CN110964159A - Star-shaped amphiphilic block copolymer and preparation method and application thereof - Google Patents
Star-shaped amphiphilic block copolymer and preparation method and application thereof Download PDFInfo
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- 229920000469 amphiphilic block copolymer Polymers 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000001514 detection method Methods 0.000 claims abstract description 32
- 239000004005 microsphere Substances 0.000 claims abstract description 18
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 229920001577 copolymer Polymers 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 54
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 31
- 239000002904 solvent Substances 0.000 claims description 28
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 22
- 239000003153 chemical reaction reagent Substances 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 20
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 20
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 16
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 12
- 239000013067 intermediate product Substances 0.000 claims description 12
- 230000001376 precipitating effect Effects 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 238000000502 dialysis Methods 0.000 claims description 11
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 claims description 10
- 239000012295 chemical reaction liquid Substances 0.000 claims description 10
- 238000007872 degassing Methods 0.000 claims description 10
- XXSPGBOGLXKMDU-UHFFFAOYSA-N 2-bromo-2-methylpropanoic acid Chemical compound CC(C)(Br)C(O)=O XXSPGBOGLXKMDU-UHFFFAOYSA-N 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 8
- 239000012989 trithiocarbonate Substances 0.000 claims description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical group C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- IMQFZQVZKBIPCQ-UHFFFAOYSA-N 2,2-bis(3-sulfanylpropanoyloxymethyl)butyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(CC)(COC(=O)CCS)COC(=O)CCS IMQFZQVZKBIPCQ-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 6
- -1 tetrafluoroborate Chemical compound 0.000 claims description 6
- 238000010791 quenching Methods 0.000 claims description 5
- 230000000171 quenching effect Effects 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- JJSYPAGPNHFLML-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;3-sulfanylpropanoic acid Chemical compound OC(=O)CCS.OC(=O)CCS.OC(=O)CCS.CCC(CO)(CO)CO JJSYPAGPNHFLML-UHFFFAOYSA-N 0.000 claims description 4
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 4
- 239000002077 nanosphere Substances 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- HIZCIEIDIFGZSS-UHFFFAOYSA-L trithiocarbonate Chemical compound [S-]C([S-])=S HIZCIEIDIFGZSS-UHFFFAOYSA-L 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 2
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 1
- 150000004820 halides Chemical group 0.000 claims 1
- 239000010842 industrial wastewater Substances 0.000 abstract description 5
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 229920001002 functional polymer Polymers 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 3
- 238000011896 sensitive detection Methods 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 9
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000000705 flame atomic absorption spectrometry Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 238000010257 thawing Methods 0.000 description 2
- 229910021554 Chromium(II) chloride Inorganic materials 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- XBWRJSSJWDOUSJ-UHFFFAOYSA-L chromium(ii) chloride Chemical compound Cl[Cr]Cl XBWRJSSJWDOUSJ-UHFFFAOYSA-L 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
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- G01—MEASURING; TESTING
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- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
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Abstract
The invention discloses a star-shaped amphiphilic block copolymer, a preparation method and application thereof, the structural formula of the star-shaped amphiphilic block copolymer is shown as I,
the star-shaped amphiphilic block copolymer can be self-assembled into nano microspheres when metal ions in water are detected, and functional groups on a copolymer chain segment can identify the metal ions, so that the detection of the metal ions is realized. The star-shaped amphiphilic block copolymer has high selectivity in detecting metal ions in waterThe method has the advantages of sensitive detection, no need of pretreatment of a detection sample and simple operation, solves the problems of complex operation, low detection sensitivity, harsh detection conditions and the like in the conventional industrial wastewater detection system, and has potential application value in the application fields of functional polymer materials, industrial wastewater detection and the like.
Description
Technical Field
The invention belongs to the technical field of functional polymer materials, and particularly relates to a star-shaped amphiphilic block copolymer, and a preparation method and application thereof.
Background
Heavy metal ions in industrial wastewater are easy to accumulate in organisms, and serious threats are caused to agricultural production and human health. Current methods for heavy metal ion detection include inductively coupled plasma mass spectrometry (ICP-MS), Flame Atomic Absorption Spectrometry (FAAS), ultraviolet-visible spectrophotometry, electrochemical sensors, and the like. The ultraviolet-visible spectrophotometry method for detecting the heavy metal ions in the wastewater is widely concerned by people due to the advantages of simplicity and rapidness in detection, low cost and the like.
