2 and test condition to 3-hydroxy-2-naphthoic acid sodium salt and the embodiment of the present invention 3 Synthetic 3-hydroxy-2-naphthoic acid/1-perfluoroetane sulfonic acid/LYH complex carries out fluorometric investigation, and fluorescence spectrum as shown in Figure 4;
In Fig. 4, (a) is the emission spectrum of 3-hydroxy-2-naphthoic acid sodium salt in formamide solution, wherein, and 3-hydroxyl-2-Naphthoic acid sodium salt is by by 3-hydroxy-2-naphthoic acid and NaOH, (mol ratio of 3-hydroxy-2-naphthoic acid and NaOH is 1:1.5) after water-soluble, evaporating solvent is separated out solid, and solid filtering is dry and obtain again, by the 3-hydroxyl of 0.025g gained-2-naphthoic acid sodium salt solid is dissolved in and in 10ml formamide, carries out fluorescence spectrum test; In Fig. 4, (b) is that complex is scattered in formamide Emission spectrum in colloidal suspensions, wherein, formamide colloidal suspensions is by being dispersed in 10ml formyl by 0.025g complex In amine and obtain;
From Fig. 4 (a), 3-hydroxy-2-naphthoic acid sodium salt is the green emission of 512nm in formamide solution, from Fig. 4, (b) is known, and complex is in formamide colloidal suspensions time, and emission peak is displaced to 480nm, belong to blue emission, blue shift 32nm, and surprisingly, complex chart 4 is known, the emissive porwer of the complex of the present embodiment synthesized is much larger than the emissive porwer of 3-hydroxy-2-naphthoic acid sodium salt, and the former can reach 3 times of left and right of the latter.
The synthesis and structure of embodiment 4 complexs characterizes
By the NaOH of the 3-hydroxy-2-naphthoic acid of 0.0607g (0.3225mmol), 0.0258g (0.645mmol) and The 1-perfluorooctane sulfonate of 0.3778g (1.6125mmol) joins in the deionized water of 12ml, ultrasonic 3-hydroxyl-2-naphthalene first that makes Acid, NaOH and 1-perfluorooctane sulfonate dissolve, and the mixing that obtains containing 3-hydroxy-2-naphthoic acid sodium and 1-perfluorooctane sulfonate is molten Liquid;
By the NO of 0.1656g (0.90mmol)3-LYH is scattered in 150ml deionized water, add mixed solution, after mixing, be transferred in reactor, hydro-thermal reaction 12 hours at 98 DEG C. after reaction finishes, decompress filter, then carries out carrying out washing treatment to product by deionized water, 3 times repeatedly, then vacuum drying 24 hours at 40 DEG C, obtains 3-hydroxy-2-naphthoic acid/1-perfluoroetane sulfonic acid/LYH complex 0.1935g, with NO3-LYH is benchmark, and productive rate is 90.6%.
Elementary analysis:
3- hydroxyl -2- naphthalene the first gone out synthesized by the present embodiment is determined using instrument same as Example 1 and test condition
The content of C, H, N and Y of acid/1- perfluoroetane sulfonic acids/LYH complexs, so that calculate the complex synthesized in the embodiment of the present invention
Chemical composition be Y (OH)2.5(C11H6O3)0.07(C8H17O3S)0.36·1.3H2O.
