CN112457481B - Polyether macromolecule with conductive activity and end-epoxy-group hyperbranched structure and preparation method thereof - Google Patents

Polyether macromolecule with conductive activity and end-epoxy-group hyperbranched structure and preparation method thereof Download PDF

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CN112457481B
CN112457481B CN201910844595.1A CN201910844595A CN112457481B CN 112457481 B CN112457481 B CN 112457481B CN 201910844595 A CN201910844595 A CN 201910844595A CN 112457481 B CN112457481 B CN 112457481B
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epoxy
polyethylene glycol
polyether
glycol diglycidyl
diglycidyl ether
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CN112457481A (en
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王玮
邹阳
刘文广
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Tianjin University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
    • C08G65/3331—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group cyclic
    • C08G65/33313—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group cyclic aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
    • C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
    • C08G65/2624—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aliphatic amine groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2696—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the process or apparatus used

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Abstract

The invention discloses polyether macromolecules AT-EHBPE with an epoxy-terminated hyperbranched structure and a preparation method thereof. Specifically, polyethylene glycol diglycidyl ether (PEGDE-500) with molecular weight of 500 and Ethylenediamine (EDA) are used as raw materials, oligomer Aniline Tetramer (AT) of polyaniline is used as a conductive active substance, the PEGDE-500 and the EDA are initiated to carry out ring opening reaction (A2+ B4) of epoxy groups under certain reaction conditions, so that polyether macromolecule EHBPE with a terminal epoxy group and a hyperbranched structure is prepared, and then AT is added into the reactant to be grafted onto the EHBPE to endow the macromolecule with conductive activity. The invention utilizes a reaction system of a one-pot method, has simple preparation method and mild reaction conditions, and the prepared hyperbranched polymer has good water solubility, conductivity and biocompatibility, has numerous branch points and contains a plurality of terminal epoxy functional groups and can be further modified to obtain the expected functional material.

Description

Polyether macromolecule with conductive activity and end-epoxy-group hyperbranched structure and preparation method thereof
Technical Field
The invention relates to an epoxy-terminated hyperbranched polyether macromolecule AT-EHBPE with conductive activity and a preparation method thereof, in particular to a method for preparing hyperbranched polyether macromolecule AT-EHBPE by using polyethylene glycol diglycidyl ether (PEGDE), Ethylenediamine (EDA) and Aniline Tetramer (AT) through utilizing the ring-opening reaction of epoxy groups under alkaline conditions, wherein the hyperbranched macromolecule contains a plurality of epoxy-terminated groups and aniline tetramer as electroactive substances.
Background
The ring-opening reaction activity of the epoxy group is high, and the ring-opening reaction can be carried out under acidic or alkaline conditions. Polyethylene glycol diglycidyl ether (PEGDE) can endow the material with good water solubility, cell adhesion resistance and protein adhesion resistance due to more ether bond structures, so that the polyethylene glycol diglycidyl ether (PEGDE) can be used for preparing hydrogel and constructing a carrier system for biological medicine, and can perform ring-opening reaction due to the fact that two ends of a molecular chain of the PEGDE are provided with bifunctional epoxy groups.
Ethylenediamine (EDA) is a commonly used epoxy resin curing agent, and has tetra-functional amino active hydrogen as a nucleus for constructing a hyperbranched structure in the preparation method. Meanwhile, the strong basicity of the epoxy resin provides a proper alkaline environment for the ring-opening reaction of the epoxy group.