The star amphiphilic block polymer is a branched polymer having amphiphilic segments, having a plurality of linear polymers connected to a central core. The star-shaped amphiphilic block copolymer is capable of forming nano-assemblies with smaller particle sizes than linear block copolymers of the same molecular weight and composition. The nano microspheres assembled based on the star amphiphilic block copolymer have the characteristics of uniform distribution, stable structure, easy functionalization and the like, and have wide application prospects in the fields of nano containers, drug delivery, catalysis, detection and the like.
Bai et al synthesized 4- (2-azopyridine) resorcinol functionalized magnetic polyvinyl alcohol microspheres and used UV-visible spectrophotometry to treat Cu in aqueous solution2+Sensitive detection was performed with a detection limit of 160 nM. Li et al synthesized functionalized hexagonal mesoporous silica (HMS-TMAC-PAR), which can be used for treating Cu in alkaline aqueous solution by ultraviolet-visible spectrophotometry2+Sensitive detection was performed with a detection limit of 13 nM. Du et al synthesized 4- (2-azopyridine) resorcinol functionalized thermo-sensitive ionic microgel, which can detect Mn in water at a temperature lower than 37 ℃ by ultraviolet-visible spectrophotometry2+、Pb2+、Zn2+And Ni2+The detection limit in the environment of pH value 11 is 14, 79, 20 and 21nM respectively. However, the detection conditions are relatively harshThe etching and detection limits are higher. In the heavy metal ion detection, the operation is simple, the detection condition is mild, the selectivity is high, and the nano-microspheres with low detection limit are not reported.
Disclosure of Invention
The invention aims to provide a star-shaped amphiphilic block copolymer with mild detection conditions, high selectivity and low detection limit, and a preparation method and application thereof.
The star-shaped amphiphilic block copolymer has the structure shown as I:
wherein: a is 4- (2-azopyridine) resorcinol;
b is one of halogen negative ions, tetrafluoroborate and hexafluorophosphate;
m is 1 to 500;
n is 1 to 200.
Preferably, B is halogen anion.
The preparation method of the star-shaped copolymer comprises the following steps:
1) carrying out nucleophilic substitution reaction on trimethylolpropane tris (3-mercaptopropionate), carbon disulfide and 2-bromo-2-methylpropanoic acid to synthesize a three-arm chain transfer reagent;
2) carrying out RAFT polymerization reaction on the three-arm chain transfer reagent prepared in the step 1) with N-isopropylacrylamide (NIPAM) and 4-chloromethylstyrene (VBC) in sequence to obtain a polymerization product, and then modifying the polymerization product with 4- (2-azopyridine) resorcinol (PAR) to obtain the star-shaped amphiphilic block copolymer.
The specific reaction process of the step 1) is as follows: adding triethylamine and trimethylolpropane tris (3-mercaptopropionate) into a solvent, stirring for reaction, adding carbon disulfide and 2-bromo-2-methylpropanoic acid, uniformly mixing, then dropwise adding a solution containing triethylamine at a set temperature, adjusting the reaction temperature after dropwise adding, continuing stirring for reaction, adding hydrochloric acid for quenching reaction after the reaction is finished, and purifying a reaction product to obtain a three-arm chain transfer reagent;
the synthetic route is as follows:
the molar ratio of trimethylolpropane tris (3-mercaptopropionate), carbon disulfide and 2-bromo-2-methylpropanoic acid is 1 (2-10) to (5-30); the molar ratio of trimethylolpropane tri (3-mercaptopropionate) to the total triethylamine is 1 (8-15); the molar ratio of the triethylamine to the first dropwise addition is 1 (0.5-1.5); the solvent is one of chloroform, dichloromethane or tetrahydrofuran; the molar ratio of trimethylolpropane tri (3-mercaptopropionate) to the solvent is 1 (5-30); stirring and reacting for 1-3 h, setting the temperature to be-1 ℃, adjusting the reaction temperature to be room temperature, and continuously stirring and reacting for 8-24 h.
