CN110003481B - Preparation method of eight-arm hetero-arm star polymer - Google Patents

Preparation method of eight-arm hetero-arm star polymer Download PDF

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CN110003481B
CN110003481B CN201910245801.7A CN201910245801A CN110003481B CN 110003481 B CN110003481 B CN 110003481B CN 201910245801 A CN201910245801 A CN 201910245801A CN 110003481 B CN110003481 B CN 110003481B
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何金林
晏雪生
倪沛红
戴礼兴
徐俊
张明祖
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Suzhou University
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Abstract

The invention discloses a preparation method of an eight-arm hetero-arm star polymer. Synthesizing a polystyrene lithium compound by an active anion polymerization method, and performing an addition reaction on the polystyrene lithium compound and monohydroxy heptavinyl polyhedral oligomeric silsesquioxane in benzene to obtain a seven-arm star-shaped polystyrene crude product; removing slightly excessive low addition products by using a fractional precipitation method to obtain pure monohydroxy functionalized seven-arm star polystyrene, and performing azide modification on hydroxyl groups of the low monohydroxy functionalized seven-arm star polystyrene to obtain the azide group-containing seven-arm star polystyrene. On the other hand, polycaprolactone, polyethylene glycol, poly (N, N-dimethylaminoethyl methacrylate) and poly (tert-butyl methacrylate) with alkynyl at the tail end are respectively synthesized, and the polycaprolactone, the polyethylene glycol, the poly (N, N-dimethylaminoethyl methacrylate) and the poly (tert-butyl methacrylate) are utilized to carry out cycloaddition reaction of terminal alkynyl and azide with seven-arm star-shaped polystyrene containing azide groups to prepare products; the method has the characteristics of high reaction efficiency, mild reaction conditions and less side reactions, and the star polymer prepared by the method has controllable structure and molecular weight and narrower molecular weight distribution.

