CN100444946C - Method for preparing micro-capsule containing high light-effect rare earth compounding matter - Google Patents
Method for preparing micro-capsule containing high light-effect rare earth compounding matter Download PDFInfo
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- CN100444946C CN100444946C CNB2007100142500A CN200710014250A CN100444946C CN 100444946 C CN100444946 C CN 100444946C CN B2007100142500 A CNB2007100142500 A CN B2007100142500A CN 200710014250 A CN200710014250 A CN 200710014250A CN 100444946 C CN100444946 C CN 100444946C
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Abstract
A process for preparing the RE match microcapsules with high optical effect includes such steps as choosing a main luminous body from Eu(III) beta-biketone matches Eu(acac)3Phen, Eu(TFA)3Phen, Eu(HFA)3Phen, Eu(TTA)3Phen, Eu(DBM)3Phen and Eu(PTA)3Phen, preparing the solid microcapsule whose shell layer contains said RE matches, and preparing the hollow microcapsules whose shell contains RE matches by dissolving the central core.
Description
Technical field
The present invention relates to a kind of preparation method who contains the high light-effect rare earth compounding microcapsules, relate in particular to and a kind ofly utilize the package technique preparation on the molecular level to have the solid microcapsules that contain high light-effect rare earth compounding of stable nucleus shell structure and the new technique of hollow microcapsules.
Background technology
The luminous big and good characteristics of rare earth luminescence monochromaticjty of organic matter dyestuff luminous intensity that have concurrently of rare earth compounding.Absorption coefficient to ultraviolet light is very big, can transmit to rare earth ion generation high efficiency energy.And dye molecule has the glow peak that span reaches tens nanometers even nanometers up to a hundred.Therefore, rare earth compounding has the absolute predominance of luminous monochromaticjty aspect than dyestuff, be the desirable luminescent substance of observing the multiple mark color of red, green, blue picture rich in detail at visible region simultaneously, can be used as molecular fluorescence device material, working-laser material and bioanalysis fluorescence probe.
General colloid of German horse in 1998 and interface science research institute
People such as professor, doctor Donath adopt the kernel template of colloidal solid as assembling, by the package technique on the molecular level---successively assemble (layer-by-layer, LbL) technology on the kernel template, has successfully been assembled the solid microcapsules with stable nucleus shell structure with anionic polyelectrolyte, cationic polyelectrolyte alternating deposit.Then template particles is removed, prepared the hollow microcapsules of structural integrity.
Yet, with the LbL technology is the assembling means, the selection diameter is several microns different kernel mould materials, procedure parameters such as the chemical constituent of setting deposition polyelectrolyte and rare earth compounding, ratio, different phase in assembling is introduced different shells with rare earth compounding, obtain containing in the shell method of the microcapsules of photism rare earth compounding, yet there are no report by retrieval.
Summary of the invention
At above-mentioned the deficiencies in the prior art, the problem to be solved in the present invention is that selecting high light-effect rare earth europium (III) β-complex is illuminator, proposes a kind of method that contains the high light-effect rare earth compounding microcapsules with the preparation of LbL technology.
The preparation method of the above-mentioned microcapsules that provide, the mainly purpose of inventing by following technology path realization:
(1) selects europium (III) beta-diketone complex, make it and in solution, dissociate not only to have intermolecular interaction between the charged polyelectrolyte in back, and have dipole-charge interaction;
(2) prepare the microcapsules that contain high light-effect rare earth compounding in the shell, on the kernel template, contain the solid microcapsules of rare earth compounding in the preparation shell, prepare the hollow microcapsules that contains rare earth compounding in the shell then.
The preparation method of the photism rare earth compounding microcapsules that relate among the present invention, specifically be made up of following step:
(1) selecting dipole moment is 1～6 europium that must visit (III) beta-diketone complex Eu (acac)
3Phen, Eu (TFA)
3Phen, Eu (HFA)
3Phen, Eu (TTA)
3Phen, Eu (DBM)
3Phen, Eu (PTA)
3One of Phen joins its alcohol saturated solution respectively, and is standby;
Wherein: above-mentioned beta-diketonate ligand acac=acetylacetone,2,4-pentanedione, TFA=trifluoroacetylacetone (TFA), HFA=hexafluoroacetylacetone, the TTA=TTA, DBM=dibenzoyl methane, PTA=benzoyltrifluoroacetone, collaborative part Phen=1, the 10-o-phenanthroline;
(2) join the sodium-chloride water solution that concentration is 3-300mg/ml, standby;
(3) selecting molecular weight is 20,000～200, one of 000 anionic polyelectrolyte kayexalate (PSS), sodium alginate (SA), PAMA (APAA), anionic starch (AS), sodium apolate (SPES), with step (2) solution is solvent, join concentration and be the anionic polyelectrolyte solution of 0.2～20.00mg/ml, standby;
(4) selecting molecular weight is 20,000～200, one of ammonium chloride (PAH), polymine (PEI), cation polyacrylamide (CPAA), cationic starch (CS), cationic chitosan (CC) in 000 cationic polyelectrolyte diallyl dimethyl ammoniumchloride (PDADMH), the polyene, with step (2) solution is solvent, join concentration and be the cationic polyelectrolyte solution of 0.2～20.00mg/ml, standby;
(5) be the solution that 1: 10～3: 1 solution that obtains of blend step (1) and step (3) obtain by europium (III) beta-diketone complex and anionic polyelectrolyte mass ratio, standby;
(6) be the solution that 1: 10～3: 1 solution that obtains of blend step (1) and step (4) obtain by europium (III) beta-diketone complex and cationic polyelectrolyte mass ratio, standby;
(7) join the hydrochloric acid solution that concentration is 2～400mg/ml, standby;
(8) choosing diameter is 0.50～10.00 micron melamino-formaldehyde condensation oligomer (MF), manganese carbonate (MnCO
3), calcium carbonate (CaCO
3) one of microballoon is as the kernel template;
(9) A, prepare the microcapsules that all contain high light-effect rare earth compounding in each shell:
1. deposit ground floor: get one of described kernel template of step (8), place contain with its surface the solution that obtains of electrically charged opposite step (5) or step (6), make in every ml soln to contain 10
6～10
9Individual microballoon, sedimentation time 60～1800 seconds is under the 3000rps centrifugal 120～1200 seconds at rotating speed then, washs in ultra-pure water 1～5 time, obtains the microcapsules that template coats one deck rare earth compounding/polyelectrolyte outward;
2. deposit the second layer: the microcapsules that 1. step (9) A is obtained place and the 1. used step (6) of the polyelectrolyte of opposite charges or the solution that step (5) obtains of containing of step (9) A, make in every ml soln to contain 10
6～10
9Individual microballoon, sedimentation time 60～1800 seconds is under the 3000rps centrifugal 120～1200 seconds at rotating speed then, washs in ultra-pure water 1～5 time, obtains the outer microcapsules that coat two layers of rare earth compounding/polyelectrolyte of template;
3. the 3rd layer of deposition: the microcapsules that 2. step (9) A is obtained place and the 2. used step (5) of the polyelectrolyte of opposite charges or the solution that step (6) obtains of containing of step (9) A, make in every ml soln to contain 10
6～10