The specific reaction process in the step 2) comprises the following steps:
2-1, dissolving a three-arm chain transfer reagent, N-isopropylacrylamide and an initiator in a solvent, then carrying out freezing-unfreezing cycle degassing on reaction liquid, then carrying out reaction, after the reaction is finished, cooling the reaction liquid in an ice bath, exposing the reaction liquid to air to terminate polymerization, concentrating the obtained product, precipitating the product in N-hexane for 3 times, and drying the precipitate to obtain an intermediate product b, wherein the synthetic route is as follows:
2-2, dissolving the intermediate product b, 4-chloromethyl styrene and an initiator in a solvent, then carrying out freezing-unfreezing cycle degassing on a reaction solution, then carrying out reaction, cooling the reaction solution in an ice bath after the reaction is finished, exposing the reaction solution to the air to terminate polymerization, precipitating the obtained product in n-hexane for 3 times after the obtained product is concentrated, and drying the precipitate to obtain an intermediate product c, wherein the synthetic route is as follows:
2-3, dissolving the intermediate product c and 4- (2-azopyridine) resorcinol in a solvent, stirring and reacting under an inert atmosphere, after the reaction is finished, putting reaction liquid into a dialysis bag for dialysis, and after the dialysis is finished, freeze-drying the reaction liquid to obtain the star-shaped amphiphilic block copolymer, wherein the synthetic route is as follows:
in the step 2-1, the initiator is azobisisobutyronitrile, and the molar ratio of the initiator to the three-arm chain transfer reagent is 1 (1-10); the molar ratio of trithiocarbonate to N-isopropyl acrylamide in the three-arm chain transfer reagent is 1 (1-500); the solvent is 1, 4-dioxane, the molar ratio of the three-arm chain transfer reagent to the solvent is 1 (1000-3000), the molar ratio of the N-isopropylacrylamide to the solvent is 1 (2-10), the number of times of freezing-unfreezing cycle degassing is 2-6, the reaction condition is 60-90 ℃ oil bath, and the reaction time is 8-16 h.
In the step 2-2, the initiator is azobisisobutyronitrile, and the molar ratio of the initiator to the three-arm chain transfer reagent is 1 (1-10); the molar ratio of trithiocarbonate to 4-chloromethyl styrene in the three-arm chain transfer reagent is 1 (1-200); the solvent is THF, the molar ratio of the three-arm chain transfer reagent to the solvent is 1 (1000-10000), and the molar ratio of the 4-chloromethyl styrene to the solvent is 1 (2-10); the number of times of freezing-unfreezing cycle degassing is 2-6, the reaction condition is 60-90 ℃ oil bath, and the reaction time is 12-24 hours.
In the step 2-3, the molar ratio of benzyl halide in the intermediate product c to 4- (2-azopyridine) resorcinol is 100 (3-20); the solvent is one of DMF, DMAC and DMSO, and the molar ratio of the intermediate product c to the solvent is 1 (100-300); the inert atmosphere is nitrogen atmosphere or helium atmosphere; stirring and reacting at the temperature of 70-90 ℃ in an oil bath for 18-30 h.
The method for preparing the nano microspheres by adopting the star-shaped amphiphilic block copolymer comprises the following steps:
dissolving the star amphiphilic block copolymer in DMF, and dropwise adding deionized water under stirring to obtain the self-assembled nano microsphere.
The application of the star amphiphilic block copolymer and the nano microsphere in detecting metal ions.
The application of the star-shaped amphiphilic block copolymer and the nano-microsphere in detecting copper ions in water.
The method for detecting the metal copper ions in the water by the star-shaped amphiphilic block copolymer comprises the following steps:
dissolving the star-shaped amphiphilic block copolymer in DMF, and then dissolving Cu in the mixture2+Dropwise adding the water sample to be detected into the DMF solution of the polymer, oscillating, standing for a period of time, placing the mixture into a cuvette, detecting the mixture by an ultraviolet spectrophotometer, and calculating Cu in the water sample to be detected2+And (4) concentration.
The concentration of the star-shaped amphiphilic block copolymer in DMF is 0.06-0.09 mg/mL; the shaking time is 9-11 min, and the standing time is 9-11 min.
The principle of the invention is as follows: the specific structure of the nano microsphere assembled by the star-shaped amphiphilic block copolymer is shown in fig. 1, and the nano microsphere comprises a 4- (2-azopyridine) modified poly (4-chloromethylstyrene) (PVBPAR) block at a hydrophobic end and a poly N-isopropylacrylamide block (PNIPAM) at a hydrophilic end, wherein the PVBPAR block can be complexed with metal ions to have selectivity and pH responsiveness, and the PNIPAM block and the metal ions are also coordinated. Star-like amphiphilic block copolymers modified by PAR in DMF and H2Self-assembling in the O mixed solution to form nano microspheres with hydrophobic PVBPAR as a core and PNIPAM as a shell, and treating the Cu in water by the nano microspheres under the mild conditions of 25 ℃ and pH 72+Has higher sensitivity and lower detection limit.