The Aniline Tetramer (AT) is an oligomer with a polyaniline structure, and can be used for enhancing the conjugation of a molecular chain due to the alternate arrangement of benzene rings and quinone rings on the molecular structure, wherein the aniline tetramer in an intermediate oxidation state has excellent conductive activity equivalent to that of polyaniline after being doped with protonic acid, and has more excellent biocompatibility due to the fact that the molecular weight of the aniline tetramer is much smaller than that of polyaniline. When AT is prepared, the scheme adopts an N-phenyl-p-phenylenediamine oxidative coupling method, the operation is simple, the mixed solvent of acetone and hydrochloric acid is adopted, the solubility of N-phenyl-p-phenylenediamine is enhanced, the reaction rate is delayed, the product yield is improved, and compared with other oxidants, the purity of the product is improved by adopting ammonium persulfate. AT is grafted in epoxy group-terminated hyperbranched structure polyether macromolecules (EHBPE), so that the good electric activity can be endowed, and meanwhile, the terminal groups contain abundant epoxy groups, so that the AT can be further reacted with other substances to realize the expected application.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and aims to prepare the epoxy-terminated hyperbranched polyether macromolecule AT-EHBPE with conductive activity by using the high ring-opening activity of epoxy groups, using polyethylene glycol diglycidyl ether-500 (PEGDE-500) and Ethylenediamine (EDA) as raw materials and using Aniline Tetramer (AT) as an electroactive substance.
The technical purpose of the invention is realized by the following technical scheme.
The invention relates to an epoxy-terminated hyperbranched polyether macromolecule AT-EHBPE with conductive activity and a preparation method thereof, which comprises the following steps:
(1) uniformly mixing an acetone/hydrochloric acid solution of N-phenyl-p-phenylenediamine with an aqueous solution of ammonium persulfate, and reacting in an ice bath to enable the N-phenyl-p-phenylenediamine to generate a coupling reaction under the oxidation action of the ammonium persulfate to generate an aniline tetramer in an intermediate oxidation state;
(2) uniformly mixing an absolute ethanol solution of polyethylene glycol diglycidyl ether and an absolute ethanol solution of ethylenediamine, wherein the molar ratio of the polyethylene glycol diglycidyl ether to the ethylenediamine is (2-5):1, reacting in an oil bath in a sealed environment to enable epoxy groups at two ends of a molecular chain of the polyethylene glycol diglycidyl ether to perform an open-loop reaction, and then reacting with amino groups at two ends of the ethylenediamine to generate the epoxy-terminated hyperbranched polyether;
(3) and (3) adding the dimethylformamide solution of the aniline tetramer generated in the step (1) into the reaction system in the step (2), and reacting in an oil bath to react the amino group of the aniline tetramer with the epoxy group of the epoxy-terminated hyperbranched structural polyether generated in the step (2) and graft the aniline tetramer onto the epoxy-terminated hyperbranched structural polyether.
The reaction in steps (1), (2) and (3) is fully carried out by stirring at the speed of 800-1200 rpm.
In the step (1), the volume ratio of acetone to deionized water to concentrated hydrochloric acid is 4:4: 1; stirring N-phenyl-p-phenylenediamine and ammonium persulfate in an ice bath at the temperature of between 5 ℃ below zero and 0 ℃ for reaction for 3 to 5 hours; and after the reaction is finished, carrying out suction filtration, washing the precipitate by using hydrochloric acid solution and acetone in sequence, reacting with ammonia water to remove impurities, and washing by using deionized water.
The molar ratio of the polyethylene glycol diglycidyl ether to the ethylenediamine in the step (2) is preferably (2.5-3) to 1; the number average molecular weight of the polyethylene glycol diglycidyl ether is 500; the mass fraction of the polyethylene glycol diglycidyl ether absolute ethyl alcohol solution is 30 percent; the mass fraction of the ethylenediamine absolute ethyl alcohol solution is 5 percent; the polyethylene glycol diglycidyl ether and the ethylenediamine react for 1 to 3 hours in an oil bath at the temperature of between 40 and 60 ℃.
The molar ratio of the aniline tetramer in the step (3) to the polyethylene glycol diglycidyl ether in the step (2) is 1: 1; the mass fraction of the aniline tetramer dimethylformamide solution is 20 percent; reacting aniline tetramer with epoxy-terminated hyperbranched structural polyether in an oil bath at 40-60 ℃ for 1-3 h; after the reaction is finished, purifying by using a mixed solvent of glacial ethyl ether and normal hexane, and removing residual diethyl ether and normal hexane in the product; the amount of the mixed solvent of the glacial ethyl ether and the normal hexane is 8 to 12 times of the volume of the product.