9Individual microballoon, sedimentation time 60～1800 seconds is under the 3000rps centrifugal 120～1200 seconds at rotating speed then, washs in ultra-pure water 1～5 time, obtains the outer microcapsules that coat three layers of rare earth compounding/polyelectrolyte of template;
4. repeatedly deposition obtains containing the solid microcapsules of multilayer rare earth compounding: repeating step (9) A 2., (9) A 3., so deposit after 8～10 times, obtain all containing in each shell the solid microcapsules of rare earth compounding;
5. use the solid microcapsules that 4. (7) solution obtain (9) A in the step 1 to carry out molten nuclear 60～1200 seconds, obtain all containing in each shell the hollow microcapsules of rare earth compounding behind the centrifuge washing;
Or (9) B, preparation contain the solid microcapsules of high light-effect rare earth compounding in the outer shell:
1. deposit ground floor: get one of described kernel template of step (8), place contain with its surface the polyelectrolyte solution that obtains of electrically charged opposite step (3) or step (4), make in every ml soln to contain 10
6～10
9Individual microballoon, sedimentation time 60～1800 seconds is under the 3000rps centrifugal 120～1200 seconds at rotating speed then, washs in ultra-pure water 1～5 time, obtains the microcapsules that template coats one deck polyelectrolyte outward;
2. deposit the second layer: the microcapsules that 1. step (9) B is obtained place and the 1. used step (4) of the polyelectrolyte of opposite charges or the solution that step (3) obtains of containing of step (9) B, make in every ml soln to contain 10
6～10
9Individual microballoon, sedimentation time 60～1800 seconds is under the 3000rps centrifugal 120～1200 seconds at rotating speed then, washs in ultra-pure water 1～5 time, obtains the outer electrolytical microcapsules of two stratas that coat of template;
3. the 3rd layer of deposition: the microcapsules that 2. step (9) B is obtained place and the 2. used step (3) of the polyelectrolyte of opposite charges or the solution that step (4) obtains of containing of step (9) B, make in every ml soln to contain 10
6～10
9Individual microballoon, sedimentation time 60～1800 seconds is under the 3000rps centrifugal 120～1200 seconds at rotating speed then, washs in ultra-pure water 1～5 time, obtains the outer electrolytical microcapsules of three stratas that coat of template;
4. repeatedly deposition obtains not containing in the shell the solid microcapsules that contain multi-layer polyelectrolyte of rare earth compounding: repeating step (9) B 2., (9) B 3., so deposit after 8～10 times, obtain not containing in the shell the solid microcapsules of rare earth compounding;
5. the microcapsules that 4. step (9) B the is obtained rare earth compounding solution that places step 1 (1) to obtain makes in every ml soln to contain 10
6～10
9Individual microballoon, sedimentation time 60～1800 seconds is under the 3000rps centrifugal 120～1200 seconds at rotating speed then, washs in ultra-pure water 1～5 time, obtains the solid microcapsules that outer shell contains one deck rare earth compounding;
6. repeating step (9) B is 5. 1～5 time, obtains the solid microcapsules that outer shell contains 2～6 layers of rare earth compounding;
7. use the solid microcapsules that 6. (7) solution obtain (9) B in the step 1 to carry out molten nuclear 60～1200 seconds, it is under the 3000rps centrifugal 120～1200 seconds at rotating speed then, in ultra-pure water, wash 1～5 time, obtain the hollow microcapsules that outer shell contains 2～6 layers of rare earth compounding.
Wherein, above-mentioned beta-diketonate ligand most preferably is TTA.
Wherein, above-mentioned NaCl solution concentration most preferably is 30mg/ml.
Wherein, above-mentioned anionic polyelectrolyte solution most preferably is that molecular weight is 70,000, concentration is the kayexalate solution of 2.0mg/ml.
Wherein, above-mentioned cationic polyelectrolyte solution most preferably is that molecular weight is 70,000, concentration is the diallyl dimethyl ammoniumchloride solution of 2.0mg/ml.
Wherein, the mass ratio of (5) or (6) described rare earth compounding and polyelectrolyte most preferably is 1: 2 in the step 1.
Wherein, most preferably to be diameter be 5 microns manganese carbonate for above-mentioned kernel template.
Wherein, above-mentioned sedimentation time most preferably is 600 seconds.
Wherein, above-mentioned centrifugation time most preferably is 600 seconds.
Wherein, above-mentioned washing times in ultra-pure water most preferably is 3 times.
After utilizing the inventive method to obtain containing the microcapsules of rare earth compounding, measure fluorescence spectrum on U.S. Perkin Elmer LS55 instrument, excitation wavelength 350nm excites slit and emission slit to be respectively 10nm, 5nm.Use the mercury lamp light source, 60 times of oily mirrors, exciter filter 330-385nm, emission optical filter 610nm, DP70CCD obtains the microcapsules fluorescence micrograph on Japanese Olympus IX81.With 3KeV voltage at the enterprising line scanning electron microscopic observation of Japanese JEOL JSM-6700F.On U.S. Nanoscope IIIa Multimode AFM, characterize the shape and the roughness of hollow microcapsules, sweep speed 0.5Hz, micro-cantilever resonant frequency 200-300kHz with the pattern of rapping.
Fig. 1 has provided solid microcapsules { MnCO on the manganese carbonate kernel template
3| [(PAH) (PSS)]
4[Eu (DBM)
3Phen]
2The ESEM picture, rare earth compounding microcapsules rete is complete, structure is intact.The fluorescence property of microcapsules is good, and when only depositing one deck rare earth compounding in the shell, uviol lamp excites down microcapsules promptly to send macroscopic light.Fig. 2 has provided aqueous solution hollow core microcapsules [(PAH) (PSS)]
4[Eu (DBM)
3Phen]
2Fluorescence micrograph and fluorescence intensity curves, shell brightness is very big.Two end peak explanation rare earth compoundings that fluorescence intensity curves distributes are assembled in the microcapsules shell.The fluorescent emission of hollow rare earth compounding microcapsules and solid microcapsules does not have significant difference.Fig. 3 has provided dry state hollow microcapsules [(Eu (TTA)
3Phen/PSS) (Eu (TTA)
3Phen/PAH)]
4Atomic force micrograph and altitude curve.The microcapsules shell is complete rete, average thickness 32nm, and every strata electrolyte or rare earth compounding thickness are 1.6nm, and is suitable with the thicknesses of layers of the microcapsules that do not contain rare earth compounding.The rete roughness is 2.9nm only, illustrate rare earth compounding with ultrafine particle form uniform deposition in shell.Fig. 4 has provided on the MF kernel template solid microcapsules { MF|[(Eu (TTA) on the solid microcapsules MF kernel template
3Phen/PSS) (Eu (TTA)
3Phen/PAH)]
4Fluorescence spectrum (solid line) and Eu (TTA)
3The fluorescence spectrum of Phen ethanolic solution (dotted line), excitation wavelength 350nm, the hyperfluorescence peak position of microcapsules is in 612.0nm, and half-peak breadth is very narrow, belongs to Eu (III) ion excited state
5D
0To ground state
7F
2The feature emission peak.
The inventive method belongs to research contents leading in the world, has following advantage: based on dipole-charge interaction and intermolecular interaction, prepare the microcapsules that contain rare earth compounding in the shell by laminated assembling technology.Shell middle rare earth complex is distributed in the shell very equably with the ultrafine particle form, sends macroscopic hyperfluorescence under ultraviolet excitation.Good solid microcapsules of photism and the hollow microcapsules of monochromaticjty that has the stable nucleus shell structure for preparation provides an effective way.
