CN102627826B - Gold nanoparticle with core-shell structure and preparation method thereof - Google Patents
Gold nanoparticle with core-shell structure and preparation method thereof Download PDFInfo
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Abstract
The invention provides a gold nanoparticle with a core-shell structure and a preparation method thereof. The method comprises the following steps of: directly performing aminolysis on a dithioester at the tail end of a poly(glycol-segmented-N-isopropylacrylamide) copolymer of which the tail end is provided with a dithioester group to obtain a monothiol-terminated poly (glycol-segmented-N-isopropylacrylamide) copolymer; and performing ligand interchange reaction on the monothiol-terminated poly (glycol-segmented-N-isopropylacrylamide) copolymer and the gold nanoparticle with sodium citrate as a ligand, and grafting a segmented copolymer onto the surface of the gold nanoparticle to obtain the gold nanoparticle with the core-shell structure, wherein the shell of the gold nanoparticle is poly(glycol-segmented-N-isopropylacrylamide) copolymer (PEG-B-PNIPAM). Compared with the prior art, the outer layer of the block polymer has high solubility, so the formed gold nanoparticle with the core-shell structure also has high solubility. Due to the block PEG on the outer layer, the stability of the gold nanoparticle with the core-shell structure is also improved, and the aggregation among nanoparticles is inhibited.
Description
Technical field
The invention belongs to technical field of nano material, relate in particular to a kind of nucleocapsid structure golden nanometer particle and preparation method thereof.
Background technology
Core-shell material is generally by the core at center and be coated on outside shell and form.By core-shell composite means, can make on the one hand the core stabilization of unstable or less stable originally, can also obtain on the other hand function and characteristic that core and shell material do not possess itself, perhaps can obtain new material and have form.
In recent years, the golden nanometer particle of nucleocapsid structure because of it at photoelectricity, biologic medical, the potential application of the aspects such as intelligent sensing and be subject to extensive concern.The nucleocapsid structure golden nanometer particle is divided into the golden nanometer particle of organic molecule single ply protective and the golden nanometer particle of polymkeric substance protection; than the former; the golden nanometer particle of polymkeric substance protection has more advantage; as: macromolecule ligand can give golden nanometer particle good stability; workability, physiologically acceptable and environment-responsive.
Usually, the golden nanometer particle for preparing polymkeric substance protection mainly contains two kinds of methods, i.e. " graft from " and " graft to "." graft from " is mainly that the method by surperficial initiated polymerization makes monomer increase at the surface aggregate of gold particle, obtained the nucleocapsid structure golden nanometer particle of temperature-responsive by the method for " graft from " as people such as Li, simultaneously again can be as the initiator of initiated polymerization for nanoparticle, carrying out ligand exchange but the method not only needs to synthesize, but also need to use highly toxic part and catalyzer, polymerization process itself is also more loaded down with trivial details." graft to " is bonded directly to the golden nanometer particle surface with polymer, prepare the nucleocapsid structure golden nanometer particle of temperature-responsive by the method original position of " graft to " as people such as Tenhu, its preparation process is simple, can control according to expection the molecular weight of polymkeric substance again simultaneously, but in-situ reducing can not be controlled the size of nanoparticle well, and resulting golden nanometer particle distribution of sizes is wider.
the people such as present Zhu improve for the people's such as Tenhu preparation method, utilize the method for " graft to ", by being carried out ligand exchange with the polymkeric substance of the temperature-responsive of sulfydryl and pre-synthesis golden nanometer particle, end obtains the nucleocapsid structure golden nanometer particle of temperature-responsive, overcome the shortcoming of in-situ preparation method, but, because the method is only protected golden nanometer particle by the polymkeric substance (PNIPAM) of homopolymerization, the stability factor that there is no other, thereby the nucleocapsid structure golden nanometer particle of preparation is easily assembled under relatively high temperature condition, stability and solvability are poor.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of nucleocapsid structure golden nanometer particle and preparation method thereof, and the nucleocapsid structure golden nanometer particle of the method preparation also has good stability and solvability when having temperature-responsive.
The invention provides a kind of nucleocapsid structure golden nanometer particle, kernel and shell, consist of, described kernel is golden nanometer particle, and shell is poly-(ethylene glycol-block-NIPA) multipolymer.