The chemical reactions involved in the present invention are carried out according to the following chemical reaction formulae.
Figure 1
The invention has the beneficial effects that: the preparation method is simple, the material source is wide, the energy consumption is low, and the production efficiency is high; in the preparation scheme, the aniline tetramer is prepared by using a mixed solvent of acetone and hydrochloric acid, so that the solubility of N-phenyl-p-phenylenediamine is enhanced, the oxidative coupling reaction rate is delayed, the product yield is improved, and the purity of the product is improved by using ammonium persulfate compared with other oxidants; according to the invention, the micromolecule aniline tetramer with electric activity is grafted to the polyether macromolecule with the epoxy-terminated hyperbranched structure, so that the polyether macromolecule has excellent electric activity, and meanwhile, the end group contains abundant epoxy groups, and can further react with other substances to realize expected application.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of aniline tetramer AT;
FIG. 2 is nuclear magnetic hydrogen spectrum of polyether macromolecule AT-EHBPE with epoxy-terminated hyperbranched structure and conductive activity;
FIG. 3 is an ultraviolet spectrum of polyether macromolecule AT-EHBPE with epoxy-terminated hyperbranched structure having conductive activity;
FIG. 4 is an infrared spectrum of polyether macromolecule AT-EHBPE with epoxy-terminated hyperbranched structure having conductive activity.
Detailed Description
The following is a further description of the invention and is not intended to limit the scope of the invention.
Preparing the instruments needed by the experiment, cleaning the single-neck round-bottom flask, the glass and plastic beaker, the constant-pressure dropping funnel and the magneton used for the reaction, and placing the flask in an oven for drying. A100 mL graduated cylinder, Buchner funnel and filter flask were cleaned in the same way and dried. 1.84g N-phenyl p-phenylenediamine is weighed by an analytical balance, placed in a single-neck round-bottom flask, magnetons are placed in the flask, then 100mL of acetone, 100mL of deionized water and 25mL of 35% concentrated hydrochloric acid are respectively weighed by a measuring cylinder and placed in the flask, and the mixture is stirred strongly in an ice bath at 0 ℃ for 0.5h to be fully dissolved. During stirring, 4.564g of ammonium persulfate was weighed by an analytical balance and dissolved in a beaker containing 25mL of deionized water, and after sufficient dissolution the solution was poured into a 50 mL-gauge constant pressure dropping funnel, followed by slow dropwise addition of an aqueous solution of ammonium persulfate into the round bottom flask at a rate of 3 seconds per drop, and after completion of the dropwise addition, the reaction was continued with vigorous stirring under ice bath conditions for 3 h. And then, carrying out suction filtration on the reactant, washing the obtained product for 2 times by using 200mL of 0.6mol/L hydrochloric acid, then carrying out suction filtration, washing the product for 2 times by using 200mL of acetone, carrying out suction filtration, placing the product in a beaker, adding 200mL of 0.5mol/L ammonia water into the beaker for counter doping for 2 hours, washing the product for 3 times by using 600mL of deionized water after suction filtration, finally carrying out suction filtration, placing the obtained product in a 40 ℃ drying oven for drying for 48 hours, and placing the Aniline Tetramer (AT) obtained after drying into a small glass bottle for storage.
1.5g of PEGDE-500, 0.07212g of EDA and 1.098g of AT are weighed by an analytical balance respectively, the medicines are placed in plastic centrifuge tubes respectively, 4.430mL of absolute ethyl alcohol, 1.735mL of absolute ethyl alcohol and 3.990mL of DMSO are weighed by a pipette gun respectively and added into the centrifuge tubes respectively, and the medicines are swirled to be dissolved fully.
The temperature (50 ℃) and the rotation speed (1000rpm) of the oil bath pot are set, the prepared PEGDE-500 solution and the EDA solution are added into the single-neck flask, a bottle stopper is arranged on the flask, the mixture is fully stirred and mixed evenly, and the single-neck flask is placed in the oil bath pot. The bottle mouth is tangled by a sealing film and reacted for 2 hours.
