CN106432306A - Preparation methods and application of rare earth europium complex and fluorescent foam thereof - Google Patents
Preparation methods and application of rare earth europium complex and fluorescent foam thereof Download PDFInfo
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- CN106432306A CN106432306A CN201610820924.5A CN201610820924A CN106432306A CN 106432306 A CN106432306 A CN 106432306A CN 201610820924 A CN201610820924 A CN 201610820924A CN 106432306 A CN106432306 A CN 106432306A
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Abstract
The invention discloses preparation methods and application of a rare earth europium complex and fluorescent foam thereof. The preparation method of the rare earth europium complex comprises the steps that Phen is adopted as a raw material and reacts with a concentrated acid solution to generate Phen-NO2, Phen-NO2 and hydrazine hydrate react to obtain Phen-NH2, Phen-NH2 and Eu(TTA)3.2H2O are mixed and react, and then the rare earth europium complex Eu(TTA)3.Phen-NH2 is obtained. The rare earth europium complex is dissolved in a DMSO solution, anions and cations are detected through an ion titration method, and the rare earth europium complex has a good recognition function on H2PO4-, CH3COO-, F- and Cu2+. The preparation method of the fluorescent foam of the rare earth europium complex comprises the steps that Eu(TTA)3.Phen-NH2 serves as luminescent molecules to be introduced into a common foamed system of PEG600, open-loop epoxidized soybean oil polyalcohol and MDI, and the fluorescent foam of the rare earth europium complex is prepared. The preparation method of the fluorescent foam is simple, short in reaction time and environmentally friendly, and the recognition function on Cu2+ is good. Compared with a traditional product, due to the fact the amount of foam is large, the specific surface area is large, the single recognition capacity is high, the defect that a traditional fluorescence probe is quenched in an aqueous solution can be overcome, and the fluorescent foam has wide application prospects in the fields of medical treatment, agriculture, food and the like.
Description
Technical field
The invention belongs to and rare earth high polymer composite luminescent material technical field and in particular to a kind of Rare Earth Europium Complex and
The preparation method of its fluorescent foam and application.
Background technology
Rare earth is that a kind of have light, magnetic, the new function material of the multifrequency nature such as electric and biological simultaneously.Rare earth ion because
Have the luminosity of uniqueness for the unique texture of its 4f electronic shell, these unique luminosities make rare earth compound in doctor
The aspects such as treatment, bio-imaging, optical fiber, lighting device are widely used.Rare earth compounding is joined with rare earth ion by part
Position bonding and obtain, its principle of luminosity is part in ultra-violet (UV) band energy absorption, then part in the way of intramolecular charge-transfer transition,
The energy transmission of its excitation state is led to rare earth luminescence to the emission level of rare earth ion.
Although rare earth compounding has the advantages that excitation is high, up to 100% and luminescent lifetime is long for theoretical quantum efficiency,
But the fluorescent emission of rare earth compounding is easily quenched by hydrone.What therefore design synthesis can be done in aqueous for a long time is dilute
Native complex is most important.
This Patent design has synthesized a new europium complex containing amino, then passes through crosslinked method and is become
Work(is incorporated in the polyurethane foam of environment-friendly type, effectively overcomes the deficiency that europium complex fluorescent emission in water is easily quenched.
Further, since this fluorescent foam contain can with zwitterion carry out as site, therefore this foam can be in aqueous
Zwitterion is effectively identified.At present, it is rarely reported for the rare-earth fluorescent foam of main body based on polyurethane, such fluorescence
Foam has multiple advantages such as the good, environmental protection of illumination effect it is often more important that this fluorescent foam probe repeats utilization, use cost
Relatively low.
Content of the invention
There are the problems referred to above for prior art, it is an object of the present invention to provide a kind of preparation of Rare Earth Europium Complex
Method and its application.
It is a further object to provide a kind of simple, workable, high novel fluorescence foam of luminous efficiency
Preparation method and application.
To achieve these goals, the technical solution used in the present invention is as follows：
A kind of preparation method of Rare Earth Europium Complex, described Rare Earth Europium Complex is Eu (TTA)3·Phen-NH2, including
Following steps：
1) by Phen and the concentrated sulfuric acid in molar ratio 1:1～10 dissolving is placed in reflux.
