CN102643488B - Preparation method of high-polymer fluorescent microspheres - Google Patents
Preparation method of high-polymer fluorescent microspheres Download PDFInfo
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- CN102643488B CN102643488B CN201210106537.7A CN201210106537A CN102643488B CN 102643488 B CN102643488 B CN 102643488B CN 201210106537 A CN201210106537 A CN 201210106537A CN 102643488 B CN102643488 B CN 102643488B
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- 239000004005 microsphere Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920000642 polymer Polymers 0.000 title claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000008096 xylene Substances 0.000 claims abstract description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 5
- 229920002223 polystyrene Polymers 0.000 claims description 5
- 238000006277 sulfonation reaction Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000011257 shell material Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- 229940043232 butyl acetate Drugs 0.000 claims description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims description 2
- 229940005991 chloric acid Drugs 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229920000547 conjugated polymer Polymers 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000008030 elimination Effects 0.000 abstract description 3
- 238000003379 elimination reaction Methods 0.000 abstract description 3
- 239000011540 sensing material Substances 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical group C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 abstract description 2
- 229920000553 poly(phenylenevinylene) Polymers 0.000 abstract 5
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 230000001276 controlling effect Effects 0.000 abstract 1
- -1 poly(p-phenylenevinylene) Polymers 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- 239000000178 monomer Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 230000032696 parturition Effects 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000007877 drug screening Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000003534 oscillatory effect Effects 0.000 description 1
- 238000000734 protein sequencing Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- Manufacturing Of Micro-Capsules (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a preparation method of high-polymer fluorescent microspheres, particularly a preparation method of microspheres carrying fluorescence-emission poly(p-phenylenevinylene) (PPV) conjugated polymers on the surface, belonging to the field of preparation of fluorescent sensing materials. The preparation method comprises the following steps: preparing a PPV precursor solution by a sulfosalt precursor process, adding microspheres carrying the PPV sulfosalt precursor into a xylene solution, and adding a catalyst to eliminate catalytic thiophane groups in the solution. The invention provides a new way for preparing high-polymer fluorescent microspheres. Since the process different from conventional thermal elimination is adopted, the invention provides possibilities for relatively quantitatively controlling the fluorescence-emission performance of the fluorescent microspheres by regulating the structure of the PPV precursor; and meanwhile, the process of elimination in solution is utilized to prepare the fluorescent microspheres, so the invention has the advantage of lower reaction temperature and is beneficial to energy saving as compared with the prior art.
Description
Technical field
The present invention relates to a kind of area load has the preparation method of the poly-microballoon to vinylbenzene support class conjugated polymer of fluorescent emission, belongs to fluorescent sensing material preparation field.
Background technology
Fluorescent microsphere is a kind of novel fluorescent sensing material, there is good application prospect, research shows, it can be used for numerous biologic medical association areas, as gene sequencing and expression, protein sequencing, medical diagnosis on disease and drug screening, also there is a large amount of demands at the aspect such as environmental monitoring and food test, meanwhile, also for another cutting edge technology---the development of liquid-phase chip suspension technology provides the foundation.
Chinese invention patent (CN 101824191 A) discloses a kind of high molecular fluorescent microballoons and preparation method thereof, take the polystyrene microsphere of monodispersed sulfonation as raw material, by poly-the precursor polymer of conjugated polymer, vinylbenzene support presoma (pre-PPV) is adsorbed on microballoon by electrostatic attraction, under 90～140 ℃ of conditions of vacuum, heat is eliminated again, makes the fluorescent microsphere of conjugated polymer PPV load.But when should be in this way eliminating in heat the backbone structure that process cannot finely regulating conjugated polymer, as cannot be further quantitatively controlled the conjugated degree etc. of main chain by some structure of regulation and control presoma.