After reacting for 2h, the bottle stopper is opened, the prepared AT solution is added into the bottle stopper, and the reaction continues for 2h after the bottle stopper is plugged.
After the reaction, the oil bath pot was closed, the single-neck flask was taken out with a cloth glove, wiped dry with clean toilet paper, the neck of the flask was opened, and the small magnetons were sucked out with a magnet and the apparatus was allowed to cool. At the same time, the ether was chilled at-20 ℃ for 20 min. Then, 100mL of glacial ethyl ether and 50mL of n-hexane were added to the plastic beaker, magnetons were placed, and the cooled solution was added dropwise to the plastic beaker by sucking with a dropper while turning on magnetic stirring to mix them uniformly with each other. After the dropwise adding is completed, the stirring is turned off, the mixture is kept stand for 15min, and a very obvious layering phenomenon in a plastic beaker can be observed, at the moment, the liquid on the upper layer is sucked out by a dropper, and then 30mL of glacial ethyl ether and 15mL of normal hexane are added, and the operation is repeated for three times.
Transferring the black viscous liquid in the plastic beaker into a plastic centrifuge tube by using a dropper, blowing air into the plastic centrifuge tube for 2min by using a blower to accelerate the volatilization of the ether and the n-hexane, sealing the plastic centrifuge tube by using a preservative film, placing the plastic centrifuge tube in a vacuum drying oven for 2h, and taking out the plastic centrifuge tube.
Sealing the plastic centrifuge tube, and storing at-80 deg.C for use.
By using1The chemical structures of the aniline tetramer prepared in the example and the polyether macromolecule AT-EHBPE with the epoxy-terminated hyperbranched structure and the conductive activity are characterized by H NMR, and the positions of the characteristic peaks of the polyether macromolecule AT-EHBPE with the epoxy-terminated hyperbranched structure and the conductive activity are determined by ultraviolet spectrum and infrared spectrum.
As can be seen from FIG. 1, an absorption peak at 7.3ppm of a hydrogen atom on the phenyl ring on the side of the phenyl end cap, an absorption peak at 7.1ppm of a hydrogen atom on the amino group between the phenyl rings, an absorption peak at 6.7 ppm of a hydrogen atom on the phenyl ring and an absorption peak at 5.6ppm of a hydrogen atom on the amino group on the side of the amino end cap on the aniline tetramer were clearly observed from the spectra, and thus the nuclear magnetic hydrogen spectra could prove the successful synthesis of the aniline tetramer.
As can be seen from FIG. 2, the absorption peak of the aniline tetramer on AT-EHBPE AT about 7.0ppm and the hydroxyl absorption peak formed by the ring opening of the epoxy group AT 4.5ppm can be seen from the spectrum, thus proving that the aniline tetramer is successfully grafted to the epoxy-terminated hyperbranched polyether macromolecule, i.e. the epoxy-terminated hyperbranched polyether macromolecule AT-EHBPE with conductive activity is successfully synthesized.
As can be seen from FIG. 3, it can be seen from the spectrum that the absorption peak of the transition of the benzene ring pi-pi + exciton AT 325nm and the absorption peak of the conversion of the benzene ring-quinone ring AT 588nm also appear in AT-EHBPE, but the two characteristic peaks are not seen in EHBPE without AT, thus proving that the terminal epoxy hyperbranched polyether macromolecule AT-EHBPE with conductive activity is successfully synthesized.
As can be seen from FIG. 4, it can be seen from the spectrum that 3386cm was formed in AT-EHBPE due to the ring opening of the epoxy-1Broad peak of hydroxyl group at position 1506cm-1、748cm-1And 696cm-1The characteristic peak of benzene ring also appears in AT-EHBPE, and proves that the epoxy-terminated hyperbranched polyether macromolecule AT-EHBPE with conductive activity is successfully synthesized.
According to the content of the invention, the preparation of the epoxy-terminated hyperbranched polyether macromolecule AT-EHBPE with conductive activity can be realized by adjusting the process parameters, and the performance basically consistent with the embodiment of the invention is shown.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.

Claims (10)

1. An epoxy-terminated hyperbranched polyether macromolecule with conductive activity is characterized in that: the preparation method comprises the following steps:
(1) uniformly mixing deionized water/acetone/concentrated hydrochloric acid solution of N-phenyl-p-phenylenediamine with aqueous solution of ammonium persulfate, and reacting in an ice bath to enable the N-phenyl-p-phenylenediamine to generate a coupling reaction under the oxidation action of the ammonium persulfate to generate aniline tetramer in an intermediate oxidation state;
(2) uniformly mixing an absolute ethanol solution of polyethylene glycol diglycidyl ether and an absolute ethanol solution of ethylenediamine, wherein the molar ratio of the polyethylene glycol diglycidyl ether to the ethylenediamine is (2-5):1, reacting in an oil bath in a sealed environment to enable epoxy groups at two ends of a molecular chain of the polyethylene glycol diglycidyl ether to perform an open-loop reaction, and then reacting with amino groups at two ends of the ethylenediamine to generate the epoxy-terminated hyperbranched polyether;
(3) and (3) adding the dimethylformamide solution of the aniline tetramer generated in the step (1) into the reaction system in the step (2), and reacting in an oil bath to react the amino group of the aniline tetramer with the epoxy group of the epoxy-terminated hyperbranched structural polyether generated in the step (2) and graft the aniline tetramer onto the epoxy-terminated hyperbranched structural polyether.
2. The electrically conductive active polyether macromolecule with an epoxy-terminated hyperbranched structure according to claim 1, characterized in that: the reaction in steps (1), (2) and (3) is fully carried out by stirring at the speed of 800-1200 rpm.
3. The electrically conductive active polyether macromolecule with an epoxy-terminated hyperbranched structure according to claim 1, characterized in that: in the step (1), the volume ratio of acetone to deionized water to concentrated hydrochloric acid is 4:4: 1; stirring N-phenyl-p-phenylenediamine and ammonium persulfate in an ice bath at the temperature of between 5 ℃ below zero and 0 ℃ for reaction for 3 to 5 hours; and after the reaction is finished, carrying out suction filtration, washing the precipitate by using hydrochloric acid solution and acetone in sequence, reacting with ammonia water to remove impurities, and washing by using deionized water.
4. The electrically conductive active polyether macromolecule with an epoxy-terminated hyperbranched structure according to claim 1, characterized in that: in the step (2), the molar ratio of the polyethylene glycol diglycidyl ether to the ethylenediamine is (2.5-3) to 1; the number average molecular weight of the polyethylene glycol diglycidyl ether is 500; the mass fraction of the polyethylene glycol diglycidyl ether absolute ethyl alcohol solution is 30 percent; the mass fraction of the ethylenediamine absolute ethyl alcohol solution is 5 percent; the polyethylene glycol diglycidyl ether and the ethylenediamine react for 1 to 3 hours in an oil bath at the temperature of between 40 and 60 ℃.
5. The electrically conductive active polyether macromolecule with an epoxy-terminated hyperbranched structure according to claim 1, characterized in that: the molar ratio of the aniline tetramer in the step (3) to the polyethylene glycol diglycidyl ether in the step (2) is 1: 1; the mass fraction of the aniline tetramer dimethylformamide solution is 20 percent; reacting aniline tetramer with epoxy-terminated hyperbranched structural polyether in an oil bath at 40-60 ℃ for 1-3 h; after the reaction is finished, purifying by using a mixed solvent of glacial ethyl ether and normal hexane, and removing residual diethyl ether and normal hexane in the product; the amount of the mixed solvent of the glacial ethyl ether and the normal hexane is 8 to 12 times of the volume of the product.
6. A preparation method of polyether macromolecules with conductive activity and an epoxy-terminated hyperbranched structure is characterized by comprising the following steps: the method comprises the following steps:
(1) uniformly mixing deionized water/acetone/concentrated hydrochloric acid solution of N-phenyl-p-phenylenediamine with aqueous solution of ammonium persulfate, and reacting in an ice bath to enable the N-phenyl-p-phenylenediamine to generate a coupling reaction under the oxidation action of the ammonium persulfate to generate aniline tetramer in an intermediate oxidation state;
(2) uniformly mixing an absolute ethanol solution of polyethylene glycol diglycidyl ether and an absolute ethanol solution of ethylenediamine, wherein the molar ratio of the polyethylene glycol diglycidyl ether to the ethylenediamine is (2-5):1, reacting in an oil bath in a sealed environment to enable epoxy groups at two ends of a molecular chain of the polyethylene glycol diglycidyl ether to perform an open-loop reaction, and then reacting with amino groups at two ends of the ethylenediamine to generate the epoxy-terminated hyperbranched polyether;
(3) and (3) adding the dimethylformamide solution of the aniline tetramer generated in the step (1) into the reaction system in the step (2), and reacting in an oil bath to react the amino group of the aniline tetramer with the epoxy group of the epoxy-terminated hyperbranched structural polyether generated in the step (2) and graft the aniline tetramer onto the epoxy-terminated hyperbranched structural polyether.
7. The method for preparing polyether macromolecule with conductive activity and end epoxy group hyperbranched structure of claim 6, wherein the method comprises the following steps: the reaction in steps (1), (2) and (3) is fully carried out by stirring at the speed of 800-1200 rpm.
8. The method for preparing polyether macromolecule with conductive activity and end epoxy group hyperbranched structure of claim 6, wherein the method comprises the following steps: in the step (1), the volume ratio of acetone to deionized water to concentrated hydrochloric acid is 4:4: 1; stirring N-phenyl-p-phenylenediamine and ammonium persulfate in an ice bath at the temperature of between 5 ℃ below zero and 0 ℃ for reaction for 3 to 5 hours; and after the reaction is finished, carrying out suction filtration, washing the precipitate by using hydrochloric acid solution and acetone in sequence, reacting with ammonia water to remove impurities, and washing by using deionized water.
9. The method for preparing polyether macromolecule with conductive activity and end epoxy group hyperbranched structure of claim 6, wherein the method comprises the following steps: in the step (2), the molar ratio of the polyethylene glycol diglycidyl ether to the ethylenediamine is (2.5-3) to 1; the number average molecular weight of the polyethylene glycol diglycidyl ether is 500; the mass fraction of the polyethylene glycol diglycidyl ether absolute ethyl alcohol solution is 30 percent; the mass fraction of the ethylenediamine absolute ethyl alcohol solution is 5 percent; the polyethylene glycol diglycidyl ether and the ethylenediamine react for 1 to 3 hours in an oil bath at the temperature of between 40 and 60 ℃.
10. The method for preparing polyether macromolecule with conductive activity and end epoxy group hyperbranched structure of claim 6, wherein the method comprises the following steps: the molar ratio of the aniline tetramer in the step (3) to the polyethylene glycol diglycidyl ether in the step (2) is 1: 1; the mass fraction of the aniline tetramer dimethylformamide solution is 20 percent; reacting aniline tetramer with epoxy-terminated hyperbranched structural polyether in an oil bath at 40-60 ℃ for 1-3 h; after the reaction is finished, purifying by using a mixed solvent of glacial ethyl ether and normal hexane, and removing residual diethyl ether and normal hexane in the product; the amount of the mixed solvent of the glacial ethyl ether and the normal hexane is 8 to 12 times of the volume of the product.
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WO2010132876A1 (en) * 2009-05-15 2010-11-18 Arizona Board Of Regents For And On Behalf Of Arizona State University Polymers for delivering a substance into a cell
CN104602712A (en) * 2012-09-06 2015-05-06 南洋理工大学 Hyaluronic acid-based drug delivery systems
CN106519253A (en) * 2016-10-26 2017-03-22 江南大学 Preparation method of chain segment type hyperbranched polyether
CN109666109A (en) * 2017-10-16 2019-04-23 天津大学 Polyethylene glycol-glycidyl methacrylate dissaving polymer and preparation method thereof of epoxy group modification
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