Description of drawings
Solid microcapsules { MnCO on Fig. 1 manganese carbonate kernel template
3| [(PAH) (PSS)]
4[Eu (DBM)
3Phen]
2The ESEM picture, rare earth compounding microcapsules rete is complete, structure is intact.
Fig. 2 aqueous solution hollow core microcapsules [(PAH) (PSS)]
4[Eu (DBM)
3Phen]
2Fluorescence micrograph and fluorescence intensity curves, two end peaks explanation rare earth compoundings that fluorescence intensity curves distributes are assembled in the microcapsules shell.
Fig. 3 dry state hollow microcapsules [(Eu (TTA)
3Phen/PSS) (Eu (TTA)
3Phen/PAH)]
4Atomic force micrograph and altitude curve, the microcapsules shell is complete rete, average thickness 32nm, the rete roughness is 2.9nm only.
Solid microcapsules { MF[(Eu (TTA) on Fig. 4 MF kernel template
3Phen/PSS) (Eu (TTA)
3Phen/PAH)]
4And hollow microcapsules [(Eu (TTA)
3Phen/PSS) (Eu (TTA)
3Phen/PAH)]
4Fluorescence spectrum (solid line) and Eu (TTA)
3The fluorescence spectrum of Phen ethanolic solution (dotted line), excitation wavelength 350nm, the hyperfluorescence peak position of microcapsules is in 612.0nm, and half-peak breadth is very narrow.
The specific embodiment
Below in conjunction with embodiment content of the present invention is further elaborated, wherein: described beta-diketonate ligand acac=acetylacetone,2,4-pentanedione, the TFA=trifluoroacetylacetone (TFA), the HFA=hexafluoroacetylacetone, the TTA=TTA, PTA=benzoyltrifluoroacetone, DBM=dibenzoyl methane, collaborative part Phen=1, the 10-o-phenanthroline.
Embodiment 1. contains the preparation method of high light-effect rare earth compounding microcapsules, and step is as follows:
(1) selects europium (III) beta-diketone complex Eu (DBM)
3Phen;
(2) join the sodium-chloride water solution that concentration is 30mg/ml;
(3) be solvent with step (2) solution, the selection molecular weight is 70,000 anionic polyelectrolyte kayexalate (PSS), joins the solution that its concentration is 2.0mg/ml;
(4) the selection molecular weight is 70,000 cationic polyelectrolyte poly diallyldimethylammonium chloride (PAH), is solvent with step (2) solution, joins the solution that its concentration is 2.0mg/ml;
(5) press Eu (DBM)
3Phen and PSS mass ratio are the solution that 1: 2 solution that obtains of blend step (1) and step (3) obtain;
(6) press Eu (DBM)
3Phen and PAH mass ratio are the solution that 1: 2 solution that obtains of blend step (1) and step (4) obtain;
(7) join the hydrochloric acid that concentration is 20mg/ml;
(8) choosing diameter is that 5.00 microns melamino-formaldehyde condensation oligomer (MF) microballoon is as the kernel template;
(9) prepare the microcapsules that all contain high light-effect rare earth compounding in each shell:
1. deposit ground floor: get the solution that MF kernel template microsphere places step (5) to obtain, make in every ml soln to contain 2.0 * 10
8Individual microballoon, sedimentation time 600 seconds is under the 3000rps centrifugal 600 seconds at rotating speed then, washing is 3 times in ultra-pure water, obtains MF and coats [Eu (DBM) outward
3Phen/PSS] a microcapsule;
2. deposit the second layer:, make in every ml soln to contain 2.0 * 10 with (9) the 1. microcapsules solution that places step (6) to obtain
8Individual microcapsules, sedimentation time 600 seconds is under the 3000rps centrifugal 600 seconds at rotating speed then, washing is 3 times in ultra-pure water, obtains MF and coats [(Eu (DBM) outward
3Phen/PSS) (Eu (DBM)
3Phen/PAH)] two microcapsules { MF[(Eu (DBM)
3Phen/PSS) (Eu (DBM)
3Phen/PAH)] };
3. the 3rd layer of deposition: the solution that the microcapsules that (9) are 2. obtained place step (5) to obtain makes in every ml soln to contain 2.0 * 10
8Individual microballoon, sedimentation time 600 seconds is under the 3000rps centrifugal 600 seconds at rotating speed then, washing is 3 times in ultra-pure water, obtains MF and coats [(Eu (DBM) outward
3Phen/PSS) (Eu (DBM)
3Phen/PAH) (Eu (DBM)
3Phen/PSS)] three microcapsules { MF|[(Eu (DBM)
3Phen/PSS) (Eu (DBM)
3Phen/PAH) (Eu (DBM)
3Phen/PSS)] };
4. repeatedly deposition obtains containing multilayer Eu (DBM)
3The solid microcapsules of Phen: repeating step (9) 2., (9) 3., so deposit after 8 times, obtain all containing in each shell Eu (DBM)
3The solid eight microcapsules { MF|[(Eu (DBM) of Phen
3Phen/PSS) (Eu (DBM)
3Phen/PAH)]
4;
5. use the solid microcapsules that 4. (7) solution obtain (9) in the step 1 to carry out molten nuclear 600 seconds according to kernel templated chemistry composition, obtain all containing in each shell Eu (DBM) behind the centrifuge washing
3The hollow microcapsules of Phen [(Eu (DBM)
3Phen/PSS) (Eu (DBM)
3Phen/PAH)]
4
(10) the ESEM result shows, contains Eu (DBM)
3The microcapsules rete of Phen is complete, and structure is intact; The fluorescence property of microcapsules is good, only deposits one deck Eu (DBM) in the shell
3During Phen, uviol lamp excites down microcapsules promptly to send macroscopic light; Fluorescence micrograph is the result show, shell brightness is very big; Hollow Eu (DBM)
3The fluorescent emission of Phen microcapsules and solid microcapsules does not have significant difference; The atomic force micrograph result of dry state hollow microcapsules shows that the microcapsules shell is complete, every layer of Eu (DBM)
3Phen/ polyelectrolyte thickness is 1.65nm; The rete roughness is 3.0nm only, and Eu (DBM) is described
3Phen with ultrafine particle form uniform deposition in shell; The hyperfluorescence peak position of microcapsules is in 612.0nm, and half-peak breadth is very narrow, belongs to Eu (III) ion excited state
5D
0To ground state
7F
2The feature emission peak.
(1) selects rare earth compounding Eu (DBM)
3Phen; With reference to embodiment 1 step (1)-(9) method, use MnCO
3As template microsphere, make in every ml soln to contain 2.0 * 10
8Individual microcapsules, sedimentation time 600 seconds, under the 3000rps centrifugal 600 seconds, washing was 3 times in ultra-pure water, and preparation contains Eu (DBM)
3Solid microcapsules { the MnCO of Phen
3[(Eu (DBM)
3Phen/PAH) (Eu (DBM)
3Phen/PSS)]
4And hollow microcapsules [(Eu (DBM)
3Phen/PAH) (Eu (DBM)
3Phen/PSS)]
4
(2) contain Eu (DBM)
3The microcapsules rete of Phen is complete, and structure is intact; The fluorescence property of microcapsules is good, only deposits one deck Eu (DBM) in the shell
3During Phen, uviol lamp excites down microcapsules promptly to send macroscopic light; Hollow Eu (DBM)
3The fluorescent emission of Phen microcapsules and solid microcapsules does not have significant difference; The atomic force micrograph result of dry state hollow microcapsules shows that the microcapsules shell is complete, every layer of Eu (DBM)
3Phen/ polyelectrolyte thickness is 2.5nm; The rete roughness is 1.5nm only, and Eu (DBM) is described
3Phen with ultrafine particle form uniform deposition in shell; The hyperfluorescence peak position of microcapsules is in 612.0nm, and half-peak breadth is very narrow.