Document (J.Am. Chem.Soc.2000,122,2244-2251) report the PPV precursor polymer with side chain and first alcohol and carboxylic acid generation substitution reaction, then be dissolved in xylene solution, and add catalyzer quadrol, thereby eliminate and make different PPV by heating selectivity in solution.This technology yet there are no the preparation for device preparation or fluorescent microsphere.
Summary of the invention
The object of this invention is to provide a kind of stable performance, be conducive to the energy-conservation method of preparing fluorescent microsphere.
The technical solution used in the present invention is to provide a kind of preparation method of high molecular fluorescent microballoons, makes and gathers after vinylbenzene support precursor solution, then carry out the processing of following steps by the salt precursor body method of giving birth:
(1) polystyrene microsphere monodispersed, sulfonation is joined and gather fully mixing in vinylbenzene support precursor solution, then microballoon is taken out, after washing, being dried, obtain the poly-microballoon to vinylbenzene support presoma of surface adsorption;
(2) microballoon of step (1) gained is joined in solvent under anhydrous and oxygen-free condition, add catalyzer, be to take out microballoon after vibrating 1～12 hour under the condition of 60 ℃～110 ℃ in temperature, through washing, dry, obtaining a kind of Shell Materials is the poly-fluorescent microsphere that vinylbenzene is supportted to fluorescence conjugated high molecular polymer again.
The described poly-molecular structural formula to vinylbenzene support presoma is:
，
Wherein, n is the number of the effective conjugate unit of polymkeric substance, 10≤n≤50; R
1, R
2identical or different, R
1, R
2for H, OCH
2cOOH, OCH
2cOOCH
3, OC
3h
6sO
3na, F, Br or C
xh
yone in O; Described C
xh
yin O, y=2x+1, the integer that x is 0～12.
Described Shell Materials is poly-supports fluorescence conjugated high molecular polymer to vinylbenzene, and its structural formula is:
Wherein, n is the number of the effective conjugate unit of polymkeric substance, 10≤n≤50; R
1, R
2identical or different, R
1, R
2for H, OCH
2cOOH, OCH
2cOOCH
3, OC
3h
6sO
3na, F, Br or C
xh
yone in O; Described C
xh
yin O, y=2x+1, the integer that x is 0～12.
Described solvent is the one in octane, butylacetate, chlorobenzene, toluene, o-Xylol, m-xylene, p-Xylol, dimethylbenzene, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, hexalin, 1,2-propylene glycol, ethylene glycol, or their combination.
Described catalyzer is the one in mineral acid hydrogenchloride, hydrogen sulfide, chloric acid, sulfuric acid, sulfurous acid, phosphoric acid, or their combination.
Described catalyzer is the one in organic acid tosic acid, Phenylsulfonic acid, acetic acid, oxalic acid, oxyacetic acid, citric acid, ethylenediamine tetraacetic acid (EDTA), or their combination.
Principle of the present invention is: load is had and poly-the give birth microballoon of salt precursor body of vinylbenzene support class eliminated in xylene solution, when the polymer precursor of load is for poly-when vinylbenzene support, add the catalyzer can the elimination of catalysis tetramethylene sulfide group in solution.
The present invention's advantage is compared with prior art: be different from owing to having adopted the method that conventional heat is eliminated, obtain a kind of fluorescent microsphere, may for realizing that the fluorescent emission performance of carrying out relative quantification and control fluorescent microsphere by the structure of regulation and control PPV presoma provides; Meanwhile, adopt the method for eliminating in solution to prepare fluorescent microsphere, temperature of reaction is low compared with prior art, is conducive to energy-conservation.
Accompanying drawing explanation
Fig. 1 is the fluorescence emission spectrogram of the high molecular fluorescent microballoons that provides of the embodiment of the present invention;
Fig. 2 is the polymer monomer and the poly-infrared absorption spectrum comparison diagram to vinylbenzene support of the unprotected side chain that provides of the embodiment of the present invention;
Fig. 3 is the SEM figure of prepared microballoon in the each step of the embodiment of the present invention.