The elementary analysiss of the complex of the synthesis of 4 embodiment of table 4 and icp analysis data
Spectrofluorimetry
Using equipment same as Example 2 and test condition to 3- hydroxy-2-naphthoic acids sodium salt and the embodiment of the present invention 4
The 3- hydroxy-2-naphthoic acids of synthesis/1- perfluoroetane sulfonic acids/LYH complexs carry out fluorometric investigation, and fluorescence spectrum is as shown in Figure 5；
In Fig. 5, (a) is emission spectrum of the 3- hydroxy-2-naphthoic acid sodium salts in formamide solution, wherein, 3- hydroxyl -2-
Naphthoic acid sodium salt is by by 3- hydroxy-2-naphthoic acids and sodium hydroxide, (mol ratio of 3- hydroxy-2-naphthoic acids and sodium hydroxide is
1：2), after being dissolved in water, evaporation solvent separates out solid, solid is filtered re-dry and is obtained, by the 3- hydroxyl -2- of 0.025g gained
Naphthoic acid sodium salt solid is dissolved in 10ml Methanamides carries out fluorescence spectrum test；In Fig. 5, (b) is that complex is scattered in Methanamide glue
Emission spectrum in shape suspension, wherein, Methanamide colloidal suspensions are by being dispersed in 10ml Methanamides by 0.025g complexs
In and obtain；
Knowable to Fig. 5 (a), 3- hydroxy-2-naphthoic acids sodium salt is in the green emission that liquid is 511nm；From Fig. 5, (b) can
Know, when complex is in Methanamide colloidal suspensions, emission peak is displaced to 478nm, belong to blue emission, blue shift 33nm, and
It was unexpectedly determined that synthesis Fig. 5 understands, the emissive porwer of the complex synthesized by the present embodiment is much larger than 3- hydroxyl -2- naphthalene first
The emissive porwer of acid sodium-salt, the former can reach 3 times of the latter or so.
By the various embodiments described above, anion exchange method is adopted in this programme, by hydro-thermal reaction by NO3- LYH with
The 3- hydroxy-2-naphthoic acids of deprotonation and 1- perfluoroetane sulfonic acids radical ion are combined, and make 3- hydroxy-2-naphthoic acids be fixed on LYH laminates
Between, obtaining 3- hydroxy-2-naphthoic acids/1- perfluoroetane sulfonic acids/LYH complexs, the fluorescent emission intensity of the complex is apparently higher than 3-
Hydroxy-2-naphthoic acid, therefore, it is possible to reduce detecting test limit during 3- hydroxy-2-naphthoic acids using fluorescent spectrometry.
In addition, the present invention is fixed on 3- hydroxy-2-naphthoic acids between LYH laminates, it is possible to use LYH laminates to 3- hydroxyls-
2- naphthoic acids are protected, it is possible to further the guarantor being applied in the synthesis of 3- hydroxy-2-naphthoic acids derivant to Organic substance
Shield.
And, with the solution of 3- hydroxy-2-naphthoic acid sodium salts luminous compared with, complex provided by the present invention is in colloid
The obvious blue shift of state launch wavelength, is changed into blue emission from the green glow of Organic substance, can use by intercalation synthesis to regulate and control glow color
Make Multicolor light-emitting device.
Above to 3- hydroxy-2-naphthoic acids provided by the present invention/1- perfluoroetane sulfonic acids/LYH complexs and its synthetic method
It is described in detail.Specific embodiment used herein is set forth to the principle of the present invention and embodiment, above
The explanation of embodiment is only intended to help and understands the method for the present invention and its central idea.It should be pointed out that general for this area
For logical technical staff, under the premise without departing from the principles of the invention, some improvement and modification can also be carried out to the present invention, this
A little improvement and modification also fall into the protection of the claims in the present invention.
Claims (9)
1.3- hydroxy-2-naphthoic acids/1- perfluoroetane sulfonic acids/LYH complexs, it is characterised in that constitute with below formula：
Y(OH)2.5(C11H7O3)x(C8H17O3S)y·zH2O,
Wherein, X=0.07-0.13, y=0.36-0.37, z=1-2.
2. complex as claimed in claim 1, it is characterised in that the Fluorescence Characteristic of the complex includes：When described
When complex is scattered in colloidal suspensions, the complex launches blue light.
3. complex as claimed in claim 1, it is characterised in that the Fluorescence Characteristic of the complex includes：Described multiple
Compared with 3- hydroxy-2-naphthoic acid sodium salts, the former fluorescent emission intensity is 3 times or so of the latter's fluorescent emission intensity to zoarium.