2) adopt oil bath heating reflux, temperature is risen to 130～170 DEG C, then drip concentrated acid solution thereto, and
It is maintained at and carries out back flow reaction 3h at 130～170 DEG C, be cooled to room temperature and obtain reactant liquor.Described concentrated acid solution is the concentrated sulfuric acid
With red fuming nitric acid (RFNA) in molar ratio 1:1～10 is mixed；The usage amount of this concentrated acid solution be step 1) in concentrated sulfuric acid usage amount 2～
8 times.
3) making step 2) reactant liquor that obtains is cooled to room temperature, then pour in frozen water, it is 10%～50% with mass concentration
NaOH solution neutralization reaction liquid to neutral range, obtain the light-yellow precipitate separating out, suction filtration, water carried out to this light-yellow precipitate
Wash, be dried, obtain yellow solid；After ethyl alcohol recrystallization, filtration, the Phen-NO of drying to obtain yellow powder2.
4) by step 3) Phen-NO that obtains2With hydrazine hydrate in molar ratio 1:5～15 mixing, add absolute ethyl alcohol
Make Phen-NO2It is completely dissolved, form mixed solution；This mixed solution is reacted after 2～10h at 30～100 DEG C, stands 10h
Generate precipitation, then will reheat this mixed solution to 30～100 DEG C；When precipitation dissolves again, filter while hot, by filter residue
With absolute ethyl alcohol rinse several times, and by rinse the rinse liquid producing is poured in filtrate.By filtrate with revolving instrument in 60 DEG C of revolvings
Fall solvent, obtain brown solid, take out this brown solid and be dried, then use absolute ethyl alcohol recrystallization purifying, filter, be dried
Afterwards, obtain brown solid powder, i.e. Phen-NH2.
5) by step 4) Phen-NH that obtains2With Eu (TTA)3·2H2O is 1 in molar ratio:1～10 mixing, then use THF
It is dissolved into reaction solution；It is placed on reaction 1～10h at 30～100 DEG C again, is then cooled to room temperature, revolve then at 20～80 DEG C
Evaporate solvent, after drying is processed, obtain red brown solid powder, i.e. Rare Earth Europium Complex Eu (TTA)3·Phen-NH2.
Wherein：Step 1) in Phen and the concentrated sulfuric acid mol ratio 1：5.
Step 2) in back flow reaction temperature be 150 DEG C；Step 2) in dropping concentrated acid solution be the concentrated sulfuric acid and red fuming nitric acid (RFNA)
In molar ratio 1:1 is mixed.
Step 4) in Phen-NO2With hydrazine hydrate in molar ratio 1：8 mixing；, step 4) in mixed solution anti-at 75 DEG C
Answer 3h.
Step 5) in Phen-NH2With Eu (TTA)3·2H2The mol ratio of O is 1：1；, step 5) in reaction solution at 70 DEG C
Lower reaction 3h.
Application in ion detection for the above-mentioned europium complex, will be mixed into detection reagent with DMSO by above-mentioned europium complex,
Using DMSO solution to be detected as test agent to be checked, first measure fluorescent emission intensity value A1 of detection reagent, then by described detection
Reagent and test agent to be checked measure its fluorescent emission intensity value A2 after being mixed, if A2 is less than A1, judge material to be detected
In contain F-、H2PO4 -、CH3COO-.
A kind of preparation method of europium complex fluorescent foam, by the Rare Earth Europium Complex prepared as stated above Eu
(TTA)3·Phen-NH2It is incorporated into the body of the common foaming of PEG600, open loop epoxy soybean oil polyalcohol and MDI as light emitting molecule
In system, prepare europium complex fluorescent foam.
Specifically include following steps：
(1) by open loop polyalcohol and poly- hexylene glycol in molar ratio for 1:1～10 mixing, is simultaneously introduced 01～0.5mL February
Dilaurylate, stirs, and forms mixture.
(2) by Eu (TTA)3·Phen-NH2It is dissolved in appropriate THF, be configured to the solution of 0.5g～2g/L；Again should
Solution is added in the mixture of step (1), obtains mixed material.
(3) mixed material obtaining step (2) is mixed with MDI, and stirs；It is subsequently poured in mould and make it solid
Change, that is, europium complex fluorescent foam is obtained.