The invention has the beneficial effects that: 1) the star-shaped amphiphilic block copolymer can be self-assembled into nano microspheres when metal ions in water are detected, and functional groups on a copolymer chain segment can identify the metal ions, so that the detection of the metal ions is realized. 2) The star-shaped amphiphilic block copolymer has high selectivity and high detection sensitivity for detecting metal ions in water, a detected sample does not need pretreatment, the operation is simple, the problems of complex operation, low detection sensitivity, harsh detection conditions and the like in the conventional industrial wastewater detection system are solved, and the star-shaped amphiphilic block copolymer has potential application value in the application fields of functional polymer materials, industrial wastewater detection and the like. 3) The synthesis method of the star-shaped amphiphilic block copolymer is simple, mild in condition, easy to regulate and control and beneficial to industrial production.
Drawings
FIG. 1 is a schematic structural diagram of a nanoparticle of the present invention.
FIG. 2 shows the NMR spectrum of TMP-CTA synthesized in example 1 of the present invention.
FIG. 3 shows the synthesis of TMP-star- (PNIPAM) in example 1 of the present invention80)3Nuclear magnetic resonance hydrogen spectrum of (a).
FIG. 4 shows TMP-star- (PVBC) synthesized in example 1 of the present invention60-b-PNIPAM80)3Nuclear magnetic resonance hydrogen spectrum of (a).
FIG. 5 shows TMP-star- (PVB) in example 1 of the present invention60PAR-b-PNIPAM80)3Ultraviolet absorption spectrum of (2).
FIG. 6 is a particle size distribution Diagram (DLS) and a Transmission Electron Microscope (TEM) of the nanospheres in example 2 of the present invention.
FIG. 7 is a diagram of the selective detection of different metal ions by the nanospheres at different pH values in example 3 of the present invention
FIG. 8 shows the nano-microsphere pair Cu in example 3 of the present invention2+Detection, A2/A1With Cu2+Graph of concentration change.
Detailed Description
The following examples are intended to illustrate the present invention, but not to further limit the scope of the claims of the present invention.
Example 1
1. Synthesis of trimethylolpropane-3- (s-2, 2-dimethylpropionic acid-trithiocarbonate) propionate (TMP-CTA):
5.7081g of triethylamine (56.4097mmol) was added to a 100mL chloroform solution containing 5.0341g of TMP-SH (12.6307mmol), and the reaction was stirred at room temperature for 2 hours; 4.6612g of carbon disulfide (61.2188mmol) and 12.5213g of 2-bromo-2-methylpropanoic acid (74.9778mmol) are then added, and 20mL of an anhydrous chloroform solution containing 5.7081g of triethylamine solution (56.4097mmol) are added dropwise with vigorous stirring at 0 ℃, after 30min, the temperature is raised to room temperature, and the mixture is stirred overnight; then quenching with 50mL of 10% hydrochloric acid, washing for 3 times with deionized water, purifying by column chromatography, and drying in vacuum to obtain TMP-CTA.
The nuclear magnetism characterization of the prepared TMP-CTA is carried out, the result is shown in figure 2, and the nuclear magnetism spectrogram is completely consistent with the structural formula shown in figure 2.
2、TMP-star-(PNIPAM80)3Synthesis of (2)
6.0231g NIPAM (53.3018mmol), 93.7mg TMP-CTA (0.1060mmol) and AIBN (5.2mg,0.0317mmol) are dissolved in 18mL 1, 4-dioxane, the reaction solution is degassed after three freezing-unfreezing cycles, and then heated in oil bath at 70 ℃ for reaction for 12 h; cooling in ice bath, exposing to air to terminate polymerization, precipitating the obtained product in excessive n-hexane for three times, and drying to obtain TMP-star- (PNIPAM)80)3。
For the prepared TMP-star- (PNIPAM)80)3The results of the nuclear magnetic characterization are shown in fig. 3, and it can be seen from fig. 3 that the nuclear magnetic spectrum is completely consistent with the structural formula.