Description

Preparation method of eight-arm hetero-arm star polymer
The invention belongs to an eight-arm hetero-arm star polymer and a preparation method thereof, and a divisional application with the application number of 2016108799632 and the application date of 2016, 10, and 9, and belongs to the part of a preparation method of a product.
Technical Field
The invention belongs to the field of polymer synthesis, and particularly relates to a preparation method of an eight-arm hetero-arm star polymer.
Background
Star polymers generally refer to a class of branched polymers consisting of multiple linear branches attached to the same central core. The linear branches that make up the star polymer are referred to as the "arms" of the star polymer, while the central polyfunctional group is referred to as the "core" of the star polymer. Star polymers can be broadly classified into homoarm star polymers, heteroarm star polymers, and dendritic star polymers, depending on the chemical composition of the "arms" and the structure of the "core". Compared with linear polymers, the polymer with multi-arm topological structure has the characteristics of smaller hydrodynamic volume, smaller rotating radius, low crystallinity, low melt viscosity and the like, and the properties are closely related to molecular parameters such as the number, chemical composition, molecular weight distribution and the like of arms. Star polymers have potential application values in many fields, such as catalysis, optics, bioengineering, coatings, additives and the like, and attract extensive attention of researchers.
However, the synthesis of star polymers with definite structure and composition and narrow molecular weight distribution is still a challenging task in the field of high molecular synthesis, and the methods available for synthesizing star polymers at present mainly include the "arm-first-then-core method" and the "core-first-then-arm method". The basic idea of these two synthetic routes is to use a multifunctional initiator or coupling agent, and a difunctional monomer to achieve the synthesis of star polymers. The biggest characteristic of the arm-first and nucleus-second method is that the molecular weight of linear polymer can be conveniently designed and controlled, so as to obtain star polymer with consistent arm length, but the disadvantage is that the reaction usually needs longer time and is difficult to complete; the "core-first arm-second method" is characterized in that the number of arms of the star polymer is determined by the number of functional initiating groups, and the star polymer can further initiate the polymerization of monomers to obtain a star-block copolymer. However, this method has the disadvantage that it is relatively difficult to synthesize polyfunctional initiators having a well-defined structure and high purity; in addition, it is difficult to ensure that the initiation efficiency of each initiation point is consistent, so the method has poor controllability over parameters such as molecular weight and molecular weight distribution of the polymer arm. Therefore, the star polymer with a regular structure can be prepared quickly and efficiently, and the composition structure, the molecular weight and the molecular weight distribution of the star polymer can be accurately controlled, which is still a great challenge in the field of current high-molecular synthesis; there is therefore also a need to develop new processes for the synthesis of heteroarm star polymers.
Disclosure of Invention
The invention aims to provide an eight-arm hetero-arm star polymer and a preparation method thereof. The method comprises the following steps of preparing a polystyrene lithium compound with accurate structure and narrow molecular weight distribution by using an active anion polymerization method, and performing addition reaction on the polystyrene lithium compound and monohydroxy heptavinyl polyhedral oligomeric silsesquioxane to quickly prepare a monohydroxy-containing seven-arm star polymer, and performing further functional modification on the polymer to obtain azide group-containing seven-arm star polystyrene; then the cycloaddition reaction (CuAAC) of terminal alkynyl and azide is carried out between the terminal alkynyl and a plurality of alkynyl-terminated polymers to obtain eight-arm hetero-arm star polymers; the method disclosed by the invention has the characteristics of high reaction efficiency, mild reaction conditions, less side reactions and good control on the molecular weight and molecular weight distribution of the polymer.
In order to achieve the purpose, the invention adopts the technical scheme that: an eight-arm hetero-arm star polymer has the following chemical structural formula,
Figure 230114DEST_PATH_IMAGE002
；
in the formula, R1Is composed of
Figure 334205DEST_PATH_IMAGE004
（PS）；R2Is selected from
Figure 51626DEST_PATH_IMAGE006
(PEG) or
Figure 648434DEST_PATH_IMAGE008
(PCL) or
Figure 400489DEST_PATH_IMAGE010
(PDMA) or
Figure 675482DEST_PATH_IMAGE012
(PtBMA); m = 10-40, n = 10-60; denotes a connectionA site.
Preferably, in the chemical structural formula of the eight-arm hetero-arm star polymer disclosed by the invention, R2Is selected from
Figure 880198DEST_PATH_IMAGE006
Or
Figure 266049DEST_PATH_IMAGE008
。
The preparation method of the eight-arm hetero-arm star polymer comprises the following steps:
(1) preparation of monohydroxy-containing seven-arm star polystyrene: taking styrene as a monomer, sec-butyl lithium as an initiator, and anhydrous benzene or cyclohexane as a solvent, and carrying out an anionic polymerization reaction at 20-30 ℃ to obtain a polystyrene lithium compound; then, performing addition reaction on a polystyrene lithium compound and monohydroxy heptavinyl polyhedral oligomeric silsesquioxane to obtain monohydroxy-containing seven-arm star polystyrene;
(2) preparation of azide group-containing seven-arm star polystyrene: under the catalytic action of triethylamine in an inert atmosphere, taking anhydrous tetrahydrofuran or dichloromethane as a solvent, and carrying out esterification reaction on monohydroxy-containing seven-arm star polystyrene and 2-bromoisobutyryl bromide at 20-50 ℃ to obtain bromine-containing seven-arm star polystyrene; then the bromine-containing seven-arm star polystyrene is mixed with sodium azideN, NCarrying out azide reaction in dimethylformamide at 40-80 ℃ to obtain seven-arm star polystyrene containing azide groups;