Embodiment
Below in conjunction with drawings and Examples, technical solution of the present invention is further elaborated.
Embodiment 1
The present embodiment provides a kind of preparation method of high molecular fluorescent microballoons, and step is as follows:
1, adopt the salt precursor body legal system of giving birth for solution: under anhydrous and oxygen-free (nitrogen protection) condition; press document (J. Am.Chem. Soc1993; 115,10117-10124) polymer monomer of synthetic unprotected side chain, get this monomer 0.6895 g (1.965mMol) and be dissolved in 12 mL H
2in O, then the 1.7 mL NaOH aqueous solution are slowly added wherein, stir after 1 hour in ice-water bath, adding 3 mL concentration is the HCl solution termination reaction of 2 M; 1 day (2 × 500 mL deionized water H of the dialysis tubing that is 3500 with molecular weight dialysis
2o), obtain PPV precursor solution 20 mL, its synthetic route is as follows:
10≤n≤50, n is positive integer.
2, the PPV precursor solution 3 mL steps 1 being obtained mixes with the polystyrene microsphere monodispersed, sulfonation of 0.3 g diameter 35 μ m, vibrates after 1 hour, centrifugal, removes supernatant liquor; To adding in microballoon 8 mL deionized waters vibrations to wash for 1 hour, centrifugal and remove supernatant liquor; Use respectively the deionized water of same volume, the dehydrated alcohol of same volume washs once by above-mentioned steps, and finish-drying under vacuum state obtains poly-to the coated microballoon of vinylbenzene support presoma.
3, microballoon step 2 being obtained joins in 3 mL xylene solutions, add 0.2 mL tosic acid, reaction is carried out under anhydrous and oxygen-free condition, oscillatory reaction 3 hours at 80 ℃, after solution is cooling, adds 5 mL acetone, centrifugal, remove supernatant liquor, then to adding 8 mL acetone vibration 1 hour in microballoon, centrifugal and remove supernatant liquor.Use respectively the deionized water of same volume, once, finish-drying under vacuum state, obtains polystyrene microsphere monodispersed, sulfonation to the absolute ethanol washing of same volume again, and coated gathering of its surface supportted fluorescence conjugated polymer to vinylbenzene.
Referring to accompanying drawing 1, it is the fluorescence emission spectrogram of the fluorescent microsphere prepared by the present embodiment technical scheme, and as seen from Figure 1, under 405 nm exciting lights, the maximum emission wavelength of this fluorescent microsphere is 544 nm.
Referring to accompanying drawing 2, curve a is the infrared absorption spectrum of the polymer monomer of unprotected side chain in the present embodiment, and curve b is the poly-infrared absorption spectrum to vinylbenzene support in the present embodiment, as seen from Figure 2, and 2082 cm
-1the peak at place is CH in monomer
2the stretching vibration of the c h bond of Cl, 960cm
-1the peak at place is the poly-flexural vibration to the two key C-H of C=C in vinylbenzene support.
Referring to accompanying drawing 3, the figure a SEM figure that is raw material ball, figure b is before precursor polymer is carried on and does not eliminate on microballoon, i.e. the figure of the SEM of microballoon described in the present embodiment step 2, figure c is the polymer microballoon after eliminating, i.e. the figure of the SEM of microballoon described in the present embodiment step 3.Can find out: eliminate before and eliminate after microsphere surface compared with raw material ball without considerable change.
Claims (6)
1. a preparation method for high molecular fluorescent microballoons, makes and gathers vinylbenzene support precursor solution with sulfonium salt precursor process, it is characterized in that carrying out the processing of following steps again:
(1) polystyrene microsphere monodispersed, sulfonation is joined and gather fully mixing in vinylbenzene support precursor solution, then microballoon is taken out, after washing, being dried, obtain the poly-microballoon to vinylbenzene support presoma of surface adsorption;
(2) microballoon of step (1) gained is joined in solvent under anhydrous and oxygen-free condition, add catalyzer, be to take out microballoon after vibrating 1～12 hour under the condition of 60 ℃～110 ℃ in temperature, through washing, dry, obtaining a kind of Shell Materials is the poly-fluorescent microsphere that vinylbenzene is supportted to fluorescence conjugated high molecular polymer again.
2. the preparation method of a kind of high molecular fluorescent microballoons according to claim 1, is characterized in that: the described poly-molecular structural formula to vinylbenzene support presoma is:
Wherein, n is the number of the effective conjugate unit of polymkeric substance, 10≤n≤50; R
1, R
2identical or different, R
1, R
2for H, OCH
2cOOH, OCH
2cOOCH
3, OC
3h
6sO
3na, F, Br or C
xh
yone in O; Described C
xh
yin O, y=2x+1, the integer that x is 0～12.
3. the preparation method of a kind of high molecular fluorescent microballoons according to claim 1, is characterized in that: described Shell Materials is poly-supports fluorescence conjugated high molecular polymer to vinylbenzene, and its structural formula is:
Wherein, n is the number of the effective conjugate unit of polymkeric substance, 10≤n≤50; R
1, R
2identical or different, R
1, R
2for H, OCH
2cOOH, OCH
2cOOCH
3, OC
3h
6sO
3na, F, Br or C
xh
yone in O; Described C
xh
yin O, y=2x+1, the integer that x is 0～12.
4. the preparation method of a kind of high molecular fluorescent microballoons according to claim 1, it is characterized in that: described solvent is the one in octane, butylacetate, chlorine benzene,toluene,xylene, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, hexalin, 1,2-propylene glycol, ethylene glycol, or their combination.
5. the preparation method of a kind of high molecular fluorescent microballoons according to claim 1, is characterized in that: described catalyzer is the one in mineral acid hydrogenchloride, hydrogen sulfide, chloric acid, sulfuric acid, sulfurous acid, phosphoric acid, or their combination.
6. the preparation method of a kind of high molecular fluorescent microballoons according to claim 1, it is characterized in that: described catalyzer is the one in organic acid tosic acid, Phenylsulfonic acid, acetic acid, oxalic acid, oxyacetic acid, citric acid, ethylenediamine tetraacetic acid (EDTA), or their combination.
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| CN104209071B (en) * | 2014-08-08 | 2016-08-17 | 四川大学 | A kind of preparation method of biological polysaccharide polymer fluorescent microsphere |
| CN104845052B (en) * | 2015-05-08 | 2017-03-22 | 苏州大学 | Poly phenylenevinylene conjugated polymer fluorescent nanoparticles with controllable emission wavelength and preparation method |
| CN105924628A (en) * | 2016-06-20 | 2016-09-07 | 苏州大学 | Poly(p-phenylene vinylene) precursor, preparation method thereof and application of poly(p-phenylene vinylene) precursor to high-molecular fluorescent microspheres |
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| CN101824191A (en) * | 2010-04-29 | 2010-09-08 | 苏州大学 | Macromolecular fluorescent microspheres and preparation method thereof |
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|---|---|---|---|---|
| CN101824191A (en) * | 2010-04-29 | 2010-09-08 | 苏州大学 | Macromolecular fluorescent microspheres and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| G. Padmanaban et al.."Conjugation Length Control in Soluble Poly[2-methoxy -5- ((2’-ethylhexyl)oxy) -1,4-phenylenevinylene] (MEHPPV): Synthesis, Optical Properties, and Energy Transfer".《Journal of the American Chemical Society》.2000,第122卷(第10期),2244-2251. |
| G. Padmanaban et al.."Conjugation Length Control in Soluble Poly[2-methoxy-5- ((2’-ethylhexyl)oxy)-1,4-phenylenevinylene] (MEHPPV): Synthesis, Optical Properties, and Energy Transfer".《Journal of the American Chemical Society》.2000,第122卷(第10期),2244-2251. * |
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