CN106497550B - 3- hydroxy-2-naphthoic acid/1- perfluoroetane sulfonic acid/LYH complex and its synthetic method - Google Patents
3- hydroxy-2-naphthoic acid/1- perfluoroetane sulfonic acid/LYH complex and its synthetic method Download PDFInfo
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Abstract
The embodiment of the invention discloses a kind of 3- hydroxy-2-naphthoic acid/1- perfluoroetane sulfonic acid/LYH complex and its synthetic methods, the 3- hydroxy-2-naphthoic acid/1- perfluoroetane sulfonic acid/LYH complex, have following below 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.By NO in this programme3- LYH is in conjunction with the 3- hydroxy-2-naphthoic acid (i.e. 3- hydroxy-2-naphthoic acid radical ion) and 1- perfluoroetane sulfonic acid radical ion of deprotonation, obtain 3- hydroxy-2-naphthoic acid/1- perfluoroetane sulfonic acid/LYH complex, the fluorescent emission intensity of the complex is apparently higher than 3- hydroxy-2-naphthoic acid sodium salt, therefore can reduce detection limit when detecting 3- hydroxy-2-naphthoic acid using fluorescent spectrometry.
Description
Technical field
The present invention is related to organic synthesis field, in particular to 3- hydroxy-2-naphthoic acid/1- perfluoroetane sulfonic acid/LYH complex
And its synthetic method.
Background technique
(structural formula is 3- hydroxy-2-naphthoic acid) be dyestuff and organic pigment important intermediate, extensively
It is general to be applied to the fields such as dyeing industry, such as synthesizing azoic coupling component AS and other various azoic coupling components etc..With 3- hydroxy-2-naphthoic acid work
During producing dyestuff and organic pigment for intermediate, the industrial wastewater containing 3- hydroxy-2-naphthoic acid can be generated, to prevent
3- hydroxy-2-naphthoic acid in industrial wastewater pollutes environment, needs the harmless treatments such as to recycle it, degrade.And locating
Before reason, then need to detect content of the 3- hydroxy-2-naphthoic acid in waste water.
There are fluorescence emitting characteristics after generating sodium salt due to 3- hydroxy-2-naphthoic acid, fluorescent spectrometry can be used
Detect its content.But the fluorescent emission intensity of 3- hydroxy-2-naphthoic acid is lower, causes detection limit relatively high.
Therefore, the fluorescent emission intensity for how further improving 3- hydroxy-2-naphthoic acid sodium salt, becomes art technology
Personnel's urgent problem to be solved.
Summary of the invention
The embodiment of the invention discloses a kind of 3- hydroxy-2-naphthoic acid/1- perfluoroetane sulfonic acid/LYH complex and its synthesis sides
Method, the fluorescent emission intensity for solving the problems, such as 3- hydroxy-2-naphthoic acid sodium salt are lower.Technical solution is as follows:
The embodiment of the present invention provides firstly a kind of 3- hydroxy-2-naphthoic acid/1- perfluoroetane sulfonic acid/LYH complex, have 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 include: when the complex is scattered in colloidal suspensions,
The complex emits blue light.
Preferably, the Fluorescence Characteristic of the complex includes: the complex and 3- hydroxy-2-naphthoic acid sodium salt phase
Than the former fluorescent emission intensity is 3 times or so of the latter's fluorescent emission intensity.
The embodiment of the invention also provides above-mentioned 3- hydroxy-2-naphthoic acid/1- perfluoroetane sulfonic acid/LYH complex synthesis
Method, which comprises the following steps:
A) using sodium hydroxide or potassium hydroxide as base reagent, by sodium 1-octanesulfonate, base reagent and 3- hydroxy-2-naphthoic acid
It is dissolved in the water, obtains mixed solution, wherein the molar ratio of 3- hydroxy-2-naphthoic acid and base reagent is 1:(1-2)；3- hydroxyl-
The molar ratio of 2- naphthoic acid 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 small at 70-100 DEG C
Shi Hou post-processes product, wherein the sum of molal quantity of 3- hydroxy-2-naphthoic acid 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 molar ratio of sodium 1-octanesulfonate, base reagent and 3- hydroxy-2-naphthoic acid is 3:1:
1。
Preferably, in step b), the sum of molal quantity of 3- hydroxy-2-naphthoic acid and sodium 1-octanesulfonate and NO3-LYH
The ratio of molal quantity is 3:1.