Wherein：Open loop polyalcohol described in step (1) is 1 with the mol ratio of poly- hexylene glycol：1.
Application in ion detection for the above-mentioned europium complex fluorescent foam, will be mixed with water above-mentioned europium complex fluorescent foam
It is combined into detection reagent, using the aqueous solution to be detected as test agent to be checked, first measure fluorescent emission intensity value A3 of detection reagent, then
Measure its fluorescent emission intensity value A4 after described detection reagent and test agent to be checked are mixed, if A4 is less than A3, judge
Cu is contained in material to be detected2+.
Compared with prior art, the present invention has the advantages that：
1st, the environment-friendly type fluorescent foam material that the present invention is prepared can effectively overcome europium complex in aqueous
Transmitting is easily quenched and waits deficiency, and prepared fluorescence probe can recycle in aqueous.
2nd, the fluorescent foam of the present invention is stronger to the selection recognition capability of zwitterion, can be effectively to Cu2+Carry out list
One identification.
3rd, the fluorescent foam of the present invention is big compared with gel-like specific surface area, has stronger recognition reaction to zwitterion.
4th, the preparation method that the present invention provides is simple, and workable, the reaction time is short, and environmental protection, is suitable for industry
Produce, all have wide practical use in medical treatment, the field such as agricultural, food.
Brief description
Fig. 1 is Phen, Phen-NO2、Phen-NH2Infrared spectrum；
Fig. 2 is Phen-NH2、Eu(TTA)32H2O、Eu(TTA)3·Phen-NH2Infrared spectrum；
Fig. 3 is Phen-NH2、Eu(TTA)32H2O、Eu(TTA)3·Phen-NH2Fluorescence emission spectrum；
Fig. 4 is the emission spectrum of fluorescent foam；
Fig. 5 is fluorescent foam and Eu (TTA)3·Phen-NH2Thermal gravimetric analysis curve；
Fig. 6 is Eu (TTA)3·Phen-NH2Solution identifies fluorescence Spectra to the selection of anion；
Fig. 7-1 is Eu (TTA)3·Phen-NH2Solution is to CH3COO-Identification fluorescence Spectra；
Fig. 7-2 is Eu (TTA)3·Phen-NH2Solution is to F--Identification fluorescence Spectra；
Fig. 7-3 is Eu (TTA)3·Phen-NH2Solution is to H2PO4 -Identification fluorescence Spectra；
Fig. 8 is Eu (TTA)3·Phen-NH2Solution identifies fluorescence Spectra to the selection of cation；
Fig. 9 is Eu (TTA)3·Phen-NH2Solution is to Cu2+Identification fluorescence Spectra；
Figure 10 is Eu (TTA)3·Phen-NH2Solution identifies ultraviolet spectra to the selection of anion；
Figure 11 is Eu (TTA)3·Phen-NH2Fluorescent foam identifies fluorescence Spectra to the selection of cation；
Figure 12 is Eu (TTA)3·Phen-NH2Fluorescent foam is to Cu2+Identification fluorescence Spectra.
Specific embodiment
With reference to specific embodiment, the present invention is described in further detail.
Embodiment 1
Prepare Rare Earth Europium Complex Eu (TTA) using following methods3·Phen-NH2, its molecular formula is,
Synthetic route is：
Specifically include following steps：
1) 10.0g (55.5mmol) 1,10- Phen (Phen) is taken to put in 250ml there-necked flask, then at three mouthfuls
Add the 15.0mL concentrated sulfuric acid in flask and put into magnetite.
2) there-necked flask iron stand is installed on DF-101S heat collecting type constant-temperature heating magnetic stirring apparatus, burns at three mouthfuls
Install reflux condensing tube additional on bottle, and block remaining two mouthfuls of there-necked flask with glass stopper.Setting oil bath temperature is 150 DEG C and stirs,
When temperature reaches design temperature, add in there-necked flask and be slowly dropped into volume ratio for 1:1 concentrated sulfuric acid is mixed with red fuming nitric acid (RFNA)
Thing 60ml (system temperature during dropping mixture should control below 170 DEG C).It is then refluxed for reacting 3h, reaction takes after terminating
Go out there-necked flask and naturally cool to room temperature by it.