The invention provides a kind of preparation method of nucleocapsid structure golden nanometer particle, comprise the following steps:
A) end is carried out aminolysis reaction with poly-(ethylene glycol-block-NIPA) multipolymer of two thioester substrates with aminolysis reagent, obtain poly-(ethylene glycol-block-N-isopropyl acrylamide) section multipolymer of single sulfydryl end-blocking;
B) poly-(ethylene glycol-block-NIPA) multipolymer of described single sulfydryl end-blocking is carried out ligand exchange reaction with the golden nanometer particle take Trisodium Citrate as part, obtain the nucleocapsid structure golden nanometer particle.
Preferably, described end is prepared as follows with poly-(ethylene glycol-block-NIPA) multipolymer of two thioester substrates:
S1) polyoxyethylene glycol of monomethyl end-blocking and MALEIC ANHYDRIDE are carried out addition reaction, obtain adduct;
S2), with described adduct and dithiobenzoic acid reaction, obtain the macromolecular chain transfer agent based on the polyoxyethylene glycol of monomethyl end-blocking;
S3), with the macromolecular chain transfer agent of described polyoxyethylene glycol based on the monomethyl end-blocking, Diisopropyl azodicarboxylate and NIPA reaction, obtain end poly-(ethylene glycol-block-NIPA) multipolymer with two thioester substrates.
Preferably, described step S3 temperature of reaction condition is 60～80 ℃.
Preferably, in described steps A, aminolysis reagent is short-chain fat family amido alkane.
Preferably, described short-chain fat family amido alkane is ethamine, propylamine, one or more in Isopropylamine and TERTIARY BUTYL AMINE.
Preferably, in described steps A, aminolysis reaction is with tetrahydrofuran (THF) (THF), and dimethyl formamide (DMF) or methylene dichloride are reaction solvent.
Preferably, described aminolysis reaction and ligand exchange reaction carry out respectively under oxygen free condition.
Preferably, the reaction times of described aminolysis reaction is 20～30h.
Preferably, in described step B, the reaction times of ligand exchange reaction is 60～80h.
The invention provides a kind of nucleocapsid structure golden nanometer particle and preparation method thereof, the direct aminolysis of two thioesters that the method will be gathered (ethylene glycol-block-NIPA) multipolymer (PEG-b-PNIPAM) end is sulfydryl, obtains poly-(ethylene glycol-block-NIPA) multipolymer (PEG-b-PNIPAM-SH) of single sulfydryl end-blocking; Further with the golden nanometer particle take Trisodium Citrate as part, carry out ligand exchange reaction, segmented copolymer is grafted to the surface of golden nanometer particle, obtains the nucleocapsid structure golden nanometer particle of shell for poly-(ethylene glycol-block-NIPA) multipolymer.Compare with the golden nanometer particle that the polymkeric substance of homopolymerization in prior art is protected; protect golden nanometer particle in the present invention take PEG-b-PNIPAM as shell; at first, the solvability of outer block is fine, therefore the nucleocapsid structure golden nanometer particle of its formation also has good solubility.Secondly, the existence of outer block PEG also provides one deck protection for the nucleocapsid structure golden nanometer particle, has improved the stability of nucleocapsid structure golden nanometer particle, has suppressed the gathering between nanoparticle.Again, thus the solvability of internal layer block PNIPAM changes and gives the nucleocapsid structure golden nanometer particle and have temperature-responsive with the change of temperature.
Experimental result shows, the nucleocapsid structure golden nanometer particle mean hydrodynamic radius (R of the present invention's preparation
h) reduce to some extent R in the time of 25 ℃ with the increase of temperature
hBe about 26.5nm, R in the time of 50 ℃
hBe about 23nm, have good temperature-responsive.The nucleocapsid structure golden nanometer particle of the method preparation is not simultaneously all assembled in 15～55 ℃ of temperature ranges, have satisfactory stability.
Description of drawings
Fig. 1 is the transmission electron microscope photo of the golden nanometer particle take Trisodium Citrate as part of the embodiment of the present invention 1 preparation;
Fig. 2 is the transmission electron microscope photo of the nucleocapsid structure golden nanometer particle of the embodiment of the present invention 1 preparation.