Preferably, in step a) in obtained mixed solution, 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: to be filtered, washed, dry.
As it can be seen that anion exchange method is used in this programme, by hydro-thermal reaction by NO3The 3- hydroxyl-of-LYH and deprotonation
2- naphthoic acid (i.e. 3- hydroxy-2-naphthoic acid radical ion) and 1- perfluoroetane sulfonic acid radical ion combine, and fix 3- hydroxy-2-naphthoic acid
Between LYH laminate, 3- hydroxy-2-naphthoic acid/1- perfluoroetane sulfonic acid/LYH complex is obtained, the fluorescent emission intensity of the complex is bright
It is aobvious to be higher than 3- hydroxy-2-naphthoic acid sodium salt, therefore can reduce inspection when detecting 3- hydroxy-2-naphthoic acid using fluorescent spectrometry
Survey limit.
In addition, can use LYH laminate to 3- hydroxyl-between 3- hydroxy-2-naphthoic acid is fixed on LYH laminate by the present invention
2- naphthoic acid is protected, it is possible to further be applied to the guarantor in the synthesis of 3- hydroxy-2-naphthoic acid derivative to organic matter
Shield.
Moreover, complex provided by the present invention launch wavelength under different physics states is different, with 3- hydroxy-2-naphthoic acid
The luminous of sodium salt is compared, the obvious blue shift of launch wavelength, therefore can regulate and control luminescent color by intercalation, is used as Multicolor light-emitting device.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is the NO that the embodiment of the present invention 1 synthesizes33- hydroxy-2-naphthoic acid/1- octane that-LYH and embodiment 2 synthesize
Sulfonic acid/LYH complex XRD diagram；Wherein, (a) is NO in Fig. 13The XRD diagram of-LYH, (b) is 3- hydroxyl -2- naphthalene first in Fig. 1
Acid/1- perfluoroetane sulfonic acid/LYH complex XRD diagram；
The NO that Fig. 2 is 3- hydroxy-2-naphthoic acid, sodium 1-octanesulfonate, embodiment 1 synthesize3What-LYH and embodiment 2 synthesized
3- hydroxy-2-naphthoic acid/1- perfluoroetane sulfonic acid/LYH complex infrared spectrogram；Wherein, (a), (b), (c) and (d) divide in Fig. 2
It Wei not 3- hydroxy-2-naphthoic acid, sodium 1-octanesulfonate, NO3The FT-IR of-LYH and complex figure；
Fig. 3 is 3- hydroxy-2-naphthoic acid sodium salt and 3- hydroxy-2-naphthoic acid/1- octane sulphur that the embodiment of the present invention 2 synthesizes
Acid/LYH complex fluorescence spectra, wherein fluorescence of (a) 3- hydroxy-2-naphthoic acid sodium salt in formamide solution in Fig. 3
Spectrogram, (b) is fluorescence spectra when complex is scattered in formamide colloidal suspensions in Fig. 3；
Fig. 4 is 3- hydroxy-2-naphthoic acid sodium salt and 3- hydroxy-2-naphthoic acid/1- octane sulphur that the embodiment of the present invention 3 synthesizes
Acid/LYH complex fluorescence spectra, wherein fluorescence of (a) 3- hydroxy-2-naphthoic acid sodium salt in formamide solution in Fig. 4
Spectrogram, (b) is fluorescence spectra when complex is scattered in formamide colloidal suspensions in Fig. 4；
Fig. 5 is 3- hydroxy-2-naphthoic acid sodium salt and 3- hydroxy-2-naphthoic acid/1- octane sulphur that the embodiment of the present invention 4 synthesizes
Acid/LYH complex fluorescence spectra, wherein fluorescence of (a) 3- hydroxy-2-naphthoic acid sodium salt in formamide solution in Fig. 5
Spectrogram, (b) is fluorescence spectra when complex is scattered in formamide colloidal suspensions in Fig. 5.