3) again the liquid in there-necked flask is added in the deionized water of ice.Then with concentration be 30% NaOH solution in
It is 6.0 about with being titrated to pH value.Now separate out light-yellow precipitate, then pass through suction filtration, wash, be dried to obtain yellow solid.
Use ethyl alcohol recrystallization yellow solid, obtain 2.2g yellow powder after filtration drying, this powder is 5- nitro -1,10- is adjacent
Phenanthroline (Phen-NO2), yield is 24%.
4) weigh 0.64g (6.0mmol) 10% palladium/carbon as catalyst, 4.85g 80% (mass fraction) hydrazine hydrate
Add in 250mL there-necked flask with 20.0mL absolute ethyl alcohol, there-necked flask iron stand is installed to DF-101S heat collecting type constant temperature
On heating magnetic stirring apparatus, there-necked flask installs reflux condensing tube additional, and block remaining two mouthfuls of there-necked flask with glass stopper.If
Put oil bath temperature to be 72 DEG C and stir, now weigh 2.03g (9mmol) 5- nitro -1,10- Phen loads there-necked flask
In, be subsequently adding 40mL absolute ethyl alcohol and make its fully dissolve (total addition of absolute ethyl alcohol to be completely dissolved 5- nitro -1,
10- Phen is defined).When oil bath temperature reaches design temperature, the solution having dissolved is poured into rapidly in there-necked flask.Instead
After answering 10h, then stand about 10h, then oil bath pan is warming up to again 60 DEG C, after the precipitation in reaction system dissolves again,
Take off there-necked flask at once and pour out solution and filter while hot, filter residue absolute ethyl alcohol rinse 5 times about.Filtrate is taken to use revolving instrument
Revolving falls solvent, obtains brown solid, takes out after brown solid with 60 DEG C of dryings of vacuum drying oven 12 hours, finally with anhydrous
Ethyl alcohol recrystallization purified product, filters, and 60 DEG C are vacuum dried 12 hours, obtain 1.28g brown solid powder, this powder is
5- amino -1,10- Phen (Phen-NH2), yield is 72.9%.
B in Fig. 1 is 5- nitro -1, the infrared spectrogram of 10- Phen, and we will become apparent from B figure in 1286cm-1Place
There is absworption peak, this is-NO2Stretching vibration characteristic peak, in figure, 1618cm-1、1501cm-1、1444cm-1Absworption peak at three
Stretching vibration characteristic peak for C=C, and the flexural vibrations characteristic peak of c h bond occurs in 902cm-1, 828cm-1, 729cm-1Three
Place.Contrast Fig. 1 in C (infrared spectrogram of 1,10- Phen) it was demonstrated that 5- nitro -1 has been synthesized by 1,10- Phen,
10- Phen.In Fig. 1, A is 5- amino -1, the infrared spectrogram of 10- Phen, and from figure, we will become apparent from
3326cm-1And 3207cm-1There is absworption peak at place, and this is the stretching vibration characteristic peak of N-H, and in 1642cm-1And 1587cm-1Place goes out
The characteristic peak of C=N double bond, 1249cm are showed-1The absworption peak at place is the characteristic peak of C-N, and contrasts the B in Fig. 1, thus demonstrating
5- amino -1,10- Phen has been synthesized by 5- nitro -1,10- Phen.
5) 0.391g (0.002mol) 5- amino -1,10- Phen and 1.695g (0.002mol) Eu are weighed
(TTA)3·2H2O, by the two with pouring in beaker and (for ensureing dissolving fully, permissible with 50mL oxolane (THF) dissolving
It is made to dissolve fully with supersonic wave cleaning machine ultrasonic half an hour), it is subsequently poured in single-necked flask, flask iron stand is installed to
On DF-101S heat collecting type constant-temperature heating magnetic stirring apparatus additional, reflux condensing tube is installed on there-necked flask, setting oil bath temperature is 70
DEG C, use moderate-speed mixer.After reaction 3h, take out flask and be cooled to room temperature, then fall solvent, setting rotation using revolving instrument vacuum distillation
Steam temperature and be 50 DEG C.When solvent by gradually revolving is fallen after, gradually separate out red brown solid.Then using 60 DEG C of vacuum drying chamber
It is dried 12 hours, obtain 1.873g red brown solid powder, this pressed powder is Eu (TTA)3·Phen-NH2, yield 92.7%.