Embodiment
The invention provides a kind of preparation method of nucleocapsid structure golden nanometer particle, comprise the following steps: A) end is carried out aminolysis reaction with poly-(ethylene glycol-block-NIPA) multipolymer (PEG-b-PNIPAM) of two thioester substrates with aminolysis reagent, obtain poly-(ethylene glycol-block-NIPA) multipolymer (PEG-b-PNIPAM-SH) of single sulfydryl end-blocking; B) poly-(ethylene glycol-block-NIPA) multipolymer of described single sulfydryl end-blocking is carried out ligand exchange reaction with the golden nanometer particle take Trisodium Citrate as part, obtain the nucleocapsid structure golden nanometer particle.
Wherein, described PEG-b-PNIPAM preferably shifts the preparation of (RAFT) method according to reversible addition-fracture chain:
S1) polyoxyethylene glycol of monomethyl end-blocking (mPEG-OH) and dry toluene solution are added in container, under nitrogen protection, be heated to mPEG-OH and dissolve fully, then add MALEIC ANHYDRIDE (MAh), reaction is spent the night.Toluene is removed in decompression, again is dissolved in methylene dichloride, precipitates in ether, and to remove excessive MAh, vacuum-drying obtains adduct (mPEG-MAh).For mPEG-OH is reacted completely, be preferably MAh excessive, the mass ratio of mPEG-OH and MAh more preferably 6: 1～10: 1, most preferably be 8: 1.
S2) tetracol phenixin of described adduct mPEG-MAh and dithiobenzoic acid (DTBA) and drying is airtight degassed rear in 60～70 ℃ of reaction 20～24h, react after complete and add part methylene chloride, and precipitate in ether, repeat this process and remove fully to excessive DTBA, 35～45 ℃ of vacuum-drying obtains the macromolecular chain transfer agent (mPEG-CTA) based on the polyoxyethylene glycol of monomethyl end-blocking.Temperature of reaction is preferably 65 ℃, and the reaction times is preferably 24h, and the vacuum-drying temperature is preferably 40 ℃.
S3) described mPEG-CTA, Diisopropyl azodicarboxylate, NIPA (NIPAM) and dry acetonitrile solution are added in container, with reaction mixture process freeze-thaw degasification process, vacuum sealing, react 20～24h under 55～80 ℃ of conditions, the product ether sedimentation that obtains, 40～55 ℃ of vacuum-dryings obtain poly-(ethylene glycol-block-NIPA) multipolymer (PEG-b-PNIPAM) of end with two thioester substrates.Temperature of reaction is preferably 60～80 ℃, and more preferably 80 ℃, the reaction times is preferably 24h, and the vacuum-drying temperature is preferably 50 ℃.
The present invention protects golden nanometer particle take PEG-b-PNIPAM as shell, at first, the solvability of outer block is fine, therefore the nucleocapsid structure golden nanometer particle of its formation also has good solubility.Secondly, the existence of outer block PEG also provides one deck protection for the nucleocapsid structure golden nanometer particle, has improved the stability of nucleocapsid structure golden nanometer particle, has suppressed the gathering between nanoparticle.Again, thus the solvability of internal layer block PNIPAM changes and gives the nucleocapsid structure golden nanometer particle and have temperature-responsive with the change of temperature.
, in order to clearly demonstrate the present invention, below respectively the experimentation of steps A and step B is described in detail.
According to the present invention; described steps A is specially: PEG-b-PNIPAM is added in the container that reaction solvent is housed; with the degassed oxygen of removing wherein of reaction solution process freeze-thaw; add aminolysis reagent under nitrogen protection, after the vacuum sealing container, react 20～30h under room temperature; be preferably 24h; the product ether sedimentation that obtains, the vacuum-drying temperature is 30～50 ℃, is preferably 40 ℃.
Wherein, in described steps A, aminolysis reagent is preferably short-chain fat family amido alkane, ethamine more preferably, and propylamine, one or more in Isopropylamine and TERTIARY BUTYL AMINE, most preferably be propylamine and Isopropylamine.The reaction solvent of described aminolysis reaction is preferably THF, DMF or methylene dichloride, more preferably THF or methylene dichloride.
according to the present invention, described step B is specially: PEG-b-PNIPAM-SH is added in the container that deionized water is housed, the reaction solution freeze-thaw is degassed, add the golden nanometer particle take Trisodium Citrate as part under nitrogen protection and vigorous stirring, react 60～80h under room temperature, be preferably 72h, then under cold condition, be preferably 5 ℃, centrifugal 1～the 3h of 10000～15000r/min, its medium speed is preferably 11000r/min, centrifugation time is preferably 2h, remove supernatant liquor after centrifugal, repeat this process repeatedly, until remove unreacted polymkeric substance fully, be preferably three times.