Embodiment 3. contains the preparation method of high light-effect rare earth compounding microcapsules, and step is as follows:
(1) selects rare earth compounding Eu (TTA)
3Phen; With reference to embodiment 1 step (1)-(9) method, make in every ml soln to contain 5.0 * 10
7Individual microcapsules, sedimentation time 600 seconds, under the 3000rps centrifugal 600 seconds, washing was 3 times in ultra-pure water, and preparation contains Eu (TTA)
3The solid microcapsules of Phen { MF[(Eu (TTA)
3Phen/PSS) (Eu (TTA)
3Phen/PAH)]
4And hollow microcapsules [(Eu (TTA)
3Phen/PSS) (Eu (TTA)
3Phen/PAH)]
4
(2) contain Eu (TTA)
3The microcapsules rete of Phen is complete, and structure is intact; The fluorescence property of microcapsules is good, only deposits one deck Eu (TTA) in the shell
3During Phen, uviol lamp excites down microcapsules promptly to send macroscopic light; Hollow Eu (TTA)
3The fluorescent emission of Phen microcapsules and solid microcapsules does not have significant difference; The atomic force micrograph result of dry state hollow microcapsules shows that the microcapsules shell is complete, every layer of Eu (TTA)
3Phen/ polyelectrolyte thickness is 2.5nm; The rete roughness is 1.8nm only, and Eu (TTA) is described
3Phen with ultrafine particle form uniform deposition in shell; The hyperfluorescence peak position of microcapsules is in 612.0nm, and half-peak breadth is very narrow.
Embodiment 4. contains the preparation method of high light-effect rare earth compounding microcapsules, and step is as follows:
(1) selects rare earth compounding Eu (TTA)
3Phen; With reference to embodiment 1 step (1)-(9) method, use MnCO
3As template microsphere, make in every ml soln to contain 1.0 * 10
8Individual microcapsules, sedimentation time 600 seconds, under the 3000rps centrifugal 600 seconds, washing was 3 times in ultra-pure water, and preparation contains Eu (TTA)
3Solid microcapsules { the MnCO of Phen
3| [(Eu (TTA)
3Phen/PEI) (Eu (TTA)
3Phen/AS)]
4And hollow microcapsules [(Eu (TTA)
3Phen/PEI) (Eu (TTA)
3Phen/AS)]
4
(2) contain Eu (TTA)
3The microcapsules rete of Phen is complete, and structure is intact; The fluorescence property of microcapsules is good, only deposits one deck Eu (TTA) in the shell
3During Phen, uviol lamp excites down microcapsules promptly to send macroscopic light; Hollow Eu (TTA)
3The fluorescent emission of Phen microcapsules and solid microcapsules does not have significant difference; The atomic force micrograph result of dry state hollow microcapsules shows that the microcapsules shell is complete, every layer of Eu (TTA)
3Phen/ polyelectrolyte thickness is 1.6nm; The rete roughness is 2.9nm only, and Eu (TTA) is described
3Phen with ultrafine particle form uniform deposition in shell; The hyperfluorescence peak position of microcapsules is in 612.0nm, and half-peak breadth is very narrow.
Embodiment 5. contains the preparation method of high light-effect rare earth compounding microcapsules, and step is as follows:
(1) selects rare earth compounding Eu (acac)
3Phen; With reference to embodiment 1 step (1)-(9) method, make in every ml soln to contain 3.0 * 10
8Individual microcapsules, sedimentation time 800 seconds, under the 3000rps centrifugal 1000 seconds, washing was 4 times in ultra-pure water, and preparation contains Eu (acac)
3The solid microcapsules of Phen { MF|[(Eu (acac)
3Phen/PSS) (Eu (acac)
3Phen/PEI)]
4And hollow microcapsules [(Eu (acac)
3Phen/PSS) (Eu (acac)
3Phen/PEI)]
4
(2) contain Eu (acac)
3The microcapsules rete of Phen is complete, and structure is intact; The fluorescence property of microcapsules is good, only deposits one deck Eu (acac) in the shell
3During Phen, uviol lamp excites down microcapsules promptly to send macroscopic light; Hollow Eu (acac)
3The fluorescent emission of Phen microcapsules and solid microcapsules does not have significant difference; The atomic force micrograph result of dry state hollow microcapsules shows that the microcapsules shell is complete, every layer of Eu (acac)
3Phen/ polyelectrolyte thickness is 1.55nm; The rete roughness is 2.6nm only, and Eu (acac) is described
3Phen with ultrafine particle form uniform deposition in shell; The hyperfluorescence peak position of microcapsules is in 612.0nm, and half-peak breadth is very narrow.
(1) selects rare earth compounding Eu (acac)
3Phen; With reference to embodiment 1 step (1)-(9) method, use CaCO
3As template microsphere, make in every ml soln to contain 3.0 * 10
8Individual microcapsules, sedimentation time 800 seconds, under the 3000rps centrifugal 1000 seconds, washing was 4 times in ultra-pure water, and preparation contains Eu (acac)
3Solid microcapsules { the CaCO of Phen
3| [(Eu (acac)
3Phen/PAH) (Eu (acac)
3Phen/PSS)]
4And hollow microcapsules [(Eu (acac)
3Phen/PAH) (Eu (acac)
3Phen/PSS)]
4
(2) contain Eu (acac)
3The microcapsules rete of Phen is complete, and structure is intact; The fluorescence property of microcapsules is good, only deposits one deck Eu (acac) in the shell
3During Phen, uviol lamp excites down microcapsules promptly to send macroscopic light; Hollow Eu (acac)
3The fluorescent emission of Phen microcapsules and solid microcapsules does not have significant difference; The atomic force micrograph result of dry state hollow microcapsules shows that the microcapsules shell is complete, every layer of Eu (acac)
3Phen/ polyelectrolyte thickness is 1.7nm; The rete roughness is 2.8nm only, and Eu (acac) is described
3Phen with ultrafine particle form uniform deposition in shell; The hyperfluorescence peak position of microcapsules is in 612.0nm, and half-peak breadth is very narrow.
Embodiment 7. contains the preparation method of high light-effect rare earth compounding microcapsules, and step is as follows:
(1) selects rare earth compounding Eu (TFA)
3Phen; With reference to embodiment 1 step (1)-(9) method, use MnCO
3As template microsphere, make in every ml soln to contain 8.0 * 10
6Individual microcapsules, sedimentation time 640 seconds, under the 3000rps centrifugal 640 seconds, washing was 2 times in ultra-pure water, and preparation contains Eu (TFA)
3Solid microcapsules { the MnCO of Phen
3| [(Eu (TFA)
3Phen/CC) (Eu (TFA)
3Phen/SA)]
4And hollow microcapsules [(Eu (TFA)
3Phen/CC) (Eu (TFA)
3Phen/SA)]
4
(2) contain Eu (TFA)
3The microcapsules rete of Phen is complete, and structure is intact; The fluorescence property of microcapsules is good, only deposits one deck Eu (TFA) in the shell
3During Phen, uviol lamp excites down microcapsules promptly to send macroscopic light; Hollow Eu (TFA)
3The fluorescent emission of Phen microcapsules and solid microcapsules does not have significant difference; The atomic force micrograph result of dry state hollow microcapsules shows that the microcapsules shell is complete, every layer of Eu (TFA)
3Phen/ polyelectrolyte thickness is 3.5nm; The rete roughness is 3.0nm only, and Eu (TFA) is described
3Phen with ultrafine particle form uniform deposition in shell; The hyperfluorescence peak position of microcapsules is in 612.0nm, and half-peak breadth is very narrow.