Example 2 is to example 4
Using preparation method same as Example 1, except for the difference that step 4) in hen-NH2With Eu (TTA)3·2H2O's
Mol ratio, the usage amount of THF, reaction temperature and reaction time, concrete such as table 1：
Table 1
| THF consumption | Reaction temperature | Reaction time | Phen-NH2With Eu (TTA)3·2H2The mol ratio of O | |
| Embodiment 2 | 45 | 60 | 2 | 1:1 |
| Embodiment 3 | 55 | 75 | 3 | 1:2 |
| Embodiment 4 | 65 | 85 | 4 | 1:3 |
In fig. 2, A and C is in 3328cm-1And 3218cm-1There is absworption peak at place, and this is obvious N-H stretching vibration peak, says
Bright have same amino in Fig. 2A and 4C, and A and C is in 1662cm-1There is absworption peak at place, and this is the stretching vibration spy of C=N double bond
Levy peak, these all illustrate to contain Phen-NH in C2Characteristic peak.Because itself contains the water of coordination in B,
3412cm-1The characteristic absorption peak of place's hydroxyl, and in C, there is no identical broad peak, in 1609cm-1Place exists and B identical C=O
The stretching vibration peak of key, this is the carbonyl peak of TTA.It is 575cm in wavelength-1Place, B and C all occurs in that Eu3+Characteristic peak, these
All demonstrate achievement and synthesize complex Eu (TTA)3·Phen-NH2But, substantially find, complex Eu (TTA)3·Phen-
NH2In 575cm-1The absworption peak at place is compared with Eu (TTA)32H2O weakens, and this is likely due to as Eu (TTA)32H2O and Phen-NH2Join
Behind position, to Eu3+Absworption peak weakened.
In figure 3, it is respectively from left to right5D0→7F1、5D0→7F2、5D0→7F3、5D0→7F4Transition emission peak.?
Emission peak at 616nm is the strongest, and its corresponding transition emission peak is hypersensitive transition emission peak, belongs to magnetic dipole transition, here
In transition process, europium complex sends ruddiness.Can clearly find, monomer 5- amino -1,10- Phen in wavelength is
There is no emission peak at 616nm.When it is with europium complex Eu (TTA)32H2Hence it is evident that in 616nm after O cooperatively forms new part
Place occurs in that the characteristic emission peak of rare earth ion europium.It can be seen that working as Eu (TTA)32H2O and monomer Phen-NH2Formed
After complex, its emissive porwer at 616nm decreases.
As shown in Fig. 6,7-1,7-2,7-3, when respectively to europium complex Eu (TTA)3·Phen-NH2Solution titrates 8 equivalents
The DMSO solution of different anions when, F-、H2PO4 -、CH3COO-Fluorescence intensity at 616nm drastically declines, and titrates it
Change after him is negligible, this explanation europium complex Eu (TTA)3·Phen-NH2Solution is can be to F-、H2PO4 -、
CH3COO-It is identified.
As shown in Fig. 8,11, when respectively to europium complex Eu (TTA)3·Phen-NH2Solution titrate the different sun of 8 equivalents from
During the ethanol solution of daughter ion, Cu2+Fluorescence intensity at 616nm drastically declines, this explanation Eu (TTA)3·Phen-
NH2Solution can be to Cu2+It is identified.
Thus, it is possible to prove europium complex in ion detection, can preferably identification F-、H2PO4 -、CH3COO-And Cu2+,
All have wide application prospects in medical treatment, the field such as agricultural, food.
Embodiment 5
Prepare europium complex fluorescent foam (being doped with the polyurethane fluorescent foam of europium complex) using following methods, can adopt
The Rare Earth Europium Complex Eu (TTA) being prepared with embodiment 1-43·Phen-NH2As light emitting molecule.
(1) weigh 2.69g (0.0025mol) open loop epoxy soybean oil polyalcohol, 1.50g (0.0025mol) polyethylene glycol,
0.1mL dibutyl tin laurate, stirs, and forms mixture.
(2) weigh the Eu (TTA) of 0.028g3·Phen-NH2, and with a small amount of tetrahydrofuran solution dissolving, make Eu
(TTA)3·Phen-NH2Content is 0.5% europium complex solution, then adds together with mixture in plastic cup, and stirring is all
Even.
