CN105693532B - A kind of preparation method of the ammonium carboxylate salt with fluorescence - Google Patents
A kind of preparation method of the ammonium carboxylate salt with fluorescence Download PDFInfo
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- CN105693532B CN105693532B CN201610037911.0A CN201610037911A CN105693532B CN 105693532 B CN105693532 B CN 105693532B CN 201610037911 A CN201610037911 A CN 201610037911A CN 105693532 B CN105693532 B CN 105693532B
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- carboxylate salt
- ammonium carboxylate
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- carboxylic acid
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- -1 ammonium carboxylate salt Chemical class 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003208 petroleum Substances 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000012153 distilled water Substances 0.000 claims abstract description 15
- 230000010355 oscillation Effects 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 11
- 150000001412 amines Chemical class 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 239000011833 salt mixture Substances 0.000 claims abstract description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 22
- 229960001484 edetic acid Drugs 0.000 claims description 22
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 15
- 150000002500 ions Chemical class 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims 4
- 238000002604 ultrasonography Methods 0.000 claims 1
- 230000005284 excitation Effects 0.000 abstract description 9
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract description 8
- 229910001447 ferric ion Inorganic materials 0.000 abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 6
- 230000007423 decrease Effects 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 23
- 239000000203 mixture Substances 0.000 description 18
- 239000007788 liquid Substances 0.000 description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 7
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 6
- AKYHKWQPZHDOBW-UHFFFAOYSA-N (5-ethenyl-1-azabicyclo[2.2.2]octan-7-yl)-(6-methoxyquinolin-4-yl)methanol Chemical compound OS(O)(=O)=O.C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 AKYHKWQPZHDOBW-UHFFFAOYSA-N 0.000 description 5
- 239000001576 FEMA 2977 Substances 0.000 description 5
- LOUPRKONTZGTKE-UHFFFAOYSA-N cinchonine Natural products C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-UHFFFAOYSA-N 0.000 description 5
- 229960003110 quinine sulfate Drugs 0.000 description 5
- 239000013558 reference substance Substances 0.000 description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 4
- 238000006862 quantum yield reaction Methods 0.000 description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 3
- 229960004106 citric acid Drugs 0.000 description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- BYURCDANQKFTAN-UHFFFAOYSA-N n'-(3-dimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[SiH](OC)CCCNCCN BYURCDANQKFTAN-UHFFFAOYSA-N 0.000 description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000695 excitation spectrum Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- JFCSMCOOWAPNFY-UHFFFAOYSA-N C=C.C(CC(O)(C(=O)O)CC(=O)O)(=O)O Chemical group C=C.C(CC(O)(C(=O)O)CC(=O)O)(=O)O JFCSMCOOWAPNFY-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229960004543 anhydrous citric acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002284 excitation--emission spectrum Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
-
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
- C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C211/09—Diamines
- C07C211/10—Diaminoethanes
-
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
- C07C229/10—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
- C07C229/16—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of hydrocarbon radicals substituted by amino or carboxyl groups, e.g. ethylenediamine-tetra-acetic acid, iminodiacetic acids
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/235—Saturated compounds containing more than one carboxyl group
- C07C59/245—Saturated compounds containing more than one carboxyl group containing hydroxy or O-metal groups
- C07C59/265—Citric acid
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
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Abstract
The present invention provides a kind of preparation methods of ammonium carboxylate salt with fluorescence; steps are as follows: carboxylic acid and organic amine are dissolved in distilled water; it is placed in tool plug flask under nitrogen protection; ultrasonic oscillation extremely dissolves; at 0 DEG C ~ 30 DEG C; it is stirred to react 12 ~ 36h, obtains the aqueous solution that main component is ammonium carboxylate salt mixture；After being washed the aqueous solution of ammonium carboxylate salt mixture three times with petroleum ether, water phase vacuum rotary steam is obtained to the ammonium carboxylate salt with fluorescence；Ammonium carboxylate salt prepared by the present invention, preparation method is simple, and yield is high, has excellent fluorescence property, while with the variation of excitation wavelength, launch wavelength also changes therewith, has excitation wavelength dependence.And there is good identification to ferric ion, the decline of the concentration and fluorescence intensity of iron ion shows linear relationship.
Description
Technical field
The present invention relates to a kind of methods of ammonium carboxylate salt using carboxylic acid and organic amine as raw material preparation with fluorescence.
Background technique
The substance with fluorescence can be roughly divided into two kinds at present.One kind is due to having conjugation heterocycle and various lifes in molecule
Color group changes its conjugate length by introducing the fluorescence properties unsaturated groups such as ethylene linkage, phenyl ring and various chromophores, to make
The compound optoelectronic property changes.It is another then be amide, secondary amine or the tertiary amine in molecule with atypia chromophore
Dendrimer or supramolecular structure.It yet there are no the report in structure without chromophore with the ammonium carboxylate salt of photoluminescent property
Road.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of preparation methods of ammonium carboxylate salt with fluorescence.
Technical scheme is as follows:
A kind of preparation method of the ammonium carboxylate salt with fluorescence, steps are as follows:
1) carboxylic acid and organic amine are dissolved in distilled water, are placed in tool plug flask under nitrogen protection, ultrasonic oscillation is extremely
Dissolution, at 0 DEG C ~ 30 DEG C, is stirred to react 12 ~ 36h, obtains the aqueous solution that main component is ammonium carboxylate salt mixture；
2) after being washed the aqueous solution of ammonium carboxylate salt mixture three times with petroleum ether, water phase vacuum rotary steam is obtained having glimmering
The ammonium carboxylate salt of light.
Above-mentioned steps 1) in the preferred acetic acid of carboxylic acid, ethylenediamine tetra-acetic acid, citric acid, ethanedioic acid, succinic acid, glutaric acid,
Adipic acid, pimelic acid.
Above-mentioned steps 1) in the preferred ethylenediamine of organic amine, aminoethylaminopropyl dimethoxysilane, diethylamine, ethamine,
Allylamine.
Above-mentioned steps 1) in the molar ratio of preferred carboxylic acid and organic amine be 1:(0.5 ~ 1.5) n, wherein n is in carboxylic acid
The number of-COOH.Under this ratio, reaction is mildly and the usage amount of solvent is moderate.
Above-mentioned steps 1) in the mass ratio of distilled water and carboxylic acid be (5 ~ 50): 1.
Above-mentioned steps 1) in, ultrasonic oscillation time 5min ~ 60min.
Above-mentioned steps 2) in preferred ammonium carboxylate salt mixture aqueous solution and petroleum ether volume ratio be 1:(2 ~ 4), the ratio
Under example, petroleum ether dosage is moderate, and can clean up amino-compound unreacted in reaction system.
Above-mentioned steps 2) obtained in ammonium carboxylate salt be colorless and transparent solid, be dissolved in distilled water for amber transparent liquid,
Under the ultraviolet light irradiation of 365nm, fluorescence color is blue.
The ammonium carboxylate salt can be used for ion identification.
The excellent results of the method for the present invention are as follows:
1, preparation method of the present invention is simple, can be obtained by lower temperature and in the short period with fluorescence spy
Property ammonium carboxylate salt, color have excitation wavelength dependence；
2, preparation method of the present invention is simple, is easily purified.At low cost, solvent is recyclable to be recycled.What is obtained is glimmering
Light ammonium carboxylate salt is soluble easily in water, and wherein ethylenediamine tetra-acetic acid second di-ammonium salts can be used for Fe in water phase3+Ion identification has wide
Application prospect.
Detailed description of the invention
Fig. 1 be embodiment 1 prepare the ethylenediamine tetra-acetic acid second di-ammonium salts with fluorescence daylight under photo (left side),
Photo (right side) under 365nm is ultraviolet.
Fig. 2 is the formation schematic diagram of the ethylenediamine tetra-acetic acid second di-ammonium salts with fluorescence prepared by embodiment 1.
Fig. 3 is absorption spectrum, the excitation spectrum of the ethylenediamine tetra-acetic acid second di-ammonium salts with fluorescence prepared by embodiment 1
And emission spectrum.
Fig. 4 is the ethylenediamine tetra-acetic acid second di-ammonium salts with fluorescence of the preparation of embodiment 1 under different excitation wavelengths
Emission spectrum.
Fig. 5 is the nucleus magnetic hydrogen spectrum figure of the ethylenediamine tetra-acetic acid second di-ammonium salts with fluorescence prepared by embodiment 1.
Fig. 6 is the ethylenediamine tetra-acetic acid second di-ammonium salts with fluorescence of the preparation of embodiment 1 to Fe3+The fluorescence of ion identification
Spectrogram.
Fig. 7 be embodiment 1 prepare the ethylenediamine tetra-acetic acid second di-ammonium salts with fluorescence relative intensity of fluorescence with it is right
Fe3+Concentration linear relationship figure, I0It is respectively Fe with I3+Fluorescence intensity of the ion the absence and presence of under.
Specific embodiment
Below with reference to embodiment, the present invention will be further described, but not limited to this.
Raw materials used acetic acid in embodiment, ethylenediamine tetra-acetic acid, citric acid, ethanedioic acid, succinic acid, glutaric acid, adipic acid,
(organic amine of yl moiety has been directed in embodiment, reads and makes comments format for pimelic acid, ethylenediamine, diethylamine, ethamine, allylamine
), aminoethylaminopropyl dimethoxysilane and petroleum ether be commercially available.
Embodiment 1
The preparation of fluorescence ethylenediamine tetra-acetic acid-second di-ammonium salts, steps are as follows:
1) 1g ethylenediamine tetra-acetic acid and 0.4109g ethylenediamine are dissolved in 5ml distilled water, and it is true to be placed in solution under nitrogen protection
In empty bottle, sonic oscillation 10min to raw material all dissolves the clear solution that becomes colorless, this device is placed in 30 DEG C of environment and is stirred
12h, solution become amber transparent liquid, obtain mixture I；
2) after being washed mixture I three times with petroleum ether, vacuum rotary steam removes water and petroleum ether obtains transparent solid, obtains
Ethylenediamine tetra-acetic acid with fluorescence-second di-ammonium salts salt.
Fig. 1 ~ Fig. 3 characterizes ethylenediamine tetra-acetic acid-second di-ammonium salts photoluminescent property.Fig. 1 is ethylenediamine tetra-acetic acid-second diammonium
Photo of the salting liquid under natural light (left side) and ultraviolet light (right side).Fig. 2 is the ethylenediamine tetra-acetic acid with fluorescence-second di-ammonium salts
Absorption spectrum, excitation spectrum and emission spectrum.Best excitation and launch wavelength are in 320nm and 424nm.Fig. 3 is that it swashs in difference
Send out the emission spectrum under wavelength (excitation wavelength difference is 10nm).Using quinine sulfate as reference substance, fluorescence quantum yield 2.1%.
Fig. 4 is transmitting light of the ethylenediamine tetra-acetic acid second di-ammonium salts with fluorescence of preparation under different excitation wavelengths
Spectrum.
The Fe of fluorescence ethylenediamine tetra-acetic acid second di-ammonium salts3+Ion identification, steps are as follows:
Take 2ml 10-5The aqueous solution of the ethylenediamine tetra-acetic acid second di-ammonium salts of M, by 10-2The Fe of M3+20 additions of ion point,
20 μ L are added every time, while carrying out fluorometric investigation.Fig. 5 is ethylenediamine tetra-acetic acid-second di-ammonium salts to Fe3+The fluorescence of ion identification
Spectrogram.
Fig. 6 is for the relative intensity of fluorescence of ethylenediamine tetra-acetic acid second di-ammonium salts and to Fe3+Concentration linear relationship figure, I0And I
Respectively Fe3+Fluorescence intensity of the ion the absence and presence of under.
Embodiment 2
The preparation of fluorescence ethylenediamine tetra-acetic acid-second diammonium ammonium carboxylate salt, steps are as follows:
1,1g ethylenediamine tetra-acetic acid and 0.4109g ethylenediamine are dissolved in 5ml distilled water, and it is true to be placed in solution under nitrogen protection
In empty bottle, sonic oscillation to raw material all dissolves the clear solution that becomes colorless, this device is placed in 0 DEG C of environment and stirs 36h, molten
Liquid becomes amber transparent liquid, obtains mixture I；
2, after being washed mixture I three times with petroleum ether, vacuum rotary steam removes water and petroleum ether obtains transparent solid, obtains
Ammonium carboxylate salt with fluorescence.
Products therefrom characterization is similar to example 1.
Embodiment 3
The preparation of fluorescence ethylenediamine tetra-acetic acid-ethamine ammonium carboxylate salt, steps are as follows:
1,1g ethylenediamine tetra-acetic acid and 0.616g ethamine are dissolved in 5ml distilled water, are placed in solution vacuum under nitrogen protection
In bottle, sonic oscillation to raw material all dissolves the clear solution that becomes colorless, this device is placed in 30 DEG C of environment and stirs 12h, molten
Liquid becomes amber transparent liquid, obtains mixture I；
2, after being washed mixture I three times with petroleum ether, vacuum rotary steam removes water and petroleum ether obtains transparent solid, obtains
Ammonium carboxylate salt with fluorescence.
Its photoluminescent property is similar to example 1.
Embodiment 4
The preparation of fluorescence ethylenediamine tetra-acetic acid-diethylamine ammonium carboxylate salt, steps are as follows:
1,1g ethylenediamine tetra-acetic acid and 1.1g diethylamine are dissolved in 5ml distilled water, are placed in solution vacuum under nitrogen protection
In bottle, sonic oscillation to raw material all dissolves the clear solution that becomes colorless, this device is placed in 30 DEG C of environment and stirs 12h, molten
Liquid becomes amber transparent liquid, obtains mixture I；
2, after being washed mixture I three times with petroleum ether, vacuum rotary steam removes water and petroleum ether obtains transparent solid, obtains
Ammonium carboxylate salt with fluorescence.
Products therefrom characterization is similar to example 1.
Embodiment 5
The preparation of fluorescence ethylenediamine tetra-acetic acid-allylamine ammonium carboxylate salt, steps are as follows:
1,1g ethylenediamine tetra-acetic acid and 0.7808g allylamine are dissolved in 5ml distilled water, and it is true to be placed in solution under nitrogen protection
In empty bottle, sonic oscillation to raw material all dissolves the clear solution that becomes colorless, this device is placed in 30 DEG C of environment and stirs 12h,
Solution becomes amber transparent liquid, obtains mixture I；
2, after being washed mixture I three times with petroleum ether, vacuum rotary steam removes water and petroleum ether obtains transparent solid, obtains
Ammonium carboxylate salt with fluorescence.
Products therefrom characterization is similar to example 1.
] embodiment 6
The preparation of fluorescence Citrate-ethylene diamine ammonium carboxylate salt, steps are as follows:
1,1g anhydrous citric acid and 0.625g ethylenediamine are dissolved in 5ml distilled water, are placed in solution vacuum under nitrogen protection
In bottle, sonic oscillation to raw material all dissolves the clear solution that becomes colorless, this device is placed in 30 DEG C of environment and stirs 12h, molten
Liquid becomes amber transparent liquid, obtains mixture I.
2, after being washed mixture I three times with petroleum ether, vacuum rotary steam removes water and petroleum ether obtains transparent solid, obtains
Ammonium carboxylate salt with fluorescence.
Products therefrom characterization is similar to example 1, using quinine sulfate as reference substance, obtains the fluorescence quantum yield of ammonium carboxylate salt
It is 3.67%.
Embodiment 7
The preparation of fluorescence succinic acid-ethylenediamine ammonium carboxylate salt, steps are as follows:
1,1g succinic acid and 0.5136g ethylenediamine are dissolved in 5ml distilled water, are placed in solution Dewar bottle under nitrogen protection
In, sonic oscillation to raw material all dissolves the clear solution that becomes colorless, this device is placed in 30 DEG C of environment and stirs 5h, and solution becomes
For amber transparent liquid, mixture I is obtained；
2, after being washed mixture I three times with petroleum ether, vacuum rotary steam removes water and petroleum ether obtains transparent solid, obtains
Ammonium carboxylate salt with fluorescence.