Specific embodiment
Present invention firstly provides a kind of 3- hydroxy-2-naphthoic acid/1- perfluoroetane sulfonic acid/LYH complexs, have following chemistry
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, it is preferable that z=1.1-1.7.
Complex provided by the invention has following Fluorescence Characteristic:
When the complex is scattered in colloidal suspensions, emit blue light.Described colloidal suspensions refer to will be compound
Body, which is scattered in the preferred formamide of solvent, forms colloidal suspensions.The complex is preceding compared with 3- hydroxy-2-naphthoic acid sodium salt
The fluorescent emission intensity of person is 3 times or more of the latter's fluorescent emission intensity.
The present invention also provides the synthetic methods of above-mentioned complex, may comprise steps of:
A) using sodium hydroxide or potassium hydroxide as base reagent, by sodium 1-octanesulfonate, base reagent and 3- hydroxy-2-naphthoic acid
It is dissolved in the water, obtains mixed solution, wherein the molar ratio of 3- hydroxy-2-naphthoic acid and base reagent is 1:(1-2)；3- hydroxyl-
The molar ratio of 2- naphthoic acid and sodium 1-octanesulfonate is 1:(3-5)；
Since LYH laminate is positively charged, interlayer is tradable anion, easily in conjunction with anionic compound, therefore,
It needs 3- hydroxy-2-naphthoic acid deprotonation forming anionic compound, allows it to insertion LYH interlayer.Specifically,
Sodium hydroxide or potassium hydroxide can be used as base reagent, react it with 3- hydroxy-2-naphthoic acid, to make 3- hydroxyl -2-
Naphthoic acid deprotonation obtains 3- hydroxy-2-naphthoic acid sodium salt or sylvite.In practical application, sodium 1-octanesulfonate, alkali are tried
After agent and 3- hydroxy-2-naphthoic acid are added in water, sodium 1-octanesulfonate, base reagent and 3- hydroxyl-can be made by ultrasonic power
The dissolution of 2- naphthoic acid, obtains clear mixed solution.In the specific implementation process of step a), sodium 1-octanesulfonate, base reagent
Molar ratio with 3- hydroxy-2-naphthoic acid is preferably 3:1:1, in obtained mixed solution, the concentration of sodium 1-octanesulfonate
To be 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 small at 70-100 DEG C
Shi Hou post-processes product, wherein the sum of molal quantity of 3- hydroxy-2-naphthoic acid 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, make the 3- hydroxyl of sodium 1-octanesulfonate and deprotonation
Base -2- naphthoic acid and NO3NO between-LYH laminate3 -LYH interlayer is inserted into exchange.
In the specific implementation process of step b), the sum of molal quantity of 3- hydroxy-2-naphthoic acid and sodium 1-octanesulfonate with
NO3The ratio of-LYH molal quantity is preferably 3:1.In practical application, in step b), NO3Water used when-LYH is dispersed in water
Can according to the actual situation and used reaction kit determine, 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 NO3- LYH refers to interlayer yin
Ion is NO3 -Stratiform yttrium hydroxide (LYH), can by existing synthetic method be made, can also be commercially.
It after hydro-thermal reaction, needs to post-process product, may include: to be filtered, washed and dried processing.Specifically
, after hydro-thermal reaction, first product at reduced pressure can be filtered, carrying out washing treatment then carried out with water to the solid filtered, one
As repeat 3-4 times after, 3- hydroxy-2-naphthoic acid/1- octane can be obtained within vacuum drying treatment 20-30 hours at 30-50 DEG C
Sulfonic acid/LYH complex.