Wherein in steps A and step B for preventing that the end that generates from containing the curing reaction between the segmented copolymer generation sulfydryl of sulfydryl, affect ligand exchange reaction, so want absolute anaerobic in the hierarchy of control.
The nucleocapsid structure golden nanometer particle mean hydrodynamic radius (R of the present invention's preparation
h) reduce to some extent R in the time of 25 ℃ with the increase of temperature
hBe about 26.5nm, R in the time of 50 ℃
hBe about 23nm, have good temperature-responsive.The nucleocapsid structure golden nanometer particle of the method preparation is not simultaneously all assembled in 15～55 ℃ of temperature ranges, have satisfactory stability.
, in order to further illustrate the present invention, below in conjunction with embodiment, the preparation method of a kind of nucleocapsid structure golden nanometer particle provided by the invention is described in detail.
In following examples, agents useful for same is commercially available.
Embodiment 1
1.1 dithiobenzoic acid (DTBA) is synthetic
At one, stirrer is housed; the sodium methoxide solution that adds 22.5g 30% in the 250mL three neck round-bottomed flasks of constant pressure funnel and spherical condensation tube; the sulphur powder of 4g drying; slowly drip the 7.95g benzyl under room temperature and nitrogen protection; complete rear room temperature reaction 30min, then be warming up to 70 ℃ of reactions and spend the night.The ice-water bath cooled and filtered is fallen insolubles, removal of solvent under reduced pressure.Residue is again soluble in water, adds the hcl acidifying of ether and 1.0mol/L, makes it change into DTBA.Repeatedly extract three times with sodium hydroxide solution and the hydrochloric acid/diethyl ether solution of ice, the oily liquids that obtains finally the pure redness of 6.6g is DTBA, and productive rate is about 60%.
1.2mPEG-OH the addition reaction with MAh
The toluene solution of 8.0g mPEG-OH and 30mL drying is added in the round-bottomed flask of 100mL, under nitrogen protection, be heated to 70 ℃ mPEG-OH is dissolved fully after, add rapidly 1.0g MAh, reaction is spent the night.Toluene is removed in decompression, then reactant is dissolved in methylene dichloride again, precipitates in ether, repeats this process three times, and extremely excessive MAh removes fully, and under 50 ℃ of conditions, vacuum-drying is two days, obtains the product mPEG-MAh of white.
1.3mPEG-CTA synthetic
The mPEG-MAh that obtains in a polymerizing pipe that stirrer is housed adds 1.0g step 1.2, the tetracol phenixin of the DTBA that makes in 0.64g step 1.1 and 2mL drying, airtight degassed after in 65 ℃ of reaction 24h.React complete after, add part methylene chloride, and precipitate in ether, this process triplicate, remove fully to excessive DTBA.Under 40 ℃ of conditions, vacuum-drying two days later, obtains light red macromolecular chain transfer agent mPEG-CTA.
1.4PEG-b-PNIPAM synthetic
Add the 1.0mg Diisopropyl azodicarboxylate, 0.80g NIPAM, the macromolecular chain transfer agent mPEG-CTA that makes in 0.20g step 1.3 and the acetonitrile solution of 5.5mL drying in a polymerizing pipe that stirrer is housed.Through after three freeze-thaw degasification process, tube sealing under vacuum, react 24h under 80 ℃ of conditions with reaction mixture.The product that obtains ether sedimentation three times, 50 ℃ of vacuum-dryings two days later, obtain PEG-b-PNIPAM, and the monomer whose transformation efficiency is about 50%.
1.5 the aminolysis reaction of segmented copolymer end
The PEG-b-PNIPAM that makes in 0.20g step 1.4 is joined in the polymerizing pipe that 8.0mL THF solvent is housed; with degassed three times of reaction solution freeze-thaw; under nitrogen protection; after adding rapidly the 0.020g propylamine; solution colour becomes rapidly closely colourless from light red; again with degassed three times of reaction mixture freeze-thaw; vacuum sealing tube; react 24h under room temperature; obtain product ether sedimentation three times; under 40 ℃ of conditions, vacuum-drying two days later, obtains the product P EG-b-PNIPAM-SH after aminolysis, and productive rate is about 98%.
1.6 the preparation of the golden nanometer particle take Trisodium Citrate as part
0.0206g four hydration tetra chlorauric acids and 50mL deionized water are joined in the round-bottomed flask that 100mL is equipped with stirrer.Vigorous stirring is heated to boiling reflux, adds rapidly the sodium citrate aqueous solution of 5mL (33.8mmol/L), and solution colour changes the grape wine redness into by dark yellow, after boiling 10min, remove heating, continue to stir 15min, obtain the golden nanometer particle take Trisodium Citrate as part after cooling.Its particle diameter is about 12 ± 1nm.
1.7 the preparation of the nucleocapsid structure golden nanometer particle of temperature-responsive
The PEG-b-PNIPAM-SH that makes in 0.050g step 1.5 is added in the polymerization bottle that is equipped with in the 20mL deionized water; then with degassed three times of reaction solution freeze-thaw; under nitrogen protection and vigorous stirring; add rapidly the solution of gold nanoparticles take Trisodium Citrate as part that makes in 0.4mL 1mmol/L step 1.6; react 72h under room temperature; then under 5 ℃; centrifugal 2h under the rotating speed of 11000r/min; remove supernatant liquor; repeatedly repeat this process three times, until remove unreacted polymkeric substance fully.Finally, the nucleocapsid structure golden nanometer particle of purifying is dispersed in deionized water.
Be below each step reaction formula:
A. dithiobenzoic acid (DTBA) is synthetic
The addition reaction of b.mPEG-OH and maleic anhydride (MAh)
C. synthetic (mPEG-CTA) of macromolecular chain transfer agent
D. synthetic (PEG-b-PNIPAM) of segmented copolymer
E. the aminolysis reaction of segmented copolymer end (PEG-b-PNIPAM-SH)
F. the preparation of golden nanometer particle (Au NPs)
G. the preparation of the nucleocapsid structure golden nanometer particle of temperature-responsive
The method of utilizing transmission electron microscope is analyzed the nucleocapsid structure golden nanometer particle that obtains in the golden nanometer particle take Trisodium Citrate as part and 1.7 that obtains in 1.6, obtain the transmission electron microscope photo of ligand exchange front and back golden nanometer particle, respectively as depicted in figs. 1 and 2.Compare electromicroscopic photograph by analysis, can find out the existence due to nanoparticle polymkeric substance shell, the dispersiveness of golden nanometer particle improves.
Utilize X ray energy dispersion spectrum, the nucleocapsid structure golden nanometer particle that obtains in 1.7 is carried out ultimate analysis, there are Au, C, N, O and S element in the proof products therefrom, because the polymkeric substance shell is surperficial by sulfydryl grafting and the golden nanometer particle of end, and C, N, O, S are the component of segmented copolymer PEG-b-PNIPAM, have confirmed the existence of polymkeric substance shell.
Detect by temperature-responsive, result shows nucleocapsid structure golden nanometer particle mean hydrodynamic radius R
hReduce to some extent R in the time of 25 ℃ with the increase of temperature
hBe about 26.5nm, R in the time of 50 ℃
hBe about 23nm.Mainly that deliquescent change with temperature due to the block PNIPAM of internal layer causes: along with the rising of temperature, the solubleness of PNIPAM in water descends, go hydration to occur, the polymkeric substance of internal layer starts gradually to collapse and has caused the R of whole nucleocapsid structure golden nanometer particle simultaneously
hReduce.
By to Detection of Stability, result shows in 15～55 ℃ of scopes and does not assemble.This is mainly that existence due to outer block PEG has suppressed the gathering between nanoparticle.
By above experimental result as can be known, the present invention is incorporated into the segmented copolymer of environmental influence in the golden nanometer particle system,, increasing nanoparticle stability and deliquescent while, also gives the golden nanometer particle temperature-responsive.
Embodiment 2
Prepare each middle and final product in the same mode of embodiment 1, only have segmented copolymer PEG-b-PNIPAM synthetic as follows:
Add the 1.0mg Diisopropyl azodicarboxylate in a polymerizing pipe that stirrer is housed, 0.80g NIPAM, the acetonitrile solution of the mPEG-CAT that obtains in 0.20g 1.4 and 5.5mL drying, with reaction mixture through three freeze-thaw degasification process, tube sealing under vacuum, in 60 ℃ of reaction 24h.After the product use ether sedimentation that obtains three times, under 50 ℃ of conditions, vacuum-drying is two days, obtains segmented copolymer PEG-b-PNIPAM, and monomer conversion is about 30%.