(1) selects rare earth compounding Eu (TFA)
3Phen; With reference to embodiment 1 step (1)-(9) method, use CaCO
3As template microsphere, make in every ml soln to contain 8.0 * 10
6Individual microcapsules, sedimentation time 640 seconds, under the 3000rps centrifugal 640 seconds, washing was 2 times in ultra-pure water, and preparation contains Eu (TFA)
3Solid microcapsules { the CaCO of Phen
3| [(Eu (TFA)
3Phen/CC) (Eu (TFA)
3Phen/SA)]
4And hollow microcapsules [(Eu (TFA)
3Phen/CC) (Eu (TFA)
3Phen/SA)]
4
(2) contain Eu (TFA)
3The microcapsules rete of Phen is complete, and structure is intact; The fluorescence property of microcapsules is good, only deposits one deck Eu (TFA) in the shell
3During Phen, uviol lamp excites down microcapsules promptly to send macroscopic light; The fluorescent emission of hollow Eu (TFA) 3Phen microcapsules and solid microcapsules does not have significant difference; The atomic force micrograph result of dry state hollow microcapsules shows that the microcapsules shell is complete, every layer of Eu (TFA)
3Phen/ polyelectrolyte thickness is 3.2nm; The rete roughness is 2.5nm only, and Eu (TFA) is described
3Phen with ultrafine particle form uniform deposition in shell; The hyperfluorescence peak position of microcapsules is in 612.0nm, and half-peak breadth is very narrow.
Embodiment 9. contains the preparation method of high light-effect rare earth compounding microcapsules, and step is as follows:
(1) selects rare earth compounding Eu (HFA)
3Phen; With reference to embodiment 1 step (1)-(9) method, make in every ml soln to contain 8.0 * 10
6Individual microcapsules, sedimentation time 640 seconds, under the 3000rps centrifugal 640 seconds, washing was 2 times in ultra-pure water, and preparation contains Eu (HFA)
3The solid microcapsules of Phen { MF|[(Eu (HFA)
3Phen/SPES) (Eu (HFA)
3Phen/CPAA)]
4And hollow microcapsules [(Eu (HFA)
3Phen/SPES) (Eu (HFA)
3Phen/CPAA)]
4
(2) contain Eu (HFA)
3The microcapsules rete of Phen is complete, and structure is intact; The fluorescence property of microcapsules is good, only deposits one deck Eu (HFA) in the shell
3During Phen, uviol lamp excites down microcapsules promptly to send macroscopic light; Hollow Eu (HFA)
3The fluorescent emission of Phen microcapsules and solid microcapsules does not have significant difference; The atomic force micrograph result of dry state hollow microcapsules shows that the microcapsules shell is complete, every layer of Eu (HFA)
3Phen/ polyelectrolyte thickness is 1.5nm; The rete roughness is 2.9nm only, and Eu (HFA) is described
3Phen with ultrafine particle form uniform deposition in shell; The hyperfluorescence peak position of microcapsules is in 612.0nm, and half-peak breadth is very narrow.
(1) selects rare earth compounding Eu (HFA)
3Phen; With reference to embodiment 1 step (1)-(9) method, use MnCO
3As template microsphere, make in every ml soln to contain 6.0 * 10
7Individual microcapsules, sedimentation time 640 seconds, under the 3000rps centrifugal 640 seconds, washing was 2 times in ultra-pure water, and preparation contains Eu (HFA)
3Solid microcapsules { the MnCO of Phen
3| [(Eu (HFA)
3Phen/CS) (Eu (HFA)
3Phen/PSS)]
4And hollow microcapsules [(Eu (HFA)
3Phen/CS) (Eu (HFA)
3Phen/PSS)]
4
(2) contain Eu (HFA)
3The microcapsules rete of Phen is complete, and structure is intact; The fluorescence property of microcapsules is good, only deposits one deck Eu (HFA) in the shell
3During Phen, uviol lamp excites down microcapsules promptly to send macroscopic light; Hollow Eu (HFA)
3The fluorescent emission of Phen microcapsules and solid microcapsules does not have significant difference; The atomic force micrograph result of dry state hollow microcapsules shows that the microcapsules shell is complete, every layer of Eu (HFA)
3Phen/ polyelectrolyte thickness is 3.5nm; The rete roughness is 3.0nm only, and Eu (HFA) is described
3Phen with ultrafine particle form uniform deposition in shell; The hyperfluorescence peak position of microcapsules is in 612.0nm, and half-peak breadth is very narrow.
Embodiment 11. contains the preparation method of high light-effect rare earth compounding microcapsules, and step is as follows:
(1) selects rare earth compounding Eu (PTA)
3Phen; With reference to embodiment 1 step (1)-(9) method, make in every ml soln to contain 8.0 * 10
8Individual microcapsules, sedimentation time 900 seconds, under the 3000rps centrifugal 180 seconds, washing was 4 times in ultra-pure water, and preparation contains Eu (PTA)
3The solid microcapsules of Phen { MF|[(Eu (PTA)
3Phen/PSS) (Eu (PTA)
3Phen/PAH)]
4And hollow microcapsules [(Eu (PTA)
3Phen/PSS) (Eu (PTA)
3Phen/PAH)]
4
(2) contain Eu (PTA)
3The microcapsules rete of Phen is complete, and structure is intact; The fluorescence property of microcapsules is good, only deposits one deck Eu (PTA) in the shell
3During Phen, uviol lamp excites down microcapsules promptly to send macroscopic light; Hollow Eu (PTA)
3The fluorescent emission of Phen microcapsules and solid microcapsules does not have significant difference; The atomic force micrograph result of dry state hollow microcapsules shows that the microcapsules shell is complete, every layer of Eu (PTA)
3Phen/ polyelectrolyte thickness is 1.55nm; The rete roughness is 2.5nm only, and Eu (PTA) is described
3Phen with ultrafine particle form uniform deposition in shell; The hyperfluorescence peak position of microcapsules is in 612.0nm, and half-peak breadth is very narrow.
Embodiment 12. contains the preparation method of high light-effect rare earth compounding microcapsules, and step is as follows:
(1) selects rare earth compounding Eu (PTA)
3Phen; With reference to embodiment 1 step (1)-(9) method, make in every ml soln to contain 8.0 * 10
8Individual microcapsules, sedimentation time 900 seconds, under the 3000rps centrifugal 240 seconds, washing was 4 times in ultra-pure water, and preparation contains Eu (PTA)
3The solid microcapsules of Phen { MF|[(Eu (PTA)
3Phen/APAA) (Eu (PTA)
3Phen/PDADMH)]
4And hollow microcapsules [(Eu (PTA)
3Phen/APAA) (Eu (PTA)
3Phen/PDADMH)]
4
(2) contain Eu (PTA)
3The microcapsules rete of Phen is complete, and structure is intact; The fluorescence property of microcapsules is good, only deposits one deck Eu (PTA) in the shell
3During Phen, uviol lamp excites down microcapsules promptly to send macroscopic light; Hollow Eu (PTA)
3The fluorescent emission of Phen microcapsules and solid microcapsules does not have significant difference; The atomic force micrograph result of dry state hollow microcapsules shows that the microcapsules shell is complete, every layer of Eu (PTA)
3Phen/ polyelectrolyte thickness is 1.8nm; The rete roughness is 1.6nm only, and Eu (PTA) is described
3Phen with ultrafine particle form uniform deposition in shell; The hyperfluorescence peak position of microcapsules is in 612.0nm, and half-peak breadth is very narrow.