3、TMP-star-(PVBC60-b-PNIPAM80)3Synthesis of (2)
0.6002g TMP-star-(PNIPAM80)3(0.0214mmol), VBC 1.003g (6.5987mmol) and 1.0mg AIBN (0.0061mmol) were dissolved in 3mL THF, the reaction was degassed by three freeze-thaw cycles, heated in a 70 ℃ oil bath for 16h, cooled in an ice bath, and exposed to air to terminate polymerization; precipitating the obtained product in excessive n-hexane for three times, and drying to obtain TMP-star- (PVBC)60-b-PNIPAM80)3。
Wherein 80 represents a degree of polymerization m of 80.
For the prepared TMP-star- (PVBC)60-b-PNIPAM80)3The result of the nuclear magnetic characterization is shown in FIG. 3, and the comparison with the nuclear magnetic spectrum of FIG. 3 shows thatThe new characteristic peak of poly (4-chloromethylstyrene) in FIG. 4 shows that we successfully synthesized TMP-star- (PVBC)60-b-PNIPAM80)3。
Wherein 60 represents a degree of polymerization n of 60.
4. Synthesis of Star-shaped amphiphilic Block copolymer (TMP-star- (PVBC)60PAR-b-PNIPAM80)3)
30.1mgTMP-star-(PVBC60-b-PNIPAM80)3(0.5437. mu. mol) and 4.2mg PAR (0.0195mmol) in 10mL DMF; heating at 80 ℃ under the protection of nitrogen and stirring for 24 hours; cooling to room temperature, transferring into 3500 dialysis bag with molecular weight, dialyzing in DMF for 2 days, dialyzing with deionized water for 3 days (fresh external liquid is replaced every two hours), and freeze drying the obtained solution to obtain star amphiphilic block copolymer.
By applying to TMP-star- (PVBC)60PAR-b-PNIPAM80)3The UV characterization was performed, and the results are shown in FIG. 5, from which it can be seen that the copolymer shows a UV absorption peak, while pure TMP-star- (PVBC) is present60-b-PNIPAM80)3No UV absorption peak, indicating that the synthesis of TMP-star- (PVBC) is successful60PAR-b-PNIPAM80)3。
EXAMPLE 2 preparation of Nanopalls
5.0mg of TMP-star- (PVB)60PAR-b-PNIPAM80)3Dissolved in 1.0mL of DMF. Dropwise adding 1.0mL of H under magnetic stirring2And O. After stirring at room temperature for 2h, the resulting solution was dialyzed with dialysis bag (MWCO 3500) in deionized water for 2 days, with fresh deionized water being replaced every two hours. Finally, the solution is diluted to 1.0mg/mL by deionized water. The particle size distribution Diagram (DLS) and Transmission Electron Micrograph (TEM) of the nanoparticle are shown in FIG. 6, the PDI is 0.255 at room temperature, the particle size is about 40nm, and the nanoparticle is uniformly dispersed.
Example 3
Nano microsphere assembly and heavy metal ion detection
0.075mg/mL TMP-star- (PVB) is prepared60PAR-b-PNIPAM80)3DMF solution of FeCl3、CrCl2、AlCl3、MnCl2And CuCl2Metal salts and the like were dissolved in deionized water, respectively, to obtain salt solutions containing heavy metal ions (each at a concentration of 4.5. mu.M). The two liquids are mixed evenly, and the pH value of the solution is adjusted by NaOH (0.2mol/L) or HCl (0.2 mol/L). The mixed solution was transferred into a 1cm quartz cell and quantified by an ultraviolet-visible spectrophotometer. Absorbance ratio A by two wavelengths2/A1The nanospheres were found to be specific to Cu2+With stronger selectivity (fig. 7).
Nano microsphere to Cu2+Minimum detection limit of
CuCl with accurate preparation of series concentration2Aqueous solution, immobilization of TMP-star- (PVB)60PAR-b-PNIPAM80)3The content of (B) is 0.15 mg/mL. The pH of the mixed solution was adjusted to 7, and the results are shown in FIG. 8, in which Cu was added2+Concentration and A2/A1The linear relation of the nano microsphere to Cu is calculated2+The lowest detection limit of (2) was 13 nM.