It should be noted that above-mentioned hydro-thermal reaction, washing and drying process are experimental method commonly used in the art, upper
Stating laboratory apparatus used in treatment process and equipment, concrete operation method can be selected according to the actual situation by those skilled in the art
It selects, be not described in detail herein and specifically limit.In 3- hydroxy-2-naphthoic acid/1- perfluoroetane sulfonic acid/LYH complex synthesis
Drug used in journey and reagent, unless otherwise specified, can by the prior art synthesize or on the market
Purchase.
Explanation is needed further exist for, water used is preferably deionized water in this application.
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Embodiment 1NO3The synthesis and structure of-LYH characterizes
It is synthesized using sluggish precipitation, it is specific as follows: by 0.3383g (1mmol) Y (NO3)3·6H2O,1.10g
(13mmol)NaNO3, 0.14g (1mmol) hexamethylenetetramine (HMT) be dissolved in 80mL exhaust water, go in reaction kettle and logical N2
5 minutes, then 90 DEG C hydro-thermal reaction 12 hours；After reaction, the product filtered is washed with deionized after product again
It is filtered, 3 times repeatedly, is dried in vacuo 24 hours, obtains white powder NO3-LYH 0.177g.With Y (NO3)3·6H2O is
Benchmark, yield 96.2%.
The embodiment of the present invention 1 is measured using the elemental analyser (model: Vario EL) that German Elementar company produces
The NO of middle synthesis3C, H of-LYH, N content；Plasma inductive coupling using Spectro Analypical Instruments GmbH's production is former
Sub- emission spectrometer (ICP) (model: SPECTROARCOSEOP) measures the NO synthesized in the embodiment of the present invention 13The Y of-LYH contains
Amount, to 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
It is as shown in table 1 to close data.
1 NO of table3The elemental analysis and icp analysis data of-LYH
It adopts and repeats synthesis NO with the aforedescribed process3- LYH three times, it is synthesized go out NO3- LYH is applied to subsequent each implementation
Example.
The synthesis and structure of 2 complex of embodiment characterizes
By the 3- hydroxy-2-naphthoic acid 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
Acid, sodium hydroxide and sodium 1-octanesulfonate dissolution, it is molten to obtain the mixing containing 3- hydroxy-2-naphthoic acid sodium and sodium 1-octanesulfonate
Liquid；
By the NO of 0.07912g (0.43mmol)3- LYH is scattered in 130ml deionized water, and mixed solution, mixing is added
It is transferred in reaction kettle after uniformly, hydro-thermal reaction 24 hours at 70 DEG C.After reaction, decompression filters, and then uses product
Deionized water carry out carrying out washing treatment, 3 times repeatedly, be then dried in vacuo 24 hours at 40 DEG C, obtain 3- hydroxy-2-naphthoic acid/
1- perfluoroetane sulfonic acid/LYH complex 0.1011g, with NO3On the basis of-LYH, yield 91.4%.
Elemental analysis:
3- hydroxyl -2- naphthalene the first gone out synthesized by the present embodiment is measured using instrument and test condition same as Example 1
Acid/1- perfluoroetane sulfonic acid/LYH complex C, H, N and Y content, to 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.
The elemental analysis and icp analysis data of the complex of 2 embodiment 2 of table synthesis
X-ray diffraction (X-ray diffraction, XRD) analysis
Using Philips X'Pert diffractometer, in CuK α target, wavelength X=0.15418nm, flying-spot tube pressure, pipe stream difference
For 40mA, 40kV, step-length is 0.2 °, and sweep time is 10 steps/second, and scanning big angular region is 4.5-70 °, and small angular region is 0.8-
Under conditions of 6 °, the NO synthesized in embodiment 1 is measured3The XRD diagram for the complex that-LYH and embodiment 2 synthesize is as shown in Figure 1.
The NO it can be seen from (a) in Fig. 13Occur the series of features such as 0.89nm, 0.45nm, 0.29nm in the XRD diagram of-LYH
Diffraction maximum illustrates NO3- LYH is layer structure.Interlamellar spacing is 0.89nm；Diffraction peak shape is sharp, illustrates that crystallinity is very high.