Embodiment 13. contains the preparation method of high light-effect rare earth compounding microcapsules, and step is as follows:
(1) selects europium (III) beta-diketone complex Eu (DBM)
3Phen;
(2) join the sodium-chloride water solution that concentration is 30mg/ml;
(3) be solvent with step (2) solution, the selection molecular weight is 70,000 anionic polyelectrolyte kayexalate, joins the solution that its concentration is 2.0mg/ml;
(4) the selection molecular weight is 70,000 cationic polyelectrolyte poly diallyldimethylammonium chloride (PAH), is solvent with step (2) solution, joins the solution that its concentration is 2.00mg/ml;
(5) join the hydrochloric acid that concentration is 20mg/ml;
(6) choosing diameter is that 5.00 microns MF microballoon is as the kernel template;
(7) contain Eu (DBM) in the preparation outer shell
3The solid microcapsules of Phen:
1. deposit ground floor: get the solution that MF kernel template microsphere places step (3) to obtain, make in every ml soln to contain 2.0 * 10
8Individual microballoon, sedimentation time 600 seconds is under the 3000rps centrifugal 600 seconds at rotating speed then, washing is 3 times in ultra-pure water, obtains the microcapsules { MF| (PSS) } that MF coats one deck PSS outward;
2. deposit the second layer:, make in every ml soln to contain 2.0 * 10 with (7) the 1. microcapsules solution that places step (4) to obtain
8Individual microcapsules, sedimentation time 600 seconds is under the 3000rps centrifugal 600 seconds at rotating speed then, washing is 3 times in ultra-pure water, obtains two microcapsules that MF coats [(PSS) (PAH)] outward { MF|[(PSS) (PAH)] };
3. the 3rd layer of deposition: the solution that the microcapsules that (7) are 2. obtained place step (3) to obtain makes in every ml soln to contain 2.0 * 10
8Individual microballoon, sedimentation time 600 seconds is under the 3000rps centrifugal 600 seconds at rotating speed then, washing is 3 times in ultra-pure water, obtains three microcapsules that MF coats [(PSS) (PAH) (PSS)] outward { MF|[(PSS) (PAH) (PSS)] };
4. repeatedly deposition obtains not containing in the shell the solid microcapsules that contain multi-layer polyelectrolyte of rare earth compounding: so repeating step (7) 2., (7) 3., deposit 8 times after, obtain not containing in the shell rare earth compounding solid microcapsules MF|[(PSS) (PAH)]
4;
5. the microcapsules that step (7) is 4. obtained place the Eu (DBM) that step (1) obtains
3In the Phen solution, make in every ml soln to contain 2.0 * 10
8Individual microballoon, sedimentation time 600 seconds is under the 3000rps centrifugal 600 seconds at rotating speed then, washing is 3 times in ultra-pure water, obtains outer shell and contains one deck Eu (DBM)
3The solid microcapsules of Phen MF|[(PSS) (PAH)]
4[Eu (DBM)
3Phen] };
6. repeating step (7) is 5. 2 times, obtains outer shell and contains 2 layers of Eu (DBM)
3The solid microcapsules of Phen MF|[(PSS) (PAH)]
4[Eu (DBM)
3Phen]
2;
7. the solid microcapsules that use step (5) solution that (7) are 6. obtained carried out molten nuclear 600 seconds, were under the 3000rps centrifugal 600 seconds at rotating speed then, and washing is 3 times in ultra-pure water, obtains outer shell and contains 2 layers of Eu (DBM)
3The hollow microcapsules of Phen [(PSS) (PAH)]
4[Eu (DBM)
3Phen]
2
(8) the ESEM result shows, contains Eu (DBM)
3The microcapsules rete of Phen is complete, and structure is intact; The fluorescence property of microcapsules is good, only deposits one deck Eu (DBM) in the shell
3During Phen, uviol lamp excites down microcapsules promptly to send macroscopic light; Fluorescence micrograph is the result show, shell brightness is very big; Hollow Eu (DBM)
3The fluorescent emission of Phen microcapsules and solid microcapsules does not have significant difference; The atomic force micrograph result of dry state hollow microcapsules shows that the microcapsules shell is complete, every layer of Eu (DBM)
3Phen/ polyelectrolyte thickness is 1.8nm; The rete roughness is 2.6nm only, and Eu (DBM) is described
3Phen with ultrafine particle form uniform deposition in shell; The hyperfluorescence peak position of microcapsules is in 612.0nm.
Embodiment 14. contains the preparation method of high light-effect rare earth compounding microcapsules, and step is as follows:
(1) selects rare earth compounding Eu (DBM)
3Phen; With reference to embodiment 13 steps (1)-(7) method, use MnCO
3As template microsphere, make in every ml soln to contain 2.0*10
8Individual microcapsules, sedimentation time 900 seconds, under the 3000rps centrifugal 300 seconds, washing was 4 times in ultra-pure water, and preparation contains Eu (DBM)
3Solid microcapsules { the MnCO of Phen
3| [(PAH) (PSS)]
4[Eu (DBM)
3Phen]
2And hollow microcapsules [(PAH) (PSS)]
4[Eu (DBM)
3Phen]
2
(2) contain Eu (DBM)
3The microcapsules rete of Phen is complete, and structure is intact; The fluorescence property of microcapsules is good, only deposits one deck Eu (DBM) in the shell
3During Phen, uviol lamp excites down microcapsules promptly to send macroscopic light; Hollow Eu (DBM)
3The fluorescent emission of Phen microcapsules and solid microcapsules does not have significant difference; The atomic force micrograph result of dry state hollow microcapsules shows that the microcapsules shell is complete, every layer of Eu (DBM)
3Phen/ polyelectrolyte thickness is 1.65nm; The rete roughness is 1.7nm only, and Eu (DBM) is described
3Phen with ultrafine particle form uniform deposition in shell; The hyperfluorescence peak position of microcapsules is in 612.0nm, and half-peak breadth is very narrow.
Embodiment 15. contains the preparation method of high light-effect rare earth compounding microcapsules, and step is as follows:
(1) selects rare earth compounding Eu (acac)
3Phen; With reference to embodiment 13 steps (1)-(7) method, use MF as template microsphere, make in every ml soln to contain 8.0*10
8Individual microcapsules, sedimentation time 900 seconds, under the 3000rps centrifugal 300 seconds, washing was 4 times in ultra-pure water, and preparation contains Eu (acac)
3The solid microcapsules of Phen MF|[(PSS) (PAH)]
6[Eu (acac)
3Phen]
3And hollow microcapsules [(PSS) (PAH)]
6[Eu (acac)
3Phen]
3
(2) contain Eu (acac)
3The microcapsules rete of Phen is complete, and structure is intact; The fluorescence property of microcapsules is good, only deposits one deck Eu (acac) in the shell
3During Phen, uviol lamp excites down microcapsules promptly to send macroscopic light; Hollow Eu (acac)
3The fluorescent emission of Phen microcapsules and solid microcapsules does not have significant difference; The atomic force micrograph result of dry state hollow microcapsules shows that the microcapsules shell is complete, every layer of Eu (acac)
3Phen/ polyelectrolyte thickness is 1.9nm; The rete roughness is 2.2nm only, and Eu (acac) is described
3Phen with ultrafine particle form uniform deposition in shell; The hyperfluorescence peak position of microcapsules is in 612.0nm, and half-peak breadth is very narrow.