(3) it is subsequently adding 1.35g (0.005mol) MDI (methyl diphenylene diisocyanate) and stir rapidly three minutes left sides
The right side, now in plastic cup, mixture temperature is significantly raised, and viscosity becomes big.Finally mixing liquid is poured in mould, and at 60 DEG C
Baking oven in solidify half an hour.
Prepare doping europium complex Eu (TTA) by above-mentioned identical experimental technique3·Phen-NH2Content is 0.5%,
1%, 1.5%, 3%, 5% fluorescent foam, from Fig. 4, we are it can clearly be seen that this five fluorescent foams are in λem=616nm
The fluorescence intensity at place strengthens with the increase of europium complex doping.
If Fig. 5 is the TGA curve of europium complex and its fluorescent foam, the heat that we can see that europium complex from figure is divided
Solution is divided into three sections, and about to 236 DEG C, this stage may be the volatilization that water and remaining difficulty wave solvent to first paragraph, and second stage is about
Terminate to 310 DEG C, from the point of view of percent weight loss, this section accounts for overall 15%, from the point of view of the mass fraction of complex, this section
It is possible for Phen-NH2Decomposition, the 3rd section of stage to 394 DEG C about terminate to be probably the decomposition of TTA, finally for europium
The thermal decomposition of compound, remaining about 40% quality is the oxide of europium.Because being that europium complex is doped to polyurethane foam
In foam matrix, and measure seldom, therefore several foams all are starting to thermally decompose at 158 DEG C about.Foam after doping, relatively undopes
Foam slightly have a little decomposition change when 310 DEG C, and increasing with doping quality, change is more obvious, and this phenomenon should
Related to europium complex.From this, this fluorescent foam the following is more stable at 150 DEG C, can meet in uniform temperature
Under the conditions of use.
Embodiment 6 is to embodiment 8
The method preparing europium complex fluorescent foam is same as Example 5, and except for the difference that in step (1), PEG is many with open loop
THF and Rare Earth Europium Complex Eu (TTA) in the mol ratio of first alcohol, step (2)3·Phen-NH2Mol ratio, concrete as table 2：
Table 2
| PEG and open loop polyol mole ratio | THF and Rare Earth Europium Complex mol ratio | |
| Embodiment 6 | 1:2 | 0.1:1 |
| Embodiment 7 | 1:3 | 0.3:1 |
| Embodiment 8 | 1:4 | 0.7:1 |
As shown in Figure 10, after being respectively dropped into the different anions solution of 8 equivalents, find the H at 345nm2PO4- extinction
Degree change is obvious, and the change of other ions change is less, therefore passes through Eu (TTA)3·Phen-NH2The ultraviolet spectra of solution, can
With to H2PO4 -It is identified.
As shown in Figure 11,12, after instilling the aqueous solution of different ions of 8 equivalents, Cu2+Fluorescence intensity occur larger under
Fall, and the change of other ions is trickle, it is therefore believed that Eu (TTA)3·Phen-NH2Fluorescent foam is to Cu2+Have preferably
Recognition reaction.
Thus, it is possible to prove that the europium complex fluorescent foam of present invention preparation, in ion detection, can identify well
Cu2+, all have wide application prospects in medical treatment, the field such as agricultural, food.
The above embodiment of the present invention only example to illustrate the invention, and it is not the enforcement to the present invention
The restriction of mode.For those of ordinary skill in the field, can also be made other not on the basis of the above description
Change and variation with form.Here all of embodiment cannot be exhaustive.Every belong to technical scheme
The obvious change amplified out or change the row still in protection scope of the present invention.