The complex that embodiment 2 synthesizes it can be seen from (b) in Fig. 1 keeps 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 acid of deprotonation and 1- perfluoroetane sulfonic acid root are successively inserted into LYH interlayer, forming interlamellar spacing is
The complex of 2.02nm, XRD peak shape is sharp, illustrates that the crystallinity of products obtained therefrom is preferable.
Infrared spectroscopy (FT-IR) analysis
The Fourier Transform Infrared Spectrometer (FT-IR) (model: Nicolet360) produced using Nicolet company, the U.S.
The NO that 3- hydroxy-2-naphthoic acid, sodium 1-octanesulfonate, embodiment 1 are synthesized3The complex that-LYH and embodiment 2 synthesize carries out
IR Characterization (uses KBr pressed disc method, scans at room temperature, test scope 4000-400cm-1), FT-IR figure is as shown in Figure 2.
(a), (b), (c) and (d) be respectively 3- hydroxy-2-naphthoic acid, sodium 1-octanesulfonate, NO in Fig. 23- LYH and compound
The FT-IR of body schemes.
(a) in Fig. 2 is that the FT-IR of 3- hydroxy-2-naphthoic acid schemes, 3284cm in figure-1It is absorbed for the stretching vibration of-OH,
1665cm-1And 1467cm-1The symmetrical stretching vibration of respectively-COOH absorbs and antisymmetric stretching vibration absorbs, 1218cm-1For
C-O stretching vibration absorbs, 1516cm-1For naphthalene nucleus carbon skeleton absorption of vibrations；(b) in Fig. 2 is the FT-IR of sodium 1-octanesulfonate
Scheme, 2920cm in figure-1、2851cm-1For-CH2Antisymmetry and symmetrical stretching vibration absorb.1200cm-1、1065cm-1It is pungent for 1-
SO in alkyl sulfonic acid sodium3 -Characteristic absorption；(c) in Fig. 2 is NO3The FT-IR of-LYH schemes, 1384cm in figure-1For NO3 -Feature
It absorbs, 637cm-1For Y-O it is flexible/bending vibration absorbs.(d) in Fig. 2 is that the FT-IR of complex schemes, 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 acid of bright deprotonation, 606cm-1And 467cm-1For Y-O it is flexible/bending vibration absorbs.The above letter
Breath proves that embodiment 2 successfully synthesizes 3- hydroxy-2-naphthoic acid/1- perfluoroetane sulfonic acid/LYH complex.
Spectrofluorimetry
Using the sepectrophotofluorometer (model: Cary Eclipse) of Australian VARIAN company production to 3- hydroxyl
3- hydroxy-2-naphthoic acid/1- perfluoroetane sulfonic acid/LYH complex that base -2- naphthoic acid sodium salt and the embodiment of the present invention 2 synthesize carries out
Fluorometric investigation, fluorescence spectrum are as shown in Figure 3；Wherein,
(a) is emission spectrum (in test exciting slit of the 3- hydroxy-2-naphthoic acid sodium salt in formamide solution in Fig. 3
For 2.5nm, transmite slit 2.5nm, excitation wavelength 390nm), wherein 3- hydroxy-2-naphthoic acid sodium salt can be by by 3- hydroxyl
After base -2- naphthoic acid and the sodium hydroxide of same molar are dissolved in water, solid is precipitated in evaporation solvent, then by solid filtration drying
And obtain, the resulting 3- hydroxy-2-naphthoic acid sodium salt solid of 0.025g is dissolved in progress fluorescence spectrum test in 10ml formamide；Figure
(b) is emission spectrum (the exciting slit 2.5nm, transmite slit 2.5nm that complex is scattered in formamide colloidal suspensions in 3
Excitation wavelength 390nm), wherein formamide colloidal suspensions are obtained and 0.025g complex is dispersed in 10ml formamide；
(a) is it is found that the emission peak of 3- hydroxy-2-naphthoic acid sodium salt is located at 512nm, for green emission from Fig. 3；From Fig. 3
In (b) it is found that when complex is in formamide colloidal suspensions, emission peak is displaced to 480nm, belongs to blue emission, blue shift
32nm, and it was unexpectedly determined that complex chart 3 it is found that complex synthesized by the present embodiment emissive porwer be much larger than 3- hydroxyl
The emissive porwer of base -2- naphthoic acid sodium salt, the former can achieve 3 times of the latter or so.