Embodiment 16. contains the preparation method of high light-effect rare earth compounding microcapsules, and step is as follows:
(1) selects rare earth compounding Eu (HFA)
3Phen; With reference to embodiment 13 steps (1)-(7) method, use CaCO
3As template microsphere, make in every ml soln to contain 8.0 * 10
8Individual microcapsules, sedimentation time 900 seconds, under the 3000rps centrifugal 300 seconds, washing was 5 times in ultra-pure water, and preparation contains Eu (HFA)
3Solid microcapsules { the CaCO of Phen
3| [(PEI) (SA)]
4[Eu (HFA)
3Phen]
2And hollow microcapsules [(PEI) (SA)]
4[Eu (HFA)
3Phen]
2
(2) contain Eu (HFA)
3The microcapsules rete of Phen is complete, and structure is intact; The fluorescence property of microcapsules is good, only deposits one deck Eu (HFA) in the shell
3During Phen, uviol lamp excites down microcapsules promptly to send macroscopic light; Hollow Eu (HFA)
3The fluorescent emission of Phen microcapsules and solid microcapsules does not have significant difference; The atomic force micrograph result of dry state hollow microcapsules shows that the microcapsules shell is complete, every layer of Eu (HFA)
3Phen/ polyelectrolyte thickness is 2.5nm; The rete roughness is 3.0nm only, and Eu (HFA) is described
3Phen with ultrafine particle form uniform deposition in shell; The hyperfluorescence peak position of microcapsules is in 612.0nm, and half-peak breadth is very narrow.
Embodiment 17. contains the preparation method of high light-effect rare earth compounding microcapsules, and step is as follows:
(1) selects rare earth compounding Eu (PTA)
3Phen; With reference to embodiment 13 steps (1)-(7) method, use MF as template microsphere, make in every ml soln to contain 1.0 * 10
6Individual microcapsules, sedimentation time 60 seconds, under the 3000rps centrifugal 120 seconds, washing was 1 time in ultra-pure water, and preparation contains Eu (PTA)
3The solid microcapsules of Phen MF|[(SA) (PEI)]
4[Eu (PTA)
3Phen]
2And hollow microcapsules [(SA) (PEI)]
4[Eu (PTA)
3Phen]
2
(2) contain Eu (PTA)
3The microcapsules rete of Phen is complete, and structure is intact; The fluorescence property of microcapsules is good, only deposits one deck Eu (PTA) in the shell
3During Phen, uviol lamp excites down microcapsules promptly to send macroscopic light; Hollow Eu (PTA)
3The fluorescent emission of Phen microcapsules and solid microcapsules does not have significant difference; The atomic force micrograph result of dry state hollow microcapsules shows that the microcapsules shell is complete, every layer of Eu (PTA)
3Phen/ polyelectrolyte thickness is 2.7nm; The rete roughness is 1.6nm only, and Eu (PTA) is described
3Phen with ultrafine particle form uniform deposition in shell; The hyperfluorescence peak position of microcapsules is in 612.0nm, and half-peak breadth is very narrow.
Embodiment 18. contains the preparation method of high light-effect rare earth compounding microcapsules, and step is as follows:
(1) selects rare earth compounding Eu (DBM)
3Phen; With reference to embodiment 13 steps (1)-(7) method, use MnCO
3As template microsphere, make in every ml soln to contain 1.0 * 10
9Individual microcapsules, sedimentation time 1800 seconds, under the 3000rps centrifugal 1200 seconds, washing was 5 times in ultra-pure water, and preparation contains Eu (DBM)
3Solid microcapsules { the MnCO of Phen
3| [(PEI) (SA)]
4[Eu (DBM)
3Phen]
2And hollow microcapsules [(PEI) (SA)]
4[Eu (DBM)
3Phen]
2
(2) contain Eu (DBM)
3The microcapsules rete of Phen is complete, and structure is intact; The fluorescence property of microcapsules is good, only deposits one deck Eu (DBM) in the shell
3During Phen, uviol lamp excites down microcapsules promptly to send macroscopic light; Hollow Eu (DBM)
3The fluorescent emission of Phen microcapsules and solid microcapsules does not have significant difference; The atomic force micrograph result of dry state hollow microcapsules shows that the microcapsules shell is complete, every layer of Eu (DBM)
3Phen/ polyelectrolyte thickness is 2.0nm; The rete roughness is 2.0nm only, and Eu (DBM) is described
3Phen with ultrafine particle form uniform deposition in shell; The hyperfluorescence peak position of microcapsules is in 612.0nm, and half-peak breadth is very narrow.
Claims (10)
1. preparation method who contains the high light-effect rare earth compounding microcapsules, be made up of following step:
(1) selecting dipole moment is 1～6 europium that must visit (III) beta-diketone complex Eu (acac)
3Phen, Eu (TFA)
3Phen, Eu (HFA)
3Phen, Eu (TTA)
3Phen, Eu (DBM)
3Phen, Eu (PTA)
3One of Phen joins its alcohol saturated solution respectively, and is standby;
Wherein: above-mentioned beta-diketonate ligand acac=acetylacetone,2,4-pentanedione, TFA=trifluoroacetylacetone (TFA), HFA=hexafluoroacetylacetone, the TTA=TTA, DBM=dibenzoyl methane, PTA=benzoyltrifluoroacetone, collaborative part Phen=1, the 10-o-phenanthroline;
(2) join the sodium-chloride water solution that concentration is 3-300mg/ml, standby;
(3) selecting molecular weight is 20,000～200, one of 000 anionic polyelectrolyte kayexalate, sodium alginate, PAMA, anionic starch, sodium apolate, with step (2) solution is solvent, join concentration and be the anionic polyelectrolyte solution of 0.2～20.00mg/ml, standby;
(4) selecting molecular weight is 20,000～200, one of 000 cationic polyelectrolyte diallyl dimethyl ammoniumchloride, poly diallyldimethylammonium chloride, polymine, cation polyacrylamide, cationic starch, cationic chitosan, with step (2) solution is solvent, join concentration and be the cationic polyelectrolyte solution of 0.2～20.00mg/ml, standby;
(5) be the solution that 1: 10～3: 1 solution that obtains of blend step (1) and step (3) obtain by europium (III) beta-diketone complex and anionic polyelectrolyte mass ratio, standby;
(6) be the solution that 1: 10～3: 1 solution that obtains of blend step (1) and step (4) obtain by europium (III) beta-diketone complex and cationic polyelectrolyte mass ratio, standby;
(7) join the hydrochloric acid solution that concentration is 2～400mg/ml, standby;
(8) choosing diameter is that 0.50～10.00 micron one of melamino-formaldehyde condensation oligomer, manganese carbonate, calcium carbonate microspheres is as the kernel template;
(9) A, prepare the microcapsules that all contain high light-effect rare earth compounding in each shell:
1. deposit ground floor: get one of described kernel template of step (8), place contain with its surface the solution that obtains of electrically charged opposite step (5) or step (6), make in every ml soln to contain 10
6～10
9Individual microballoon, sedimentation time 60～1800 seconds is under the 3000rps centrifugal 120～1200 seconds at rotating speed then, washs in ultra-pure water 1～5 time, obtains the microcapsules that template coats one deck rare earth compounding/polyelectrolyte outward;
2. deposit the second layer: the microcapsules that 1. step (9) A is obtained place and the 1. used step (6) of the polyelectrolyte of opposite charges or the solution that step (5) obtains of containing of step (9) A, make in every ml soln to contain 10
6～10