4. the synthetic method of 3- hydroxy-2-naphthoic acids as claimed in claim 1/1- perfluoroetane sulfonic acids/LYH complexs, its feature
It is, comprises the following steps：
A) with sodium hydroxide or potassium hydroxide as base reagent, sodium 1-octanesulfonate, base reagent and 3- hydroxy-2-naphthoic acids are dissolved
Yu Shuizhong, obtains mixed solution, and the wherein mol ratio of 3- hydroxy-2-naphthoic acids and base reagent is 1：(1-2)；3- hydroxyl -2- naphthalenes
The mol ratio of formic acid and sodium 1-octanesulfonate is 1：(3-5)；
B) by NO3After-LYH is dispersed in water, the mixed solution is added, after hydro-thermal reaction 12-24 hour at 70-100 DEG C,
Post processing is carried out to product, wherein, the molal quantity sum of 3- hydroxy-2-naphthoic acids and sodium 1-octanesulfonate and NO3- LYH mole
Several ratios is (1.5-6)：1, preferably (2-4)：1.
5. synthetic method as claimed in claim 4, it is characterised in that in step a), sodium 1-octanesulfonate, base reagent and 3-
The mol ratio of hydroxy-2-naphthoic acid is 3：1：1.
6. synthetic method as claimed in claim 4, it is characterised in that in step b), 3- hydroxy-2-naphthoic acids and 1- octanes
The molal quantity sum of sodium sulfonate and NO3The ratio of-LYH molal quantitys is 3：1.
7. synthetic method as claimed in claim 4, it is characterised in that in the mixed solution obtained by step a), 1- is pungent
The concentration of alkyl sulfonic acid sodium is 0.08-0.2mmol/mL.
8. synthetic method as claimed in claim 4, it is characterised in that in step b), by NO3When-LYH is dispersed in water,
NO3The concentration of-LYH is 0.002-0.006mmol/mL.
9. synthetic method as claimed in claim 4, it is characterised in that the post processing includes：Filter, wash, dry.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610921966.8A CN106497550B (en) | 2016-10-21 | 2016-10-21 | 3- hydroxy-2-naphthoic acid/1- perfluoroetane sulfonic acid/LYH complex and its synthetic method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610921966.8A CN106497550B (en) | 2016-10-21 | 2016-10-21 | 3- hydroxy-2-naphthoic acid/1- perfluoroetane sulfonic acid/LYH complex and its synthetic method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106497550A true CN106497550A (en) | 2017-03-15 |
| CN106497550B CN106497550B (en) | 2019-03-12 |
Family
ID=58318714
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610921966.8A Expired - Fee Related CN106497550B (en) | 2016-10-21 | 2016-10-21 | 3- hydroxy-2-naphthoic acid/1- perfluoroetane sulfonic acid/LYH complex and its synthetic method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106497550B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101048467A (en) * | 2004-06-11 | 2007-10-03 | 科莱恩产品（德国）有限公司 | Hydrophobic salts of layered metal hydroxides |
| CN101244833A (en) * | 2008-03-14 | 2008-08-20 | 北京化工大学 | Method for confirming interlaminar molecular orientation of naphthaleneacetic acid intercalation zincium aluminum hydrotalcite film |
| KR20110021148A (en) * | 2009-08-25 | 2011-03-04 | 경희대학교 산학협력단 | Surface-modified layered gadolinium hydroxide, process of preparing the same and mri contrast agent including the same |
| CN105670605A (en) * | 2016-03-14 | 2016-06-15 | 北京师范大学 | Fluorescein/1-octanesulfonate/LYH complex and synthesis method thereof |
-
2016
- 2016-10-21 CN CN201610921966.8A patent/CN106497550B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101048467A (en) * | 2004-06-11 | 2007-10-03 | 科莱恩产品（德国）有限公司 | Hydrophobic salts of layered metal hydroxides |
| CN101244833A (en) * | 2008-03-14 | 2008-08-20 | 北京化工大学 | Method for confirming interlaminar molecular orientation of naphthaleneacetic acid intercalation zincium aluminum hydrotalcite film |
