CN103642485A - Preparation method of fluorescent rare earth complex modified nanometer silicon-aluminum emulsion - Google Patents
Preparation method of fluorescent rare earth complex modified nanometer silicon-aluminum emulsion Download PDFInfo
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- CN103642485A CN103642485A CN201310690028.8A CN201310690028A CN103642485A CN 103642485 A CN103642485 A CN 103642485A CN 201310690028 A CN201310690028 A CN 201310690028A CN 103642485 A CN103642485 A CN 103642485A
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- 239000000839 emulsion Substances 0.000 title claims abstract description 108
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 43
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 title abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- 239000010703 silicon Substances 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 239000012153 distilled water Substances 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 63
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 claims description 42
- 229910052782 aluminium Inorganic materials 0.000 claims description 34
- 239000004411 aluminium Substances 0.000 claims description 29
- 230000007062 hydrolysis Effects 0.000 claims description 21
- 238000006460 hydrolysis reaction Methods 0.000 claims description 21
- 238000013019 agitation Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 14
- 239000005543 nano-size silicon particle Substances 0.000 claims description 13
- -1 silicane alkane Chemical class 0.000 claims description 13
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 12
- 229960004756 ethanol Drugs 0.000 claims description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 10
- CJRMAUPUOUJYMF-UHFFFAOYSA-N 3,4-bis[4-(4,4,4-trifluoro-3-oxobutanoyl)phenyl]benzenesulfonyl chloride Chemical compound C1=CC(C(=O)CC(=O)C(F)(F)F)=CC=C1C1=CC=C(S(Cl)(=O)=O)C=C1C1=CC=C(C(=O)CC(=O)C(F)(F)F)C=C1 CJRMAUPUOUJYMF-UHFFFAOYSA-N 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical group COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 235000019253 formic acid Nutrition 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical class CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052593 corundum Inorganic materials 0.000 abstract 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 2
- 239000007822 coupling agent Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 17
- 239000002245 particle Substances 0.000 description 17
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 8
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 6
- 150000005682 diethyl carbonates Chemical class 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 229910052693 Europium Inorganic materials 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 239000002082 metal nanoparticle Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 150000003376 silicon Chemical class 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003550 marker Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000007908 nanoemulsion Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 2
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UOBPHQJGWSVXFS-UHFFFAOYSA-N [O].[F] Chemical compound [O].[F] UOBPHQJGWSVXFS-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000004064 cosurfactant Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002539 nanocarrier Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000001778 solid-state sintering Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
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- Luminescent Compositions (AREA)
Abstract
The invention provides a preparation method of a fluorescent rare earth complex modified nanometer silicon-aluminum emulsion. The method comprises the following steps: 1) preparing a modified nanometer silicon-aluminum emulsion: (1) ultrasonically and uniformly mixing ethyl orthosilicate with a modifying agent, a solvent and a catalyst, dropwise adding distilled water to prepare a modified partially-hydrolyzed nanometer silicon emulsion; (2) dissolving aluminum isopropoxide in calculated quantity into isopropanol, and then dropwise adding the mixture into the ultrasonically and sufficiently mixed solution of water, catalyst, modifying agent and solvent in calculated quantity to obtain a modified nanometer Al2O3 emulsion; (3) adding the modified nanometer Al2O3 emulsion prepared in the step (2) into the modified nanometer silicon-aluminum emulsion obtained by distilling to remove the solvent in the step (1); 2) performing surface modification on the modified nanometer silicon-aluminum emulsion, namely modifying the modified nanometer silicon-aluminum by using an organosilicon coupling agent; 3) preparing the fluorescent rare earth complex modified nanometer silicon-aluminum emulsion. The preparation process is simple and easy to operate, the exciting light wavelength of the prepared fluorescent rare earth complex modified nanometer silicon-aluminum emulsion is 330nm, the light emitting wavelength is 612nm, and the light-emitting strength is 98a.u.
Description
Technical field
That the present invention relates to is a kind of preparation method of rare earth compounding modification fluorescent material, is specifically related to a kind of preparation method of the fluorescent rare earth title complex modified Nano silicon-aluminium emulsion for quick detection test paper.
Background technology
Adopt fluorescent rare earth complex compound and improved silica-alumina composite nanoparticle by distinctive package technique, preparation has fluorescent rare earth title complex modified Nano silicon-aluminium emulsion high-luminous-efficiency, excellent hydrophilic and stability of emulsion, that luminous intensity is high, for Test paper and the in-situs tester of quick test.
The research report of the luminescent material that rare earth ion or rare earth compounding and silicon-dioxide mix is existing a lot.Application number is, in 201010225072.8 patent document, to disclose a kind of novel core-shell fluorescent material, relates to a kind of photoelectron luminescent material.Comprise: kernel is SiO
2bead, shell is fluorescent material Zn
2siO
4: Eu
3+.Application number is, in 201080066884 patent document, to disclose a kind of silicate fluorescent material, and its chemical general formula is: Ln
2siO
5: Tb, M; By introduce metal nano ion in sintered glass, with chemical reduction method, in sintered glass, separate out homodisperse metal nanoparticle, make the sintered glass that contains metal nanoparticle.With the sintered glass that contains metal nanoparticle, replace conventional high-temperature solid state sintering and prepare the raw material SiO in silicate fluorescent material technique
2, obtain the silicate fluorescent material of luminous enhancing.Application number is, in 201210443966 patent document, to disclose a kind of main peak of launching and changed adjustable fluorescent material and preparation method thereof, and this material, for the fluorescent material of LED illumination/show, is a kind of alkaline earth fluorine oxygen silico-aluminate fluorescent material.Application number is that in 201010187481 patent document, disclosed a kind of nitrogen oxide fluorescent material that is applicable to Field Emission Display, provides a kind of Eu
2+the alkaline-earth metal silicon base nitrogen oxides fluorescent material exciting, is subject to launch blue-greenish colour or yellow-green fluorescence after electron-beam excitation, and the fluorescent material of this invention is suitable as FED fluorescent material.Application number is, in 02141718 patent document, to disclose a kind of nano silicon particles that mixes up fluorescent rare earth complex compound.Its preparation method is that fluorescent rare earth complex compound is mixed up in nano silicon particles, has the long fluorescence lifetime that general fluorescent marker does not have, and possesses again high fluorescent, stability and easy mark that general rare-earth complex marker does not have.Application number is, in 200810070609 patent document, to disclose a kind of controllability good, easily realizes prepared uniform particles, the preparation method of the fluorescent rare earth complex compound silicon nano particles that fluorescence intensity is high.Fluorescent rare earth complex compound is bonded in to the surface of nano silicon particles, and by the circulation scion grafting of silane, the strategy of multiple modification, the quantity that makes to be bonded to the complex compound on nano silicon particles surface reaches maximum, so obtain that fluorescence intensity is high, good stability, the easy fluorescent rare earth complex compound silicon nano particles of mark.Concrete grammar, for preparing after nanoparticle vector, carries out the functionalization of nano grain surface; After the chemical bonding of fluorescent rare earth complex compound, carry out the scion grafting of particle surface group, then encircle scion grafting and multiple modification, the functionalization again on last fluorescence silicon nano particles surface.Application number is in 201110320221 patent document, a kind of preparation method of rare-earth fluorescent silica nano particle is disclosed, Jiang Shui, oil, tensio-active agent, cosurfactant mix, spontaneous formation anisotropy, transparent, thermodynamically stable dispersion system, obtain the surperficial nano SiO 2 particle with hydroxyl, again the silane reagent with functional group is reacted with rare earth ion title complex, obtain rare earth ion complex precursors; In the nano SiO 2 particle of the surface that adds gained after the rare earth ion complex precursors making is mixed with tetraethoxysilane with hydroxyl, rare earth ion title complex can be bonded to nano SiO 2 particle surface; In water-in-oil microemulsion system, add rare earth ion, can form the rare-earth complex with fluorescence with being fixed on the rare earth ion title complex chelating on nano SiO 2 particle surface.Although all mention nano-luminescent material in above open source literature, all do not relate to modified Nano silicon-aluminium emulsion.
Summary of the invention
The object of the present invention is to provide a kind of particle diameter evenly, the preparation method of good stability, fluorescence intensity is strong in water fluorescent rare earth title complex modified Nano silicon-aluminium emulsion.
The object of the present invention is achieved like this:
1.1 prepare modified Nano silicon-aluminium emulsion:
1.1.1 the preparation of modified Nano silicon partial hydrolystate
45 grams of tetraethoxys and tetraethoxy quality 0.1-0.4 properties-correcting agent and 0.1-0.4 diethyl carbonate doubly are doubly mixed in 100 grams of ethyl acetate or toluene, the catalyzer that adds the 0.1%-4% of tetraethoxy quality, drip tetraethoxy quality 0.2-4.0 distilled water doubly, at 150 ℃ of-240 ℃ of temperature, ultrasonic agitation reaction 6-7 hour, obtains the nano oxidized silicon emulsion of partial hydrolysis;
1.1.2 nanometer Al
2o
3the preparation of emulsion
27 grams of-40.5 grams of distilled water, 0.003 gram of-0.3 gram of diacetyl oxide and 0.075 gram of-0.15 gram of diethyl carbonate ultrasonic mixing in 10mL ethyl acetate or toluene are obtained to mixed solution A, to be no more than 1.5 grams of aluminum isopropylates joins in 10 grams of Virahols and makes mixing solutions B, mixing solutions B is added drop-wise in mixed solution A, at 180 ℃ of-220 ℃ of temperature, react, obtain modified Nano Al
2o
3emulsion;
1.1.3 by described modified Nano Al
2o
3emulsion joins in the nano oxidized silicon emulsion of described partial hydrolysis, the nano oxidized silicon emulsion of partial hydrolysis and modified Nano Al
2o
3mass ratio=the 4:1-20:1 of emulsion, the 0.8-1.2 that adds partial hydrolysis nano silicon oxide quality of the emulsion Virahol doubly, ultrasonic agitation hour, moves to and in pressure reaction still, reacts 36-120 hour, solvent evaporated ethyl acetate or toluene, obtain modified Nano silicon-aluminium emulsion;
The finishing of 1.2 modified Nano silicon-aluminium
Described nano-silicon-aluminium emulsion 0.5-2mL is joined in the ethanolic soln of silane coupling agent that 0.8-1.2mL mass percent concentration is 3-8%, heat and keep 70 ± 2 ℃ of 5-10 minute of temperature, with absolute ethanol washing, then the nano-silicon-aluminium after washing is suspended in ethanol and is obtained with amino nano-silicon-aluminium suspension;
The preparation of 1.3 fluorescent rare earth title complex modified Nano silicon-aluminium emulsions:
By 9.0 * 10
-6mmolL
-1beta-diketon class part (BTBCT) 55 μ L join 150-400 μ L with in amino nano-silicon-aluminium suspension, and 2-3 hour is stirred in excusing from death, then uses washing with alcohol, with 70 μ L0.05M, pH7.8Tris-HCl, suspend, and add 1.7 * 10
-4mmolL
-1euCl
34.9-6.0mL, in 35-37 ℃ of water bath with thermostatic control lucifuge ultrasonic agitation 30-50 minute, dehydrated alcohol is washed three times, with ethanol, suspends.
The present invention can also comprise:
1, described properties-correcting agent is tetra-n-butyl zirconium, tributyl phosphate or both mixtures.
2, described catalyzer is formic acid, acetic acid or diacetyl oxide.
3, described silane coupling agent is three aminopropyl triethoxysilanes or triuret ethyl triethoxy silicane alkane.
4, described beta-diketon class part is
4,4′-bis(1′′,1′′,1′′-trifluoro-2′′,4′′-butanedione-6′′-yl)-chlorosulfo-o-terphenyl。
Fluorescent rare earth title complex modified Nano silicon-aluminium emulsion that the present invention obtains and common fluorescent rare earth title complex nanometer SiO
2particle Phase ratio, have particle diameter more evenly, in water more stable not free settling, fluorescent rare earth title complex modified Nano SiO
2-Al
2o
3the advantages such as emulsion fluorescence intensity in water is stronger.
Common particle diameter be the particle of 50 nanometers in water, the time surpasses and sedimentation can occur in 3 months, stability is not good enough.What the present invention was prepared is that fluorescent rare earth title complex silicon-aluminum particulate is because particle is with electronegativity, the particle diameter ratio of particle is easier to be controlled at 50-60 nanometer, particle has repulsive force each other, effectively extend nano material because surface tension produces the time of sedimentation greatly, significantly increased the stability of modified silicon aluminum nanoparticles emulsion.
Technical essential of the present invention mainly comprises: first, prepare modified Nano silicon-aluminium emulsion: prepare respectively modification partial hydrolysis silicon emulsion and partial hydrolysis aluminium emulsion, partial hydrolysis aluminium emulsion is added and in partial hydrolysis silicon emulsion, obtains modified Nano silicon-aluminium emulsion; Secondly, prepare fluorescent rare earth (europium or terbium) title complex nano-silicon-aluminium emulsion: by surface with amino modified Nano silicon-aluminium emulsion through rare earth (europium or terbium) and beta-diketon class part: 4,4 '-bis (1 ' ', 1 ' ', 1 ' '-trifluoro-2 ' ', 4 ' '-butanedione-6 ' '-yl) the title complex generation bonding action that-chlorosulfo-o-terphen yl (BTBCT) forms, prepares fluorescent rare earth (europium) title complex modified Nano silicon-aluminium emulsion.
The particle diameter that the invention has the beneficial effects as follows nano-silicon-aluminium emulsion of preparation is 40-60 nanometer, and nano-silicon-aluminum particulate is after metal (Zr) or nonmetal (carbon) modification, itself has electronegativity, between particle, there is mutual repulsive force, make silicon-aluminium nanometer in the aqueous solution, there is good dispersiveness, more stable in water.
The groups such as amino, aldehyde radical, carboxyl can be modified in nano-silicon-aluminum ions surface, and these groups can react with the peptide group of biological antibody.
The fluorescence complex of modified silicon-aluminium nanoemulsions is with BTBCT:Eu
3+-modified silicon-aluminium nanoemulsions is example, and excitation wavelength is 330nm, and wavelength of transmitted light is 612nm.Luminous intensity is 98(a.u.), the emulsion-stabilizing time is greater than 3 months, and visible rare earth compounding modified Nano silicon-aluminium emulsion of the present invention has the excellent specific properties such as stable, luminous intensity is high, meets the requirement of check test strip and field monitoring instrument.
Embodiment
For example the present invention is described in more detail below.
Basic embodiment
1.1 prepare modified Nano silicon-aluminium emulsion:
1.1.1 modified Nano silicon partial hydrolystate preparation
45 grams of tetraethoxys are fully mixed with 4.5 grams of-18 grams of tetra-n-butyl zirconiums (0.1-0.4 of quality tetraethoxy doubly) and 4.5 grams of-18 grams of diethyl carbonates ((0.1-0.4 of quality tetraethoxy doubly)) with 4.5 grams of-18 grams of tetra-n-butyl zirconiums (0.1-0.4 of quality tetraethoxy doubly) or 45 grams of tetraethoxys in 100 grams of ethyl acetate (or toluene), and the concentration of tetraethoxy is not more than 45%.Formic acid, acetic acid or diacetyl oxide are catalyzer, catalyst levels is the 0.1%-4% of tetraethoxy quality, drip redistilled water, the consumption of water can regulate in 9 grams-180 grams (0.2-4.0 of tetraethoxy doubly) scopes, time for adding 120 minutes, ultrasonic agitation 6 hours, 150 ℃-240 ℃ of temperature of reaction obtain the nano oxidized silicon emulsion of partial hydrolysis, stand-by;
1.1.2 nanometer Al
2o
3the preparation of emulsion:
By 27 grams-40.5 grams redistilled waters (regulating between the 0.1-1.5 of aluminum isopropylate mole number), 0.003 gram-0.3 gram diacetyl oxide (0.2%-2% of Virahol quality), 0.075 gram-0.15 gram diethyl carbonate (5%-10% of Virahol quality) ultrasonic mixing in 10mL ethyl acetate (or toluene), stand-by; Quality is no more than 1.5 grams of aluminum isopropylates and adds in 10 grams of Virahols and make solution, then is added drop-wise to (concentration of aluminum isopropylate is not more than 15%) in above-mentioned solution.180 ℃-220 ℃ of temperature of reaction, obtain modified Nano Al
2o
3emulsion;
1.1.3 by the prepared nanometer Al of step 2
2o
3emulsion joins the modified Nano SiO of step 1 preparation
2in emulsion, ratio ranges: partial hydrolysis silicon emulsion: modified Nano Al
2o
3emulsion=4:1-20:1 (mass ratio), the 0.8-1.2 that adds partial hydrolysis silicon emulsion quality Virahol doubly, ultrasonic agitation hour, moves to and in pressure reaction still, reacts 36-120 hour, solvent evaporated ethyl acetate (or toluene), obtains modified Nano silicon-aluminium emulsion.
1.2. the finishing of modified Nano silicon-aluminium
Nano-silicon-aluminium emulsion 0.5-2mL of above-mentioned preparation is added to 0.8-1.2mL to be entered in the ethanolic soln that mass percent concentration is 3-8% aminopropyl trimethoxysilane (APTMS), heat and keep 70 ± 2 ℃ of 5-10 minute of temperature, with dehydrated alcohol, wash unreacted APTMS three times, then the nano-silicon-aluminium after washing is suspended in ethanol;
1.3. the preparation of fluorescent rare earth title complex nano-silicon-aluminium emulsion:
By 9.0 * 10
-6mmolL
-1bTBCT55 μ L joins 150-400 μ L with amino nano-silicon-aluminium suspension, and 2-3 hour is stirred in excusing from death, then uses appropriate washing with alcohol, with 70 μ LTris-HCl(0.05M, pH7.8) suspend, add 1.7 * 10
-4mmolL
-1euCl
34.9-6.0mL, in 35-37 ℃ of water bath with thermostatic control lucifuge ultrasonic agitation 30-50 minute, dehydrated alcohol is washed three times, with ethanol, suspends.
Embodiment:
1) modified silicon partial hydrolystate preparation
40 grams of tetraethoxys, 18 grams of tetra-n-butyl zirconiums (or 40 grams tetraethoxy with 18 grams of tetra-n-butyl zirconiums and 18 grams of tributyl phosphates) are fully mixed in ethyl acetate (or toluene), add 0.8 gram, formic acid, drip redistilled water 100mL, time for adding 120 minutes, ultrasonic agitation 6 hours, 150 ℃-240 ℃ of temperature of reaction obtain the nano oxidized silicon emulsion of partial hydrolysis, stand-by;
2) nanometer Al
2o
3the preparation of emulsion:
By 27 grams of redistilled waters, 0.3 gram of diacetyl oxide, 18 grams of diethyl carbonates ultrasonic mixing in 10mL ethyl acetate (or toluene), stand-by; 1.5 grams of aluminum isopropylates are added in 10 grams of Virahols and make solution, then be added drop-wise in the ethyl acetate solution of above-mentioned diacetyl oxide, diethyl carbonate.180 ℃-220 ℃ of temperature of reaction, obtain modified Nano Al
2o
3emulsion;
3) by the prepared nanometer Al of step 2
2o
3emulsion joins the modified Nano SiO of step 1 preparation
2in emulsion, 20 grams of partial hydrolysis silicon emulsions, 1 gram of modified Nano Al
2o
3emulsion, adds 20 grams of Virahols, and ultrasonic agitation hour moves in pressure reaction still and reacts 36-120 hour, and solvent evaporated ethyl acetate (or toluene) obtains modified Nano silicon-aluminium emulsion.
2. the finishing of modified Nano silicon-aluminium
Nano-silicon-aluminium emulsion 2.0mL of above-mentioned preparation is added to 1.2mL to be entered in the ethanolic soln that mass percent concentration is 3-8% aminopropyl trimethoxysilane (APTMS), heat and keep 70 ± 2 ℃ of 5-10 minute of temperature, with dehydrated alcohol, wash unreacted APTMS three times, then the nano-silicon-aluminium after washing is suspended in ethanol;
3. the preparation of fluorescent rare earth title complex nano-silicon-aluminium emulsion:
By 9.0 * 10
-6mmolL
-1bTBCT55 μ L joins 400 μ L with amino nano-silicon-aluminium suspension, and 2-3 hour is stirred in excusing from death, then uses appropriate washing with alcohol, with 70 μ L Tris-HCl(0.05M, pH7.8) suspend, add 1.7 * 10
-4mmolL
-1euCl
36.0mL, in 35-37 ℃ of water bath with thermostatic control lucifuge ultrasonic agitation 30-50 minute, dehydrated alcohol is washed three times, with ethanol, suspends.
Embodiment 2:
1. prepare modified Nano silicon-aluminium emulsion:
Step 1: modified silicon partial hydrolystate preparation
35 grams of tetraethoxys, 12 grams of tetra-n-butyl zirconiums (or 35 grams tetraethoxy with 12 grams of tetra-n-butyl zirconiums and 12 grams of tributyl phosphates) are fully mixed in ethyl acetate (or toluene), add 0.06 gram, formic acid, drip redistilled water 100mL, time for adding 120 minutes, ultrasonic agitation 6 hours, 150 ℃-240 ℃ of temperature of reaction obtain the nano oxidized silicon emulsion of partial hydrolysis, stand-by;
2) nanometer Al
2o
3the preparation of emulsion:
By 38 grams of redistilled waters, 0.076 gram of diacetyl oxide, 14 grams of diethyl carbonates ultrasonic mixing in 10mL ethyl acetate (or toluene), stand-by; 1.0 grams of aluminum isopropylates are added in 10 grams of Virahols and make solution, then be added drop-wise in the ethyl acetate solution of above-mentioned diacetyl oxide, diethyl carbonate.180 ℃-220 ℃ of temperature of reaction, obtain modified Nano Al
2o
3emulsion;
3) by the prepared nanometer Al of step 2
2o
3emulsion joins the modified Nano SiO of step 1 preparation
2in emulsion, 20 grams of partial hydrolysis silicon emulsions, 5 grams of modified Nano Al
2o
3emulsion, adds 20 grams of Virahols, and ultrasonic agitation hour moves in pressure reaction still and reacts 36-120 hour, and solvent evaporated ethyl acetate (or toluene) obtains modified Nano silicon-aluminium emulsion.
2. the finishing of modified Nano silicon-aluminium
Nano-silicon-aluminium emulsion 1.5mL of above-mentioned preparation is added to 1.0mL to be entered in the ethanolic soln that mass percent concentration is 3-8% aminopropyl trimethoxysilane (APTMS), heat and keep 70 ± 2 ℃ of 5-10 minute of temperature, with dehydrated alcohol, wash unreacted APTMS three times, then the nano-silicon-aluminium after washing is suspended in ethanol;
3. the preparation of fluorescent rare earth title complex nano-silicon-aluminium emulsion:
By 9.0 * 10
-6mmolL
-1bTBCT55 μ L joins 300 μ L with amino nano-silicon-aluminium suspension, and 2-3 hour is stirred in excusing from death, then uses appropriate washing with alcohol, with 70 μ LTris-HCl(0.05M, pH7.8) suspend, add 1.7 * 10
-4mmolL
-1euCl
35.5mL, in 35-37 ℃ of water bath with thermostatic control lucifuge ultrasonic agitation 30-50 minute, dehydrated alcohol is washed three times, with ethanol, suspends.
Embodiment 3:
1. prepare nano-silicon-aluminium emulsion:
Step 1: modified silicon partial hydrolystate preparation
35 grams of tetraethoxys, 12 grams of tetra-n-butyl zirconiums (or 35 grams tetraethoxy with 12 grams of tetra-n-butyl zirconiums and 12 grams of tributyl phosphates) are fully mixed in ethyl acetate (or toluene), add 0.06 gram, formic acid, drip redistilled water 100mL, time for adding 120 minutes, ultrasonic agitation 6 hours, 150 ℃-240 ℃ of temperature of reaction obtain the nano oxidized silicon emulsion of partial hydrolysis, stand-by;
2) nanometer Al
2o
3the preparation of emulsion:
By 32 grams of redistilled waters, 0.06 gram of diacetyl oxide, 10 grams of diethyl carbonates ultrasonic mixing in 10mL ethyl acetate (or toluene), stand-by; 0.8 gram of aluminum isopropylate is added in 10 grams of Virahols and makes solution, then be added drop-wise in the ethyl acetate solution of above-mentioned diacetyl oxide, diethyl carbonate.180 ℃-220 ℃ of temperature of reaction, obtain modified Nano Al
2o
3emulsion;
3) by the prepared nanometer Al of step 2
2o
3emulsion joins the modified Nano SiO of step 1 preparation
2in emulsion, 30 grams of partial hydrolysis silicon emulsions, 5 grams of modified Nano Al
2o
3emulsion, adds 14 grams of Virahols, and ultrasonic agitation hour moves in pressure reaction still and reacts 36-120 hour, and solvent evaporated ethyl acetate (or toluene) obtains modified Nano silicon-aluminium emulsion.
2. the finishing of modified Nano silicon-aluminium
Nano-silicon-aluminium emulsion 1mL of above-mentioned preparation is added to 0.8mL to be entered in the ethanolic soln that mass percent concentration is 3-8% aminopropyl trimethoxysilane (APTMS), heat and keep 70 ± 2 ℃ of 5-10 minute of temperature, with dehydrated alcohol, wash unreacted APTMS three times, then the nano-silicon-aluminium after washing is suspended in ethanol;
3. the preparation of fluorescent rare earth title complex nano-silicon-aluminium emulsion:
By 9.0 * 10
-6mmolL
-1bTBCT55 μ L joins 260 μ L with amino nano-silicon-aluminium suspension, and 2-3 hour is stirred in excusing from death, then uses appropriate washing with alcohol, with 70 μ LTris-HCl(0.05M, pH7.8) suspend, add 1.7 * 10
-4mmolL
-1euCl
35.0mL, in 35-37 ℃ of water bath with thermostatic control lucifuge ultrasonic agitation 30-50 minute, dehydrated alcohol is washed three times, with ethanol, suspends.
Above three BTBCT-Eu prepared by embodiment
3+: the excitation wavelength of modified Nano silicon emulsion is 330nm, and wavelength of transmitted light is 612nm.Luminous intensity is 98(a.u.), stability is all over three months.
Claims (9)
1. a preparation method for fluorescent rare earth title complex modified Nano silicon-aluminium emulsion, is characterized in that:
1.1 prepare modified Nano silicon-aluminium emulsion:
1.1.1 the preparation of modified Nano silicon partial hydrolystate
45 grams of tetraethoxys and tetraethoxy quality 0.1-0.4 properties-correcting agent and 0.1-0.4 diethyl carbonate doubly are doubly mixed in 100 grams of ethyl acetate or toluene, the catalyzer that adds the 0.1%-4% of tetraethoxy quality, drip tetraethoxy quality 0.2-4.0 distilled water doubly, at 150 ℃ of-240 ℃ of temperature, ultrasonic agitation reaction 6-7 hour, obtains the nano oxidized silicon emulsion of partial hydrolysis;
1.1.2 nanometer Al
2o
3the preparation of emulsion
27 grams of-40.5 grams of distilled water, 0.003 gram of-0.3 gram of diacetyl oxide and 0.075 gram of-0.15 gram of diethyl carbonate ultrasonic mixing in 10mL ethyl acetate or toluene are obtained to mixed solution A, to be no more than 1.5 grams of aluminum isopropylates joins in 10 grams of Virahols and makes mixing solutions B, mixing solutions B is added drop-wise in mixed solution A, at 180 ℃ of-220 ℃ of temperature, react, obtain modified Nano Al
2o
3emulsion;
1.1.3 by described modified Nano Al
2o
3emulsion joins in the nano oxidized silicon emulsion of described partial hydrolysis, the nano oxidized silicon emulsion of partial hydrolysis and modified Nano Al
2o
3mass ratio=the 4:1-20:1 of emulsion, the 0.8-1.2 that adds partial hydrolysis nano silicon oxide quality of the emulsion Virahol doubly, ultrasonic agitation hour, moves to and in pressure reaction still, reacts 36-120 hour, solvent evaporated ethyl acetate or toluene, obtain modified Nano silicon-aluminium emulsion;
The finishing of 1.2 modified Nano silicon-aluminium
Described nano-silicon-aluminium emulsion 0.5-2mL is joined in the ethanolic soln of silane coupling agent that 0.8-1.2mL mass percent concentration is 3-8%, heat and keep 70 ± 2 ℃ of 5-10 minute of temperature, with absolute ethanol washing, then the nano-silicon-aluminium after washing is suspended in ethanol and is obtained with amino nano-silicon-aluminium suspension;
The preparation of 1.3 fluorescent rare earth title complex modified Nano silicon-aluminium emulsions
By 9.0 * 10
-6mmolL
-1beta-diketon class part (BTBCT) 55 μ L join 150-400 μ L with in amino nano-silicon-aluminium suspension, and 2-3 hour is stirred in excusing from death, then uses washing with alcohol, with 70 μ L0.05M, pH7.8Tris-HCl, suspend, and add 1.7 * 10
-4mmolL
-1euCl
34.9-6.0mL, in 35-37 ℃ of water bath with thermostatic control lucifuge ultrasonic agitation 30-50 minute, dehydrated alcohol is washed three times, with ethanol, suspends.
2. the preparation method of fluorescent rare earth title complex modified Nano silicon-aluminium emulsion according to claim 1, is characterized in that: described properties-correcting agent is tetra-n-butyl zirconium, tributyl phosphate or both mixtures.
3. the preparation method of fluorescent rare earth title complex modified Nano silicon-aluminium emulsion according to claim 1 and 2, is characterized in that: described catalyzer is formic acid, acetic acid or diacetyl oxide.
4. the preparation method of fluorescent rare earth title complex modified Nano silicon-aluminium emulsion according to claim 1 and 2, is characterized in that: described silane coupling agent is three aminopropyl triethoxysilanes or triuret ethyl triethoxy silicane alkane.
5. the preparation method of fluorescent rare earth title complex modified Nano silicon-aluminium emulsion according to claim 3, is characterized in that: described silane coupling agent is three aminopropyl triethoxysilanes or triuret ethyl triethoxy silicane alkane.
6. the preparation method of fluorescent rare earth title complex modified Nano silicon-aluminium emulsion according to claim 1 and 2, is characterized in that described beta-diketon class part is:
4,4′-bis(1′′,1′′,1′′-trifluoro-2′′,4′′-butanedione-6′′-yl)-chlorosulfo-o-terphenyl。
7. the preparation method of fluorescent rare earth title complex modified Nano silicon-aluminium emulsion according to claim 3, is characterized in that described beta-diketon class part is:
4,4′-bis(1′′,1′′,1′′-trifluoro-2′′,4′′-butanedione-6′′-yl)-chlorosulfo-o-terphenyl。
8. the preparation method of fluorescent rare earth title complex modified Nano silicon-aluminium emulsion according to claim 4, is characterized in that described beta-diketon class part is:
4,4′-bis(1′′,1′′,1′′-trifluoro-2′′,4′′-butanedione-6′′-yl)-chlorosulfo-o-terphenyl。
9. the preparation method of fluorescent rare earth title complex modified Nano silicon-aluminium emulsion according to claim 5, is characterized in that described beta-diketon class part is:
4,4′-bis(1′′,1′′,1′′-trifluoro-2′′,4′′-butanedione-6′′-yl)-chlorosulfo-o-terphenyl。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101225306A (en) * | 2008-02-02 | 2008-07-23 | 厦门大学 | Method for preparing fluorescent rare earth complex compound silicon nano particles |
| CN101368097A (en) * | 2008-10-09 | 2009-02-18 | 同济大学 | Process for producing luminous rare earth-beta-diketone-polyvinyl pyridine macromolecule composite material |
| US20130231468A1 (en) * | 2010-11-22 | 2013-09-05 | Takeshi Yamashita | Rare earth metal complex |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101225306A (en) * | 2008-02-02 | 2008-07-23 | 厦门大学 | Method for preparing fluorescent rare earth complex compound silicon nano particles |
| CN101368097A (en) * | 2008-10-09 | 2009-02-18 | 同济大学 | Process for producing luminous rare earth-beta-diketone-polyvinyl pyridine macromolecule composite material |
| US20130231468A1 (en) * | 2010-11-22 | 2013-09-05 | Takeshi Yamashita | Rare earth metal complex |
Non-Patent Citations (1)
| Title |
|---|
| 于春暖 等: "4,4′-二(1,″1″,1″-三氟-2″,4″-丁二酮-6″-酰基)-氯磺化邻-三联苯的合成与表征", 《标记免疫分析与临床》, vol. 16, no. 2, 15 April 2009 (2009-04-15) * |
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