9Individual microballoon, sedimentation time 60～1800 seconds is under the 3000rps centrifugal 120～1200 seconds at rotating speed then, washs in ultra-pure water 1～5 time, obtains the outer microcapsules that coat two layers of rare earth compounding/polyelectrolyte of template;
3. the 3rd layer of deposition: the microcapsules that 2. step (9) A is obtained place and the 2. used step (5) of the polyelectrolyte of opposite charges or the solution that step (6) obtains of containing of step (9) A, make in every ml soln to contain 10
6～10
9Individual microballoon, sedimentation time 60～1800 seconds is under the 3000rps centrifugal 120～1200 seconds at rotating speed then, washs in ultra-pure water 1～5 time, obtains the outer microcapsules that coat three layers of rare earth compounding/polyelectrolyte of template;
4. repeatedly deposition obtains containing the solid microcapsules of multilayer rare earth compounding: repeating step (9) A 2., (9) A 3., so deposit after 8～10 times, obtain all containing in each shell the solid microcapsules of rare earth compounding;
5. the solid microcapsules that use step (7) solution that 4. (9) A is obtained carried out molten nuclear 60～1200 seconds, obtained all containing in each shell the hollow microcapsules of rare earth compounding behind the centrifuge washing;
Or (9) B, preparation contain the solid microcapsules of high light-effect rare earth compounding in the outer shell:
1. deposit ground floor: get one of described kernel template of step (8), place contain with its surface the polyelectrolyte solution that obtains of electrically charged opposite step (3) or step (4), make in every ml soln to contain 10
6～10
9Individual microballoon, sedimentation time 60～1800 seconds is under the 3000rps centrifugal 120～1200 seconds at rotating speed then, washs in ultra-pure water 1～5 time, obtains the microcapsules that template coats one deck polyelectrolyte outward;
2. deposit the second layer: the microcapsules that 1. step (9) B is obtained place and the 1. used step (4) of the polyelectrolyte of opposite charges or the solution that step (3) obtains of containing of step (9) B, make in every ml soln to contain 10
6～10
9Individual microballoon, sedimentation time 60～1800 seconds is under the 3000rps centrifugal 120～1200 seconds at rotating speed then, washs in ultra-pure water 1～5 time, obtains the outer electrolytical microcapsules of two stratas that coat of template;
3. the 3rd layer of deposition: the microcapsules that 2. step (9) B is obtained place and the 2. used step (3) of the polyelectrolyte of opposite charges or the solution that step (4) obtains of containing of step (9) B, make in every ml soln to contain 10
6～10
9Individual microballoon, sedimentation time 60～1800 seconds is under the 3000rps centrifugal 120～1200 seconds at rotating speed then, washs in ultra-pure water 1～5 time, obtains the outer electrolytical microcapsules of three stratas that coat of template;
4. repeatedly deposition obtains not containing in the shell the solid microcapsules that contain multi-layer polyelectrolyte of rare earth compounding: repeating step (9) B 2., (9) B 3., so deposit after 8～10 times, obtain not containing in the shell the solid microcapsules of rare earth compounding;
5. the microcapsules that 4. step (9) B the is obtained rare earth compounding solution that places step (1) to obtain makes in every ml soln to contain 10
6～10
9Individual microballoon, sedimentation time 60～1800 seconds is under the 3000rps centrifugal 120～1200 seconds at rotating speed then, washs in ultra-pure water 1～5 time, obtains the solid microcapsules that outer shell contains one deck rare earth compounding;
6. repeating step (9) B is 5. 1～5 time, obtains the solid microcapsules that outer shell contains 2～6 layers of rare earth compounding;
7. the solid microcapsules that use step (7) solution that 6. (9) B is obtained carried out molten nuclear 60～1200 seconds, it is under the 3000rps centrifugal 120～1200 seconds at rotating speed then, in ultra-pure water, wash 1～5 time, obtain the hollow microcapsules that outer shell contains 2～6 layers of rare earth compounding.
2. the preparation method who contains the high light-effect rare earth compounding microcapsules as claimed in claim 1 is characterized in that, the described beta-diketonate ligand of step (1) is TTA.
3. the preparation method who contains the high light-effect rare earth compounding microcapsules as claimed in claim 1 is characterized in that, the described NaCl solution concentration of step (2) is 30mg/ml.
4. the preparation method who contains the high light-effect rare earth compounding microcapsules as claimed in claim 1 is characterized in that, the described anionic polyelectrolyte solution of step (3) is that molecular weight is 70,000, concentration is the kayexalate solution of 2.0mg/ml.
5. the preparation method who contains the high light-effect rare earth compounding microcapsules as claimed in claim 1 is characterized in that, the described cationic polyelectrolyte solution of step (4) is that molecular weight is 70,000, concentration is the diallyl dimethyl ammoniumchloride solution of 2.0mg/ml.
6. the preparation method who contains the high light-effect rare earth compounding microcapsules as claimed in claim 1 is characterized in that, the mass ratio of step (5) or (6) described rare earth compounding and polyelectrolyte is 1: 2.
7. the preparation method who contains the high light-effect rare earth compounding microcapsules as claimed in claim 1 is characterized in that, the described kernel template of step (8) is that diameter is 5 microns a manganese carbonate.
8. the preparation method who contains the high light-effect rare earth compounding microcapsules as claimed in claim 1 is characterized in that, the described sedimentation time of step (9) is 600 seconds.
9. the preparation method who contains the high light-effect rare earth compounding microcapsules as claimed in claim 1 is characterized in that, the described centrifugation time of step (9) is 600 seconds.
10. the preparation method who contains the high light-effect rare earth compounding microcapsules as claimed in claim 1 is characterized in that, step (9) described in ultra-pure water washing times be 3 times.
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| CN104667883B (en) * | 2015-01-29 | 2016-09-21 | 南昌航空大学 | A kind of can detect and Adsorption water body ferrous ions and the preparation method of copper ion material simultaneously |
| CN108930075A (en) * | 2018-07-11 | 2018-12-04 | 苏州市天翱特种织绣有限公司 | A kind of radiation-proof fabric |
| CN111270520B (en) * | 2020-01-17 | 2022-03-18 | 青岛大学 | Flexible fabric capable of efficiently emitting light to detect bacteria and preparation method and application thereof |
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| CN1718668A (en) * | 2005-07-06 | 2006-01-11 | 太原理工大学 | Preparation method of organic electro luminous material rare earth europium organic metal complex |
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| CN1562456A (en) * | 2004-04-14 | 2005-01-12 | 浙江大学 | Method for embedding water-soluble matter into microcapsule |
| CN1718668A (en) * | 2005-07-06 | 2006-01-11 | 太原理工大学 | Preparation method of organic electro luminous material rare earth europium organic metal complex |
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