Products therefrom characterization is similar to example 1, and using quinine sulfate as reference substance, the fluorescent quantum for obtaining ammonium carboxylate salt object is produced
Rate is 8.67%.
Embodiment 8
The preparation of fluorescence acetic acid-ethylenediamine ammonium carboxylate salt, steps are as follows:
1,1.5ml acetic acid and 1.5ml ethylenediamine are dissolved in 5ml distilled water, are placed in solution Dewar bottle under nitrogen protection,
Sonic oscillation to raw material all dissolves the clear solution that becomes colorless, this device is placed in 30 DEG C of environment and stirs 12h, solution becomes
Yellow transparent liquid obtains mixture I；
2, after being washed mixture I three times with petroleum ether, vacuum rotary steam removes water and petroleum ether obtains yellow transparent solid body,
Obtain the ammonium carboxylate salt with fluorescence.
Products therefrom characterization is similar to example 1, using quinine sulfate as reference substance, obtains the fluorescence quantum yield of ammonium carboxylate salt
It is 17.8%.
Embodiment 9
The preparation of fluorescence citric acid-aminoethylaminopropyl dimethoxysilane ammonium carboxylate salt, steps are as follows:
1,1g citric acid and 3.218g aminoethylaminopropyl dimethoxysilane are dissolved in 10ml distilled water, in nitrogen protection
Under be placed in solution Dewar bottle, all dissolution becomes colorless clear solution sonic oscillation to raw material, this device is placed in 30 DEG C of rings
Stir 6h in border, solution becomes colorless transparency liquid, obtains mixture I；
2, after being washed mixture I three times with petroleum ether, vacuum rotary steam removes water and petroleum ether obtains colorless and transparent solid,
Obtain the ammonium carboxylate salt with fluorescence.
Products therefrom characterization is similar to example 1, using quinine sulfate as reference substance, obtains the fluorescence quantum yield of ammonium carboxylate salt
It is 0.8%.
Ammonium carboxylate salt prepared by the present invention with blue-fluorescence, preparation method is simple, and yield is high, has excellent fluorescence
Performance issues blue-fluorescence under the ultraviolet light irradiation of 365nm.Simultaneously with excitation wavelength variation, launch wavelength also with
Variation, have excitation wavelength dependence.And there is good identification, the concentration and fluorescence of iron ion to ferric ion
The decline of intensity shows linear relationship, this has great importance for accurate detection ferric ion.
Claims (4)
1. a kind of application of ammonium carboxylate salt as fluorescent material, which is characterized in that the ammonium carboxylate salt uses following methods system
At:
1) carboxylic acid and organic amine are dissolved in distilled water, are placed in tool plug flask under nitrogen protection, ultrasonic oscillation to dissolution,
At 0 DEG C ~ 30 DEG C, it is stirred to react 12 ~ 36hr, obtains the aqueous solution that main component is ammonium carboxylate salt mixture；
2) after being washed the aqueous solution of ammonium carboxylate salt mixture three times with petroleum ether, water phase vacuum rotary steam is obtained having fluorescence
Ammonium carboxylate salt, structural formula are
Carboxylic acid in the step 1) is ethylenediamine tetra-acetic acid；Organic amine in the step 1) is ethylenediamine；
The molar ratio of carboxylic acid and organic amine is 1:(2 ~ 6 in step 1))；
The mass ratio of distilled water and carboxylic acid is (5 ~ 50) in step 1): 1.
2. application of the ammonium carboxylate salt according to claim 1 as fluorescent material, which is characterized in that in step 1), ultrasound
Wave shakes time 5min ~ 60min.
3. application of the ammonium carboxylate salt according to claim 1 as fluorescent material, which is characterized in that in step 2, mixing
The aqueous solution and petroleum ether volume ratio of object are 1:(2 ~ 4).
4. application of the ammonium carboxylate salt according to claim 1 to 3 as fluorescent material, which is characterized in that the carboxylic acid ammonium
Salt is for Fe in water phase3+Ion identification.
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