Example 4
1、TMP-star-(PNIPAM200)3Synthesis of (2)
14.3736g NIPAM (127.2mmol), 93.7mg TMP-CTA (0.1060mmol) prepared in example 1 and AIBN (5.2mg,0.0317mmol) were dissolved in 55mL 1, 4-dioxane, and after degassing the reaction solution through 4 freeze-thaw cycles, it was heated in an oil bath at 80 ℃ for 16 hours; cooling in ice bath, exposing to air to terminate polymerization, precipitating the obtained product in excessive n-hexane for three times, and drying to obtain TMP-star- (PNIPAM)200)3。
2、TMP-star-(PVBC200-b-PNIPAM200)3Synthesis of (2)
1.0000g TMP-star-(PNIPAM200)3(0.0145mmol), VBC 2.204g (14.5mmol) and 0.7mg AIBN (0.00435mmol) in 9mL THF, degassing the reaction solution through 4 freeze-thaw cycles, heating the reaction in a 70 ℃ oil bath for 16h with ice cooling and exposure to air to terminate the polymerization; precipitating the obtained product in excessive n-hexane for three times, and drying to obtain TMP-star- (PVBC)200-b-PNIPAM200)3。
3. Synthesis of Star-shaped amphiphilic Block copolymer (TMP-star- (PVBC)200PAR-b-PNIPAM200)3)
TMP-star-(PVBC200-b-PNIPAM200)3(0.5437. mu. mol) and PAR (0.0195mmol) were dissolved in 20mL of DMF; heating at 90 ℃ under the protection of nitrogen and stirring for 20 hours; cooling to room temperature, transferring into 3500 dialysis bag with molecular weight, dialyzing in DMF for 2 days, dialyzing with deionized water for 3 days (fresh external liquid is replaced every two hours), and freeze drying the obtained solution to obtain star amphiphilic block copolymer.
Example 5
1. Synthesis of trimethylolpropane-3- (s-2, 2-dimethylpropionic acid-trithiocarbonate) propionate (TMP-CTA):
triethylamine (48.3126mmol) was added to a 130mL chloroform solution containing 5.0341g TMP-SH (12.6307mmol) and the reaction was stirred at room temperature for 2 h; then adding carbon disulfide (100.2247mmol) and 2-bromo-2-methylpropanoic acid (100.43mmol), dropwise adding 20mL of anhydrous chloroform solution containing triethylamine solution (54.7321mmol) under vigorous stirring at-1 ℃, after 30min, heating to room temperature, and stirring overnight; then quenching with 50mL of 10% hydrochloric acid, washing for 3 times with deionized water, purifying by column chromatography, and drying in vacuum to obtain TMP-CTA.
2、TMP-star-(PNIPAM120)3Synthesis of (2)
NIPAM (91.2461mmol), TMP-CTA (0.1060mmol) and AIBN (0.0612mmol) are dissolved in 25mL of 1, 4-dioxane, the reaction solution is degassed by 4 times of freezing-thawing cycles, and then heated in oil bath at 90 ℃ for reaction for 16 hours; cooling in ice bath, exposing to air to terminate polymerization, precipitating the obtained product in excessive n-hexane for three times, and drying to obtain TMP-star- (PNIPAM)120)3。
3、TMP-star-(PVBC150-b-PNIPAM120)3Synthesis of (2)
TMP-star-(PNIPAM120)3(0.0214mmol), VBC (31.5478mmol) and AIBN (0.0061mmol) were dissolved in 4mL THF, the reaction was degassed by 6 freeze-thaw cycles, and then oil was added at 60 deg.CHeating in a bath for 18h, then cooling in an ice bath, and exposing in air to terminate the polymerization; precipitating the obtained product in excessive n-hexane for three times, and drying to obtain TMP-star- (PVBC)150-b-PNIPAM120)3。
4. Synthesis of Star-shaped amphiphilic Block copolymer (TMP-star- (PVBC)150PAR-b-PNIPAM120)3)
TMP-star-(PVBC150-b-PNIPAM120)3(0.5437. mu. mol) and PAR (0.0195mmol) were dissolved in 10mL of DMAC; heating at 90 ℃ under the protection of nitrogen and stirring for 18 hours; cooling to room temperature, transferring into 3500 dialysis bag with molecular weight, dialyzing in DMF for 2 days, dialyzing with deionized water for 3 days (fresh external liquid is replaced every two hours), and freeze drying the obtained solution to obtain star amphiphilic block copolymer.