Embodiment 3
Prepare each middle and final product in the same mode of embodiment 1, only have the aminolysis reaction of segmented copolymer end as follows:
The PEG-b-PNIPAM that obtains in 1.0g 1.5 is joined in the polymerizing pipe that the 10mL dichloromethane solvent is housed; with degassed three times of reaction solution freeze-thaw; under nitrogen protection; add rapidly the 0.11g propylamine; solution colour becomes rapidly closely colourless from light red; again with degassed three times of reaction mixture freeze-thaw, vacuum sealing tube, room temperature reaction 24h.The product that obtains is with ether sedimentation three times, and 40 ℃ of vacuum-drying two days obtains the product P EG-b-PNIPAM-SH after aminolysis, and productive rate is about 98%.
Embodiment 4
Prepare each middle and final product in the same mode of embodiment 1, only have the aminolysis reaction of segmented copolymer end as follows:
1.0g PEG-b-PNIPAM is joined in the polymerizing pipe that the 10mL dichloromethane solvent is housed; with degassed three times of reaction solution freeze-thaw; under nitrogen protection; add rapidly the 0.12g isopropylamine; solution colour becomes rapidly closely colourless from light red; again with degassed three times of reaction mixture freeze-thaw, vacuum sealing tube, room temperature reaction 24h.Obtain product with ether sedimentation three times, 40 ℃ of vacuum-drying two days, obtain the product P EG-b-PNIPAM-SH after aminolysis, and productive rate is about 98%.
The above is only the preferred embodiment of the present invention; should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (8)
1. the preparation method of a nucleocapsid structure golden nanometer particle, described nucleocapsid structure golden nanometer particle is comprised of kernel and shell, and described kernel is golden nanometer particle, and described shell is poly-(ethylene glycol-block-NIPA) multipolymer, it is characterized in that, comprise the following steps:
A) end is carried out aminolysis reaction with poly-(ethylene glycol-block-NIPA) multipolymer of two thioester substrates with aminolysis reagent, what obtain single sulfydryl end-blocking gathers (ethylene glycol-block-NIPA) multipolymer;
B) poly-(ethylene glycol-block-NIPA) multipolymer of described single sulfydryl end-blocking is carried out ligand exchange reaction with the golden nanometer particle take Trisodium Citrate as part, obtain the nucleocapsid structure golden nanometer particle.
2. preparation method according to claim 1, is characterized in that, described end is prepared as follows with poly-(ethylene glycol-block-NIPA) multipolymer of two thioester substrates:
S1) polyoxyethylene glycol of monomethyl end-blocking and MALEIC ANHYDRIDE are carried out addition reaction, obtain adduct;
S2), with described adduct and dithiobenzoic acid reaction, obtain the macromolecular chain transfer agent based on the polyoxyethylene glycol of monomethyl end-blocking;
S3), with the macromolecular chain transfer agent of described polyoxyethylene glycol based on the monomethyl end-blocking, Diisopropyl azodicarboxylate and NIPA reaction, obtain end poly-(ethylene glycol-block-NIPA) multipolymer with two thioester substrates.
3. preparation method according to claim 2, is characterized in that, described step S3) temperature of reaction be 60～80 ℃.
4. preparation method according to claim 1, is characterized in that, described aminolysis reagent is short-chain fat family amido alkane, and described short-chain fat family amido alkane is one or more in ethamine, propylamine, Isopropylamine and TERTIARY BUTYL AMINE.
5. preparation method according to claim 1, is characterized in that, described aminolysis reaction is with tetrahydrofuran (THF), and dimethyl formamide or methylene dichloride are reaction solvent.
6. preparation method according to claim 1, is characterized in that, described aminolysis reaction and ligand exchange reaction carry out respectively under oxygen free condition.
7. preparation method according to claim 1, is characterized in that, the reaction times of described aminolysis reaction is 20～30h.
8. preparation method according to claim 1, is characterized in that, the reaction times of described ligand exchange reaction is 60～80h.
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