The synthesis and structure of 3 complex of embodiment characterizes
By the 3- hydroxy-2-naphthoic acid of 0.0607g (0.3225mmol), the sodium hydroxide of 0.0194g (0.4838mmol)
It is added in the deionized water of 10ml with the sodium 1-octanesulfonate of 0.3023g (1.29mmol), ultrasound makes 3- hydroxyl -2- naphthalene first
Acid, sodium hydroxide and sodium 1-octanesulfonate dissolution, it is molten to obtain the mixing containing 3- hydroxy-2-naphthoic acid sodium and sodium 1-octanesulfonate
Liquid；
By the NO of 0.0736g (0.40mmol)3- LYH is scattered in 130ml deionized water, and mixed solution is added, and mixing is equal
It is transferred in reaction kettle after even, hydro-thermal reaction 14 hours at 90 DEG C.After reaction, decompression filters, and then spends to product
Ionized water carries out carrying out washing treatment, 3 times repeatedly, is then dried in vacuo 24 hours at 40 DEG C, obtains 3- hydroxy-2-naphthoic acid/1-
Perfluoroetane sulfonic acid/LYH complex 0.0891g, with NO3On the basis of-LYH, yield 92.2%.
Elemental analysis:
3- hydroxyl -2- naphthalene the first gone out synthesized by the present embodiment is measured using instrument and test condition same as Example 1
Acid/1- perfluoroetane sulfonic acid/LYH complex C, H, N and Y content, to calculate the complex synthesized in the embodiment of the present invention
Chemical composition be Y (OH)2.5(C11H7O3)0.11(C8H17O3S)0.36·1.12H2O。
The elemental analysis and icp analysis data of the complex of 3 embodiment 3 of table synthesis
Spectrofluorimetry
Using equipment and test condition same as Example 2 to 3- hydroxy-2-naphthoic acid sodium salt and the embodiment of the present invention 3
The 3- hydroxy-2-naphthoic acid of synthesis/1- perfluoroetane sulfonic acid/LYH complex carries out fluorometric investigation, and fluorescence spectrum is as shown in Figure 4；
(a) is emission spectrum of the 3- hydroxy-2-naphthoic acid sodium salt in formamide solution in Fig. 4, wherein 3- hydroxyl -2-
Naphthoic acid sodium salt is by the way that by 3- hydroxy-2-naphthoic acid and sodium hydroxide, (molar ratio of 3- hydroxy-2-naphthoic acid and sodium hydroxide is
After 1:1.5) being dissolved in water, solid is precipitated in evaporation solvent, and solid is filtered re-dry and is obtained, by the resulting 3- hydroxyl-of 0.025g
2- naphthoic acid sodium salt solid is dissolved in progress fluorescence spectrum test in 10ml formamide；(b) is that complex is scattered in formamide in Fig. 4
Emission spectrum in colloidal suspensions, wherein formamide colloidal suspensions are by being dispersed in 10ml formyl for 0.025g complex
It is obtained in amine；
From Fig. 4 (a) it is found that 3- hydroxy-2-naphthoic acid sodium salt is the green emission of 512nm in formamide solution, from Fig. 4
In (b) it is found that when complex is in formamide colloidal suspensions, emission peak is displaced to 480nm, belongs to blue emission, blue shift
32nm, and it was unexpectedly determined that complex chart 4 it is found that complex synthesized by the present embodiment emissive porwer be much larger than 3- hydroxyl
The emissive porwer of base -2- naphthoic acid sodium salt, the former can achieve 3 times of the latter or so.
The synthesis and structure of 4 complex of embodiment characterizes
By the 3- hydroxy-2-naphthoic acid of 0.0607g (0.3225mmol), 0.0258g (0.645mmol) sodium hydroxide and
The sodium 1-octanesulfonate of 0.3778g (1.6125mmol) is added in the deionized water of 12ml, and ultrasound makes 3- hydroxyl -2- naphthalene first
Acid, sodium hydroxide and sodium 1-octanesulfonate dissolution, it is molten to obtain the mixing containing 3- hydroxy-2-naphthoic acid sodium and sodium 1-octanesulfonate
Liquid；
By the NO of 0.1656g (0.90mmol)3- LYH is scattered in 150ml deionized water, and mixed solution is added, and mixing is equal
It is transferred in reaction kettle after even, hydro-thermal reaction 12 hours at 98 DEG C.After reaction, decompression filters, and then spends to product
Ionized water carries out carrying out washing treatment, 3 times repeatedly, is then dried in vacuo 24 hours at 40 DEG C, obtains 3- hydroxy-2-naphthoic acid/1-
Perfluoroetane sulfonic acid/LYH complex 0.1935g, with NO3On the basis of-LYH, yield 90.6%.
Elemental analysis:
3- hydroxyl -2- naphthalene the first gone out synthesized by the present embodiment is measured using instrument and test condition same as Example 1
Acid/1- perfluoroetane sulfonic acid/LYH complex C, H, N and Y content, to 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 elemental analysis and icp analysis data of the complex of 4 embodiment 4 of table synthesis
Spectrofluorimetry
Using equipment and test condition same as Example 2 to 3- hydroxy-2-naphthoic acid sodium salt and the embodiment of the present invention 4
The 3- hydroxy-2-naphthoic acid of synthesis/1- perfluoroetane sulfonic acid/LYH complex carries out fluorometric investigation, and fluorescence spectrum is as shown in Figure 5；
(a) is emission spectrum of the 3- hydroxy-2-naphthoic acid sodium salt in formamide solution in Fig. 5, wherein 3- hydroxyl -2-
Naphthoic acid sodium salt is by the way that by 3- hydroxy-2-naphthoic acid and sodium hydroxide, (molar ratio of 3- hydroxy-2-naphthoic acid and sodium hydroxide is
After 1:2) being dissolved in water, solid is precipitated in evaporation solvent, and solid is filtered re-dry and is obtained, by the resulting 3- hydroxyl -2- of 0.025g
Naphthoic acid sodium salt solid is dissolved in progress fluorescence spectrum test in 10ml formamide；(b) is that complex is scattered in formamide glue in Fig. 5
Emission spectrum in shape suspension, wherein formamide colloidal suspensions are by being dispersed in 10ml formamide for 0.025g complex
In and obtain；
From Fig. 5 (a) it is found that 3- hydroxy-2-naphthoic acid sodium salt is in the green emission that liquid is 511nm；(b) can from Fig. 5
To know, when complex is in formamide colloidal suspensions, emission peak is displaced to 478nm, belong to blue emission, blue shift 33nm, and
It was unexpectedly determined that complex chart 5 is it is found that the emissive porwer of 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 achieve 3 times of the latter or so.
By the various embodiments described above it is found that using anion exchange method in this programme, by hydro-thermal reaction by NO3- LYH with
The 3- hydroxy-2-naphthoic acid and 1- perfluoroetane sulfonic acid radical ion of deprotonation combine, and 3- hydroxy-2-naphthoic acid is made to be fixed on LYH laminate
Between, 3- hydroxy-2-naphthoic acid/1- perfluoroetane sulfonic acid/LYH complex is obtained, the fluorescent emission intensity of the complex is apparently higher than 3-
Hydroxy-2-naphthoic acid, therefore can reduce detection limit when detecting 3- hydroxy-2-naphthoic acid using fluorescent spectrometry.
In addition, can use LYH laminate to 3- hydroxyl-between 3- hydroxy-2-naphthoic acid is fixed on LYH laminate by the present invention
2- naphthoic acid is protected, it is possible to further be applied to the guarantor in the synthesis of 3- hydroxy-2-naphthoic acid derivative to organic matter
Shield.
Moreover, with the solution of 3- hydroxy-2-naphthoic acid sodium salt it is luminous compared with, complex provided by the present invention is in colloid
The obvious blue shift of state launch wavelength becomes blue emission from the green light of organic matter, and luminescent color can be regulated and controled by intercalation synthesis, uses
Make Multicolor light-emitting device.
Above to 3- hydroxy-2-naphthoic acid provided by the present invention/1- perfluoroetane sulfonic acid/LYH complex and its synthetic method
It is described in detail.Principle and implementation of the present invention are described for specific embodiment used herein, above
The explanation of embodiment is merely used to help understand method and its central idea of the invention.It should be pointed out that for the general of this field
, without departing from the principle of the present invention, can be with several improvements and modifications are made to the present invention for logical technical staff, 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 acid/1- perfluoroetane sulfonic acid/LYH complex, which is characterized in that there is following below formula composition:
Y(OH)2.5(C11H7O3)x(C8H17O3S)y·zH2O,
Wherein, X=0.07-0.13, y=0.36-0.37, z=1.1-1.7；
The Fluorescence Characteristic of the complex includes: the complex when the complex is scattered in colloidal suspensions
Emit blue light.
2. complex as described in claim 1, which is characterized in that the Fluorescence Characteristic of the complex includes: described multiple
For zoarium compared with 3- hydroxy-2-naphthoic acid sodium salt, the former fluorescent emission intensity is 3 times or so of the latter's fluorescent emission intensity.
3. 3- hydroxy-2-naphthoic acid as described in claim 1/1- perfluoroetane sulfonic acid/LYH complex synthetic method, feature
It is, comprising the following steps:
A) using sodium hydroxide or potassium hydroxide as base reagent, sodium 1-octanesulfonate, base reagent and 3- hydroxy-2-naphthoic acid are dissolved
Yu Shuizhong obtains mixed solution, and wherein the molar ratio of 3- hydroxy-2-naphthoic acid and base reagent is 1:(1-2)；3- hydroxyl -2- naphthalene
The molar 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, at 70-100 DEG C after hydro-thermal reaction 12-24 hours,
Product is post-processed, wherein the sum of molal quantity of 3- hydroxy-2-naphthoic acid and sodium 1-octanesulfonate and NO3- LYH moles
Several ratios is (1.5-6): 1.
4. synthetic method as claimed in claim 3, which is characterized in that in step a), sodium 1-octanesulfonate, base reagent and 3-
The molar ratio of hydroxy-2-naphthoic acid is 3:1:1.
5. synthetic method as claimed in claim 3, which is characterized in that in step b), 3- hydroxy-2-naphthoic acid and 1- octane
The sum of molal quantity of sodium sulfonate and NO3The ratio of-LYH molal quantity is 3:1.
6. synthetic method as claimed in claim 3, which is characterized in that in step a) in obtained mixed solution, 1- is pungent
The concentration of alkyl sulfonic acid sodium is 0.08-0.2mmol/mL.
7. synthetic method as claimed in claim 3, which is characterized in that in step b), by NO3When-LYH is dispersed in water,
NO3The concentration of-LYH is 0.002-0.006mmol/mL.
8. synthetic method as claimed in claim 3, which is characterized in that the post-processing includes: to be filtered, washed, dry.
9. synthetic method as claimed in claim 3, which is characterized in that 3- hydroxy-2-naphthoic acid and sodium 1-octanesulfonate rub
The sum of your number and NO3The ratio of-LYH molal quantity is (2-4): 1.
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| 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 |
| CN105670605A (en) * | 2016-03-14 | 2016-06-15 | 北京师范大学 | Fluorescein/1-octanesulfonate/LYH complex and synthesis method thereof |
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| 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 |
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