Example 6
1. Synthesis of trimethylolpropane-3- (s-2, 2-dimethylpropionic acid-trithiocarbonate) propionate (TMP-CTA):
triethylamine (63.3126mmol) was added to a 120mL chloroform solution containing 5.0341g TMP-SH (12.6307mmol) and the reaction was stirred at room temperature for 3 h; then adding carbon disulfide (33.2247mmol) and 2-bromo-2-methylpropanoic acid (160.43mmol), dropwise adding 20mL of anhydrous chloroform solution containing triethylamine solution (71.7321mmol) under vigorous stirring at-1 ℃, after 30min, heating to room temperature, and stirring for 18 h; then quenching with 50mL of 10% hydrochloric acid, washing for 3 times with deionized water, purifying by column chromatography, and drying in vacuum to obtain TMP-CTA.
2、TMP-star-(PNIPAM250)3Synthesis of (2)
NIPAM (120.2368mmol), TMP-CTA (0.1060mmol) and AIBN (0.0612mmol) are dissolved in 30mL of 1, 4-dioxane, the reaction solution is degassed by 6 times of freezing-thawing cycles, and then heated in an oil bath at 80 ℃ for reaction for 16 hours; cooling in ice bath, exposing to air to terminate polymerization, precipitating the obtained product in excessive n-hexane for three times, and drying to obtain TMP-star- (PNIPAM)250)3。
3、TMP-star-(PVBC200-b-PNIPAM250)3Synthesis of (2)
TMP-star-(PNIPAM250)3(0.0214mmol), VBC (54.2488mmol) and AIBN (0.0061mmol) were dissolved in 7mL THF, the reaction was degassed by 5 freeze-thaw cycles, heated in an oil bath at 90 ℃ for 24h, cooled in an ice bath, and exposed to air to terminate the polymerization; precipitating the obtained product in excessive n-hexane for three times, and drying to obtain TMP-star- (PVBC)200-b-PNIPAM250)3。
4. Synthesis of Star-shaped amphiphilic Block copolymer (TMP-star- (PVBC)200PAR-b-PNIPAM250)3)TMP-star-(PVBC200-b-PNIPAM250)3(0.5437. mu. mol) and PAR (0.0834mmol) in 10mL of DMAC; heating at 70 ℃ under the protection of nitrogen and stirring for 30 hours; cooling to room temperature, transferring into 3500 dialysis bag with molecular weight, dialyzing in DMF for 2 days, dialyzing with deionized water for 3 days (fresh external liquid is replaced every two hours), and freeze drying the obtained solution to obtain star amphiphilic block copolymer.
Claims (10)
1. A star-shaped amphiphilic block copolymer is characterized in that the structure of the star-shaped amphiphilic block copolymer is shown as I:
wherein: a is 4- (2-azopyridine) resorcinol;
b is one of halogen negative ions, tetrafluoroborate and hexafluorophosphate;
m is 1 to 500;
n is 1 to 200.
2. A process for the preparation of the star copolymer of claim 1 comprising the steps of:
1) carrying out nucleophilic substitution reaction on trimethylolpropane tris (3-mercaptopropionate), carbon disulfide and 2-bromo-2-methylpropanoic acid to synthesize a three-arm chain transfer reagent;
2) carrying out RAFT polymerization reaction on the three-arm chain transfer reagent prepared in the step 1) with N-isopropylacrylamide and 4-chloromethylstyrene in sequence to obtain a polymerization product, and then modifying the polymerization product with 4- (2-azopyridine) resorcinol to obtain the star-shaped amphiphilic block copolymer.
3. The method for preparing star copolymer according to claim 2, wherein the specific reaction process of step 1) is as follows: adding triethylamine and trimethylolpropane tris (3-mercaptopropionate) into a solvent, stirring for reaction, adding carbon disulfide and 2-bromo-2-methylpropanoic acid, uniformly mixing, then dropwise adding a solution containing triethylamine at a set temperature, adjusting the reaction temperature after dropwise adding, continuing stirring for reaction, adding hydrochloric acid for quenching reaction after the reaction is finished, and extracting a reaction product to obtain a three-arm chain transfer reagent;
the synthetic route is as follows:
4. the method for preparing star-shaped copolymer according to claim 3, wherein the molar ratio of trimethylolpropane tris (3-mercaptopropionate), carbon disulfide and 2-bromo-2-methylpropanoic acid is 1 (2-10) to (5-30); the molar ratio of trimethylolpropane tri (3-mercaptopropionate) to the total triethylamine is 1 (8-15); the molar ratio of the triethylamine to the first dropwise addition is 1 (0.5-1.5); the solvent is one of chloroform, dichloromethane or tetrahydrofuran; the molar ratio of trimethylolpropane tri (3-mercaptopropionate) to the solvent is 1 (5-30); stirring and reacting for 1-3 h, setting the temperature to be-1 ℃, adjusting the reaction temperature to be room temperature, and continuously stirring and reacting for 8-24 h.