Claims (10)
1. a kind of preparation method of Rare Earth Europium Complex is it is characterised in that described Rare Earth Europium Complex is Eu (TTA)3·
Phen-NH2, comprise the following steps：
1）By Phen and the concentrated sulfuric acid in molar ratio 1:1～10 dissolving is placed in reflux；
2）Using oil bath heating reflux, temperature is risen to 130～170 DEG C, then drip concentrated acid solution thereto, and keep
Carry out back flow reaction 3h at 130～170 DEG C, be cooled to room temperature and obtain reactant liquor；
Described concentrated acid solution is the concentrated sulfuric acid and red fuming nitric acid (RFNA) in molar ratio 1:1～10 is mixed；The usage amount of this concentrated acid solution is
Step 1）2 ~ 8 times of middle concentrated sulfuric acid usage amount；
3）Make step 2）The reactant liquor obtaining is cooled to room temperature, then pours in frozen water, the NaOH being 10%～50% with mass concentration
Solution neutralization reaction liquid, to neutral range, obtains the light-yellow precipitate separating out, and this light-yellow precipitate is carried out with suction filtration, washing, does
Dry, obtain yellow solid；After ethyl alcohol recrystallization, filtration, the Phen-NO of drying to obtain yellow powder2；
4）By step 3）The Phen-NO obtaining2With hydrazine hydrate in molar ratio 1:5～15 mixing, adding absolute ethyl alcohol makes
Phen-NO2It is completely dissolved, form mixed solution；This mixed solution is reacted after 2～10h at 30～100 DEG C, standing 10h life
Become precipitation, then will reheat this mixed solution to 30～100 DEG C；When precipitation dissolves again, filter while hot, filter residue is used
Several times, and the rinse liquid that rinse is produced is poured in filtrate for absolute ethyl alcohol rinse；
Filtrate is fallen solvent with revolving instrument in 60 DEG C of revolvings, obtains brown solid, take out this brown solid and be dried, then use
Absolute ethyl alcohol recrystallization purifying, after filtration, drying, obtains brown solid powder, i.e. Phen-NH2；
5）By step 4）The Phen-NH obtaining2With Eu (TTA)3·2H2O is 1 in molar ratio:1～10 mixing, then dissolved with THF
Become reaction solution；It is placed on reaction 1～10h at 30～100 DEG C again, be then cooled to room temperature, fall then at 20～80 DEG C of revolvings
Solvent, after drying is processed, obtains red brown solid powder, i.e. Rare Earth Europium Complex Eu (TTA)3·Phen-NH2.
2. the preparation method of Rare Earth Europium Complex according to claim 1 is it is characterised in that step 1）Middle Phen and dense sulphur
The mol ratio 1 of acid：5.
3. the preparation method of Rare Earth Europium Complex according to claim 1 is it is characterised in that step 2）Middle back flow reaction
Temperature is 150 DEG C；Step 2）The concentrated acid solution of middle dropping is the concentrated sulfuric acid and red fuming nitric acid (RFNA) in molar ratio 1:1 is mixed.
4. the preparation method of Rare Earth Europium Complex according to claim 1 is it is characterised in that step 4）Middle Phen-NO2With
Hydrazine hydrate in molar ratio 1：8 mixing；, step 4）Middle mixed solution reacts 3h at 75 DEG C.
5. the preparation method of Rare Earth Europium Complex according to claim 1 is it is characterised in that step 5）Middle Phen-NH2With
Eu(TTA)3·2H2The mol ratio of O is 1：1；, step 5）Middle reaction solution reacts 3h at 70 DEG C.
6. application in ion detection for a kind of europium complex.
7. a kind of preparation method of europium complex fluorescent foam is it is characterised in that the Rare Earth Europium Complex of preparing claim 1
Eu(TTA)3·Phen-NH2It is incorporated into the common foaming of PEG600, open loop epoxy soybean oil polyalcohol and MDI as light emitting molecule
In system, prepare europium complex fluorescent foam.
8. the preparation method of fluorescent foam according to claim 7 is it is characterised in that comprise the following steps：
（1）Open loop polyalcohol and poly- hexylene glycol are 1 in molar ratio:1～10 mixing, is simultaneously introduced 01 ~ 0.5mL tin dilaurate two
Butyl tin, stirs, and forms mixture；
（2）By Eu (TTA)3·Phen-NH2It is dissolved in appropriate THF, be configured to the solution of 0.5g～2g/L；Again that this is molten
Liquid is added to step（1）Mixture in, obtain mixed material；
（3）By step（2）The mixed material obtaining is mixed with MDI, and stirs；It is subsequently poured in mould and so that it is solidified, that is,
Prepared europium complex fluorescent foam.
9. the preparation method of europium complex fluorescent foam according to claim 8 is it is characterised in that step（1）Described in
The mol ratio of open loop polyalcohol and poly- hexylene glycol be 1：1.
10. application in ion detection for a kind of europium complex fluorescent foam.
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