| KR20110021148A (en) * | 2009-08-25 | 2011-03-04 | 경희대학교 산학협력단 | Surface-modified layered gadolinium hydroxide, process of preparing the same and mri contrast agent including the same |
| CN105670605A (en) * | 2016-03-14 | 2016-06-15 | 北京师范大学 | Fluorescein/1-octanesulfonate/LYH complex and synthesis method thereof |
Non-Patent Citations (1)
| Title |
|---|
| FEIFEI SU等: "Delaminated layered rare-earth hydroxide composites with ortho-coumaric acid: color-tunable luminescence and blue emission due to energy transfer", 《J. MATER. CHEM. C》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106497550B (en) | 2019-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ma et al. | Anionic porous metal–organic framework with novel 5-connected vbk topology for rapid adsorption of dyes and tunable white light emission | |
| EP3212576A1 (en) | Methods of preparing high purity aluminum hydroxide and high purity aluminum oxide | |
| Silva et al. | Supramolecular luminescent hydrogels based on β-amino acid and lanthanide ions obtained by self-assembled hydrothermal reactions | |
| CN105885827B (en) | Fluorescent red-orange material zinc coordination polymer [Zn (HL) (HBPEP)]nAnd its synthetic method | |
| CN109970990B (en) | Terbium coordination polymer and preparation method and application thereof | |
| Zhang et al. | Multi-step tandem functionalization assembly of MOFs-based hybrid polymeric films for color tuning luminescence and responsive sensing on organic vapors | |
| CN106497548B (en) | 3- hydroxy-2-naphthoic acid/1- perfluoroetane sulfonic acid/LTbH complex and its synthetic method | |
| CN105670605B (en) | Fluorescein/1 perfluoroetane sulfonic acid/LYH complexs and its synthetic method | |
| CN112592358A (en) | Blue light luminescent crystal material and preparation method and application thereof | |
| Zhou et al. | Polyurethane-based Eu (iii) luminescent foam as a sensor for recognizing Cu 2+ in water | |
| CN110551291B (en) | Porous interpenetrating zinc-organic supramolecular polymer and preparation method and application thereof | |
| CN106497550A (en) | 3 hydroxyl, 2 naphthoic acid/1 perfluoroetane sulfonic acid/LYH complexs and its synthetic method | |
| CN105330680B (en) | A kind of method for preparing Gd2 O3 Rare Earth Europium Complex | |
| CN104877682B (en) | Trimesic acid-LTbH complex and synthesis method thereof | |
| CN111591977A (en) | Application of polyepoxysuccinic acid as carbon source in preparation of carbon quantum dots | |
| Li et al. | A turn-on fluorescence sensing strategy for rapid detection of flumequine in water environments using covalent-coordination functionalized MOFs | |
| Yang et al. | The influence of preparation conditions on the fluorescence properties of Eu (Sal) 3Phen | |
| CN100457852C (en) | Nanotube, nano bar-shape aluminate long afterglow materials and method for preparing same | |
| CN105733558B (en) | The carboxylic acid of cumarin 3/1 perfluoroetane sulfonic acid/LEuH complexs and its synthetic method | |
| Arroyos et al. | Rare earth phosphors based on spherical infinite coordination polymers | |
| CN106497545B (en) | Tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs and its synthetic method | |
| CN105694844B (en) | The carboxylic acid of cumarin 3/1 perfluoroetane sulfonic acid/LGdH complexs and its synthetic method | |
| CN104263350B (en) | HPTS/OS-LEuH complex and synthetic method thereof | |
| CN106085431A (en) | A kind of preparation method of strontium doping C 12 A 7 rare earth luminescent material | |
| CN106947464B (en) | Fluorescein/1- perfluoroetane sulfonic acid/LTbH complex, its synthetic method and purposes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190312 Termination date: 20211021 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |