CN103642485B - 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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- CN103642485B CN103642485B CN201310690028.8A CN201310690028A CN103642485B CN 103642485 B CN103642485 B CN 103642485B CN 201310690028 A CN201310690028 A CN 201310690028A CN 103642485 B CN103642485 B CN 103642485B
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- 239000000839 emulsion Substances 0.000 title claims abstract description 104
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 46
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 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 46
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 claims description 38
- 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 19
- 239000005543 nano-size silicon particle Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 229960004756 ethanol Drugs 0.000 claims description 16
- -1 silicane alkane Chemical class 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 10
- 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
- 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
- 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
- OIAQMFOKAXHPNH-UHFFFAOYSA-N 1,2-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC=C1C1=CC=CC=C1 OIAQMFOKAXHPNH-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 5
- 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
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification 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 15
- 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
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 5
- 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 description 4
- 150000005682 diethyl carbonates Chemical class 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000000377 silicon dioxide 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
- 229910004298 SiO 2 Inorganic materials 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
- 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
- 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
- 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
- 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
- 238000007689 inspection Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004020 luminiscence type Methods 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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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 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, that preparation has high-luminous-efficiency, excellent hydrophilic and stability of emulsion, that luminous intensity is high fluorescent rare earth complex modified Nano silicon-aluminium emulsion, 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 the patent document of 201010225072.8, discloses 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 the patent document of 201080066884, discloses a kind of silicate fluorescent material, and its chemical general formula is: Ln
2siO
5: Tb, M; By introducing metal nano ion in sintered glass, in sintered glass, separate out homodisperse metal nanoparticle with chemical reduction method, the obtained sintered glass containing metal nanoparticle.The raw material SiO in silicate fluorescent material technique is prepared with the sintered glass replacement conventional high-temperature solid state sintering containing metal nanoparticle
2, obtain the silicate fluorescent material of luminescence enhancement.Application number is in the patent document of 201210443966, discloses a kind of main peak of launching and changes adjustable fluorescent material and preparation method thereof, and this material is used for the fluorescent material of LED illumination/display, is a kind of alkaline earth fluorine oxygen silico-aluminate fluorescent material.Application number is in the patent document of 201010187481, and disclosed a kind of nitrogen oxide fluorescent material being applicable to Field Emission Display, provides a kind of Eu
2+the alkaline-earth metal silicon base nitrogen oxides fluorescent material excited, by launching blue-greenish colour or yellow-green fluorescence after electron-beam excitation, the fluorescent material of this invention is suitable as FED fluorescent material.Application number is in the patent document of 02141718, discloses a kind of nano silicon particles mixing up fluorescent rare earth complex compound.Its preparation method mixes up in nano silicon particles by fluorescent rare earth complex compound, has the long fluorescence lifetime that general fluorescent marker does not have, and possesses again high fluorescent that general rare-earth complex marker do not have, stability and easily markup.Application number is in the patent document of 200810070609, discloses 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 the surface of nano silicon particles, and pass through the circulation scion grafting of silane, the strategy of multiple modification, make the quantity of the complex compound being bonded to nano silicon particles surface reach maximum, and then acquisition fluorescence intensity is high, the fluorescent rare earth complex compound silicon nano particles of good stability, easily mark.Concrete grammar, for after preparing 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 ring scion grafting and multiple modification, the functionalization again on last fluorescence silicon nano particles surface.Application number is in the patent document of 201110320221, disclose a kind of preparation method of rare-earth fluorescent silica nano particle, 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, react with the silane reagent of functional group and rare earth ion title complex again, obtain rare earth ion complex precursors; Add the surface of gained after being mixed with tetraethoxysilane by obtained rare earth ion complex precursors with in the nano SiO 2 particle of hydroxyl, rare earth ion title complex can be bonded to silica nanoparticle surface; In water-in-oil microemulsion system, add rare earth ion, the rare-earth complex with fluorescence can be formed with the rare earth ion title complex chelating being fixed on silica nanoparticle 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 uniform particle sizes, good stability, the preparation method of fluorescent rare earth complex modified Nano silicon-aluminium emulsion that fluorescence intensity is strong in water.
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 doubly and 0.1-0.4 diethyl carbonate are doubly mixed in 100 grams of ethyl acetate or toluene, add the catalyzer of the 0.1%-4% of tetraethoxy quality, drip tetraethoxy quality 0.2-4.0 distilled water doubly, at 150 DEG C of-240 DEG C 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 mixed solution A, 1.5 grams of aluminum isopropylates will be no more than join in 10 grams of Virahols and make mixing solutions B, mixing solutions B is added drop-wise in mixed solution A, react at 180 DEG C of-220 DEG C of temperature, 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 Virahol doubly of adding portion hydrolysis nano silicon oxide quality of the emulsion, ultrasonic agitation hour, moves in pressure reaction still and 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
It is in the ethanolic soln of the silane coupling agent of 3-8% that described nano-silicon-aluminium emulsion 0.5-2mL is joined 0.8-1.2mL mass percent concentration, heat and keep temperature 70 ± 2 DEG C of 5-10 minute, with absolute ethanol washing, then the nano-silicon-aluminium after washing is suspended in ethanol the nano-silicon-aluminium suspension obtained with amino;
The preparation of 1.3 fluorescent rare earth complex modified Nano silicon-aluminium emulsions:
By 9.0 × 10
-6mmolL
-1beta-diketon class part (BTBCT) 55 μ L joins 150-400 μ L with in the nano-silicon-aluminium suspension of amino, and 2-3 hour is stirred in excusing from death, then uses washing with alcohol, suspends, add 1.7 × 10 with 70 μ L0.05M, pH7.8Tris-HCl
-4mmolL
-1euCl
34.9-6.0mL, in 35-37 DEG C of water bath with thermostatic control lucifuge ultrasonic agitation 30-50 minute, dehydrated alcohol washes three times, uses ethanol suspension.
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 complex modified Nano silicon-aluminium emulsion that the present invention obtains and common fluorescent rare earth complex Nano-meter SiO_2
2particle Phase ratio, there is particle diameter evenly, in water more stable not free settling, fluorescent rare earth 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, can there is sedimentation more than 3 months in the time, stability is not good enough.Prepared by the present invention is that fluorescent rare earth complex silicon-aluminum particulate is because particle is with electronegativity, the particle diameter ratio of particle is easier to control in 50-60 nanometer, particle has repulsive force each other, effectively extend nano material produces sedimentation time because surface tension is large, significantly increase modified silicon aluminum nanoparticles emulsion intercalation method.
Technical essential of the present invention mainly comprises: first, prepares modified Nano silicon-aluminium emulsion: prepare modifying moieties hydrolysis silicon emulsion and partial hydrolysis aluminium emulsion respectively, partial hydrolysis aluminium emulsion added in partial hydrolysis silicon emulsion and obtain modified Nano silicon-aluminium emulsion; Secondly, prepare fluorescent rare earth (europium or terbium) title complex nano-silicon-aluminium emulsion: by surface with the modified Nano silicon-aluminium emulsion of amino through rare earth (europium or terbium) and beta-diketon class part: 4,4 '-bis (1 ' ', 1 ' ', 1 ' '-trifluoro-2 ' ', 4 ' '-butanedione-6 ' '-yl) title complex generation bonding action that-chlorosulfo-o-terphenyl (BTBCT) is formed, prepare fluorescent rare earth (europium) title complex modified Nano silicon-aluminium emulsion.
The particle diameter that the invention has the beneficial effects as follows the nano-silicon-aluminium emulsion of preparation is 40-60 nanometer, and nano-silicon-aluminum particulate through metal (Zr) or nonmetal (carbon) modified, itself has electronegativity, mutual repulsive force is there is between particle, silicon-aluminium nanometer is made to have good dispersiveness in aqueous, 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 inspection test strip and field monitoring instrument.
Embodiment
Illustrate below and the present invention is described in more detail.
Basic embodiment
1.1 prepare modified Nano silicon-aluminium emulsion:
1.1.1 modified Nano silicon partial hydrolystate preparation
Fully mixed in 100 grams of ethyl acetate (or toluene) with 4.5 grams-18 grams 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-18 grams tetra-n-butyl zirconiums (0.1-0.4 of quality tetraethoxy doubly) or 45 grams of tetraethoxys by 45 grams of tetraethoxys, 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, temperature of reaction 150 DEG C-240 DEG C obtains the nano oxidized silicon emulsion of partial hydrolysis, stand-by;
1.1.2 nanometer Al
2o
3the preparation of emulsion:
By 27 grams of-40.5 grams of redistilled waters (regulating between the 0.1-1.5 of aluminum isopropylate mole number), 0.003 gram of-0.3 gram of diacetyl oxide (0.2%-2% of Virahol quality), 0.075 gram of-0.15 gram of diethyl carbonate (5%-10% of Virahol quality) is ultrasonic in 10mL ethyl acetate (or toluene) mixes, 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.Temperature of reaction 180 DEG C-220 DEG C, obtains modified Nano Al
2o
3emulsion;
1.1.3 by the nanometer Al prepared by step 2
2o
3emulsion joins modified Nano SiO prepared by step 1
2in emulsion, ratio ranges: partial hydrolysis silicon emulsion: modified Nano Al
2o
3emulsion=4:1-20:1 (mass ratio), the 0.8-1.2 Virahol doubly of adding portion hydrolysis silicon emulsion quality, ultrasonic agitation hour, moves in pressure reaction still and 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
The nano-silicon of above-mentioned preparation-aluminium emulsion 0.5-2mL being added 0.8-1.2mL, to enter mass percent concentration be in the ethanolic soln of 3-8% aminopropyl trimethoxysilane (APTMS), heat and keep temperature 70 ± 2 DEG C of 5-10 minute, wash three unreacted APTMS with dehydrated alcohol, then the nano-silicon-aluminium after washing is suspended in ethanol;
1.3. the preparation of fluorescent rare earth complex nano-silicon-aluminium emulsion:
By 9.0 × 10
-6mmolL
-1bTBCT55 μ L joins the nano-silicon-aluminium suspension of 150-400 μ L with amino, and 2-3 hour is stirred in excusing from death, then with ethanol in proper amount washing, with 70 μ LTris-HCl(0.05M, pH7.8) suspend, add 1.7 × 10
-4mmolL
-1euCl
34.9-6.0mL, in 35-37 DEG C of water bath with thermostatic control lucifuge ultrasonic agitation 30-50 minute, dehydrated alcohol washes three times, uses ethanol suspension.
Embodiment:
1) modified silicon partial hydrolystate preparation
40 grams of tetraethoxys, 18 grams of tetra-n-butyl zirconiums (or 40 grams of tetraethoxys and 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, temperature of reaction 150 DEG C-240 DEG C obtains 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 are ultrasonic in 10mL ethyl acetate (or toluene) mixes, stand-by; 1.5 grams of aluminum isopropylates are 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.Temperature of reaction 180 DEG C-220 DEG C, obtains modified Nano Al
2o
3emulsion;
3) by the nanometer Al prepared by step 2
2o
3emulsion joins modified Nano SiO prepared by step 1
2in emulsion, 20 grams of partial hydrolysis silicon emulsions, 1 gram of modified Nano Al
2o
3emulsion, add 20 grams of Virahols, 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
The nano-silicon of above-mentioned preparation-aluminium emulsion 2.0mL being added 1.2mL, to enter mass percent concentration be in the ethanolic soln of 3-8% aminopropyl trimethoxysilane (APTMS), heat and keep temperature 70 ± 2 DEG C of 5-10 minute, wash three unreacted APTMS with dehydrated alcohol, then the nano-silicon-aluminium after washing is suspended in ethanol;
3. the preparation of fluorescent rare earth complex nano-silicon-aluminium emulsion:
By 9.0 × 10
-6mmolL
-1bTBCT55 μ L joins the nano-silicon-aluminium suspension of 400 μ L with amino, and 2-3 hour is stirred in excusing from death, then with ethanol in proper amount washing, with 70 μ L Tris-HCl(0.05M, pH7.8) suspend, add 1.7 × 10
-4mmolL
-1euCl
36.0mL, in 35-37 DEG C of water bath with thermostatic control lucifuge ultrasonic agitation 30-50 minute, dehydrated alcohol washes three times, uses ethanol suspension.
Embodiment 2:
1. prepare modified Nano silicon-aluminium emulsion:
Step 1: prepared by modified silicon partial hydrolystate
35 grams of tetraethoxys, 12 grams of tetra-n-butyl zirconiums (or 35 grams of tetraethoxys and 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, temperature of reaction 150 DEG C-240 DEG C obtains 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 are ultrasonic in 10mL ethyl acetate (or toluene) mixes, stand-by; 1.0 grams of aluminum isopropylates are 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.Temperature of reaction 180 DEG C-220 DEG C, obtains modified Nano Al
2o
3emulsion;
3) by the nanometer Al prepared by step 2
2o
3emulsion joins modified Nano SiO prepared by step 1
2in emulsion, 20 grams of partial hydrolysis silicon emulsions, 5 grams of modified Nano Al
2o
3emulsion, add 20 grams of Virahols, 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
The nano-silicon of above-mentioned preparation-aluminium emulsion 1.5mL being added 1.0mL, to enter mass percent concentration be in the ethanolic soln of 3-8% aminopropyl trimethoxysilane (APTMS), heat and keep temperature 70 ± 2 DEG C of 5-10 minute, wash three unreacted APTMS with dehydrated alcohol, then the nano-silicon-aluminium after washing is suspended in ethanol;
3. the preparation of fluorescent rare earth complex nano-silicon-aluminium emulsion:
By 9.0 × 10
-6mmolL
-1bTBCT55 μ L joins the nano-silicon-aluminium suspension of 300 μ L with amino, and 2-3 hour is stirred in excusing from death, then with ethanol in proper amount washing, with 70 μ LTris-HCl(0.05M, pH7.8) suspend, add 1.7 × 10
-4mmolL
-1euCl
35.5mL, in 35-37 DEG C of water bath with thermostatic control lucifuge ultrasonic agitation 30-50 minute, dehydrated alcohol washes three times, uses ethanol suspension.
Embodiment 3:
1. prepare nano-silicon-aluminium emulsion:
Step 1: prepared by modified silicon partial hydrolystate
35 grams of tetraethoxys, 12 grams of tetra-n-butyl zirconiums (or 35 grams of tetraethoxys and 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, temperature of reaction 150 DEG C-240 DEG C obtains 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 are ultrasonic in 10mL ethyl acetate (or toluene) mixes, 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.Temperature of reaction 180 DEG C-220 DEG C, obtains modified Nano Al
2o
3emulsion;
3) by the nanometer Al prepared by step 2
2o
3emulsion joins modified Nano SiO prepared by step 1
2in emulsion, 30 grams of partial hydrolysis silicon emulsions, 5 grams of modified Nano Al
2o
3emulsion, add 14 grams of Virahols, 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
The nano-silicon of above-mentioned preparation-aluminium emulsion 1mL being added 0.8mL, to enter mass percent concentration be in the ethanolic soln of 3-8% aminopropyl trimethoxysilane (APTMS), heat and keep temperature 70 ± 2 DEG C of 5-10 minute, wash three unreacted APTMS with dehydrated alcohol, then the nano-silicon-aluminium after washing is suspended in ethanol;
3. the preparation of fluorescent rare earth complex nano-silicon-aluminium emulsion:
By 9.0 × 10
-6mmolL
-1bTBCT55 μ L joins the nano-silicon-aluminium suspension of 260 μ L with amino, and 2-3 hour is stirred in excusing from death, then with ethanol in proper amount washing, with 70 μ LTris-HCl(0.05M, pH7.8) suspend, add 1.7 × 10
-4mmolL
-1euCl
35.0mL, in 35-37 DEG C of water bath with thermostatic control lucifuge ultrasonic agitation 30-50 minute, dehydrated alcohol washes three times, uses ethanol suspension.
BTBCT-Eu prepared by above three embodiments
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 more than three months.
Claims (5)
1. a preparation method for fluorescent rare earth 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 doubly and 0.1-0.4 diethyl carbonate are doubly mixed in 100 grams of ethyl acetate or toluene, add the catalyzer of the 0.1%-4% of tetraethoxy quality, drip tetraethoxy quality 0.2-4.0 distilled water doubly, at 150 DEG C of-240 DEG C 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 mixed solution A, 1.5 grams of aluminum isopropylates will be no more than join in 10 grams of Virahols and make mixing solutions B, mixing solutions B is added drop-wise in mixed solution A, react at 180 DEG C of-220 DEG C of temperature, 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 Virahol doubly of adding portion hydrolysis nano silicon oxide quality of the emulsion, ultrasonic agitation, moves in pressure reaction still and reacts 36-120 hour, solvent evaporated ethyl acetate or toluene, obtains modified Nano silicon-aluminium emulsion;
The finishing of 1.2 modified Nano silicon-aluminium
It is in the ethanolic soln of the silane coupling agent of 3-8% that described nano-silicon-aluminium emulsion 0.5-2mL is joined 0.8-1.2mL mass percent concentration, heat and keep temperature 70 ± 2 DEG C, 5-10 minute, with absolute ethanol washing, then the nano-silicon-aluminium after washing is suspended in ethanol the nano-silicon-aluminium suspension obtained with amino;
The preparation of 1.3 fluorescent rare earth complex modified Nano silicon-aluminium emulsions
By 9.0 × 10
-6mmolL
-14; 4 '-two (1 "; 1 " 1 "-three fluoro-2 "; 4 "-dimethyl diketone-6 "-acyl groups)-chlorosulphonation o-terphenyl 55 μ L joins 150-400 μ L with in the nano-silicon-aluminium suspension of amino, ultrasonic agitation 2-3 hour, then uses washing with alcohol; suspend with 70 μ L0.05M, pH 7.8Tris-HCl, add 1.7 × 10
-4mmolL
-1euCl
34.9-6.0mL, in 35-37 DEG C of water bath with thermostatic control lucifuge ultrasonic agitation 30-50 minute, dehydrated alcohol washes three times, uses ethanol suspension.
2. the preparation method of fluorescent rare earth 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 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 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 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.
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