5. The method for preparing star copolymer according to claim 2, wherein the specific reaction process in step 2) comprises the following steps:
2-1, dissolving a three-arm chain transfer reagent, N-isopropylacrylamide and an initiator in a solvent, then carrying out freezing-unfreezing cycle degassing on reaction liquid, then carrying out reaction, after the reaction is finished, cooling the reaction liquid in an ice bath, exposing the reaction liquid to air to terminate polymerization, concentrating the obtained product, precipitating the product in N-hexane for 3 times, and drying the precipitate to obtain an intermediate product b, wherein the synthetic route is as follows:
2-2, dissolving the intermediate product b, 4-chloromethyl styrene and an initiator in a solvent, then carrying out freezing-unfreezing cycle degassing on a reaction solution, then carrying out reaction, cooling the reaction solution in an ice bath after the reaction is finished, exposing the reaction solution to the air to terminate the polymerization, concentrating the obtained product, precipitating the product in n-hexane for 3 times, and drying the precipitate to obtain an intermediate product c, wherein the synthetic route is as follows:
2-3, dissolving the intermediate product c and 4- (2-azopyridine) resorcinol in a solvent, stirring and reacting under an inert atmosphere, after the reaction is finished, putting reaction liquid into a dialysis bag for dialysis, and after the dialysis is finished, freeze-drying the reaction liquid to obtain the star-shaped amphiphilic block copolymer, wherein the synthetic route is as follows:
6. the method for preparing the star-like copolymer according to claim 5, wherein in the step 2-1, the initiator is azobisisobutyronitrile, and the molar ratio of the initiator to the three-arm chain transfer reagent is 1 (1-10); the molar ratio of trithiocarbonate to N-isopropyl acrylamide in the three-arm chain transfer reagent is 1 (1-500); the solvent is 1, 4-dioxane, the molar ratio of the three-arm chain transfer reagent to the solvent is 1 (1000-3000), the molar ratio of the N-isopropylacrylamide to the solvent is 1 (2-10), the number of times of freezing-unfreezing cycle degassing is 2-6, the reaction condition is 60-90 ℃ oil bath, and the reaction time is 8-16 h.
7. The method for preparing the star-like copolymer according to claim 5, wherein in the step 2-2, the initiator is azobisisobutyronitrile, and the molar ratio of the initiator to the three-arm chain transfer reagent is 1 (1-10); the molar ratio of trithiocarbonate to 4-chloromethyl styrene in the three-arm chain transfer reagent is 1 (1-200); the solvent is THF, the molar ratio of the three-arm chain transfer reagent to the solvent is 1 (1000-10000), and the molar ratio of the 4-chloromethyl styrene to the solvent is 1 (2-10); the number of times of freezing-unfreezing cycle degassing is 2-6, the reaction condition is 60-90 ℃ oil bath, and the reaction time is 12-24 hours.
8. The method for preparing star-shaped copolymer according to claim 5, wherein in the step 2-3, the molar ratio of benzyl halide group to 4- (2-azo pyridine) resorcinol in the intermediate product c is 100 (3-20); the solvent is DMF, DMAC or DMSO, and the molar volume ratio of the intermediate product c to the solvent is 1 (100-300) mmol/mL; the inert atmosphere is nitrogen atmosphere or helium atmosphere; the stirring reaction temperature is 70-90 ℃, and the reaction time is 18-30 h.
9. A method for preparing nanospheres using said star amphiphilic block copolymer of claim 1 or 2, comprising the steps of:
dissolving the star amphiphilic block copolymer in DMF, and dropwise adding deionized water under stirring to obtain the self-assembled nano microsphere.
10. Use of the star amphiphilic block copolymer according to claim 1 or 2 for the detection of metal ions.
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