(3) preparation of alkynyl terminated polycaprolactone: in an inert atmosphere, under the catalytic action of stannous octoate, initiating an epsilon-caprolactone ring-opening polymerization reaction by taking absolute toluene as a solvent and propiolic alcohol as an initiator at the temperature of 60-80 ℃ to obtain alkynyl-terminated polycaprolactone;
(4) preparation of alkynyl terminated polyethylene glycol: in an inert atmosphere, taking polyethylene glycol monomethyl ether as a raw material, taking anhydrous tetrahydrofuran as a solvent, taking potassium hydride as a catalyst, reacting for 0.5-2 hours at 20-30 ℃, then dropwise adding a tetrahydrofuran solution of bromopropyne, and reacting for 12-24 hours at 30-50 ℃ to obtain alkynyl-terminated polyethylene glycol;
(5) preparation of alkynyl-terminated polymethacrylic acid-N, N-dimethylaminoethyl ester: under the catalytic action of triethylamine in an inert atmosphere, carrying out esterification reaction on propargyl alcohol and 2-bromoisobutyryl bromide serving as raw materials under the condition of 60-80 ℃ by taking anhydrous tetrahydrofuran or dichloromethane as a solvent and preparing a bromine compound with a modified alkynyl at the tail end; taking a bromine compound with a modified alkynyl at the tail end as an initiator, cuprous bromide andN, N, N′, N′′, N′′pentamethyldiethylenetriamine as catalyst, anhydrous tetrahydrofuran or isopropanol as solvent, and at 20-40 deg.c to initiate methacrylic acid-N, NAtom transfer radical polymerization of dimethylaminoethyl ester to obtain alkynyl-terminated polymethacrylic acid-N, N-dimethylaminoethyl ester;
(6) preparation of alkynyl-terminated poly (tert-butyl methacrylate): in an inert atmosphere, taking the bromine compound with the terminal modified alkynyl prepared in the step (5) as an initiator, and cuprous bromide andN, N, N′, N′′, N′′initiating tert-butyl methacrylate to carry out atom transfer radical polymerization reaction at 25-40 ℃ by taking pentamethyl diethylenetriamine as a catalyst and anhydrous tetrahydrofuran or isopropanol as a solvent to obtain alkynyl-terminated tert-butyl methacrylate;
(7) preparation of eight-arm hetero-arm star polymer: in an inert atmosphere, using the seven-arm star-shaped polystyrene (7 PS-POSS-N) containing the azide group prepared in the step (2)3) Taking the alkynyl-terminated polycaprolactone prepared in the step (3), the alkynyl-terminated polyethylene glycol prepared in the step (4) and the alkynyl-terminated polymethacrylic acid prepared in the step (5) as first raw materialsN, NOne of dimethylamino ethyl ester and alkynyl-terminated poly (tert-butyl methacrylate) prepared in the step (6) is used as a second raw material, and anhydrous tetrahydrofuran is used as a solvent to react for 12-24 hours at 40-60 ℃ in the presence of a cycloaddition click reaction catalyst of terminal alkynyl and azide and a catalyst ligand; obtaining the eight-arm hetero-arm star polymer;
according to the invention, the multi-arm star polymer can be prepared more quickly by using an anionic polymerization method, and the structure of the star polymer is better controlled; hydroxyl and high-activity acyl bromide are subjected to esterification reaction, so that the hydroxyl can be completely converted into a bromine group, and the bromine group is further converted into an azide group through nucleophilic substitution reaction; the structural integrity of the eight-arm hetero-arm star polymer can be ensured by utilizing the characteristics of mild reaction conditions, simplicity, high efficiency and the like of click chemistry; thereby having the technical effects of high reaction efficiency, mild reaction conditions, less side reactions and good control on the molecular weight and molecular weight distribution of the polymer.
In the technical scheme, the preparation method specifically comprises the following steps:
(1) preparing monohydroxy-containing seven-arm star polystyrene (7 PS-POSS-OH): taking styrene as a monomer, sec-butyl lithium as an initiator and anhydrous benzene as a solvent, and carrying out anionic polymerization reaction for 6-12 hours at the temperature of 20-30 ℃ to obtain a polystyrene lithium compound (PSLi); then, PSLi and monohydroxy heptavinyl polyhedral oligomeric silsesquioxane (VPOSS-OH) are directly subjected to addition reaction for 0.5-2 hours to obtain monohydroxy-containing seven-arm star-shaped polystyrene 7 PS-POSS-OH;
the above reaction formula is as follows:
Figure DEST_PATH_IMAGE014
(2) preparation of azide group-containing seven-arm star polystyrene (7 PS-POSS-N)3）：
(i) In an inert atmosphere, under the catalytic action of triethylamine, carrying out esterification reaction on 7PS-POSS-OH and 2-bromoisobutyryl bromide at 20-50 ℃ for 12-24 hours by using anhydrous tetrahydrofuran as a solvent to obtain bromine-containing seven-arm star polystyrene (7 PS-POSS-Br);
(ii) the above-mentioned 7PS-POSS-Br and sodium azide are used as raw materialsN, NReacting in dimethylformamide at 40-80 ℃ for 12-24 hours to obtain azide group-containing seven-arm star polystyrene (7 PS-POSS-N)3）；
(3) Preparation of alkynyl terminated polycaprolactone (propagyl-PCL): under the catalytic action of stannous octoate in an inert atmosphere, initiating epsilon-caprolactone ring-opening polymerization by taking absolute toluene as a solvent and propiolic alcohol as an initiator at the temperature of 60-80 ℃, and reacting for 5-8 hours to obtain the alkynyl-terminated polycaprolactone (propagyl-PCL);
the above reaction formula is as follows:
Figure DEST_PATH_IMAGE016
(4) preparation of alkynyl-terminated polyethylene glycol (propagyl-PEG): in an inert atmosphere, taking polyethylene glycol monomethyl ether as a raw material, taking anhydrous tetrahydrofuran as a solvent, taking potassium hydride as a catalyst, reacting for 0.5-2 hours at 20-30 ℃, dissolving bromopropyne in tetrahydrofuran, dropwise adding the bromopropyne from a constant-pressure dropping funnel, and reacting for 12-24 hours at 30-50 ℃ to obtain alkynyl-terminated polyethylene glycol (propagyl-PEG);
Figure DEST_PATH_IMAGE018
(5) preparation of alkynyl-terminated polymethacrylic acid-N, N-dimethylaminoethyl ester (propagyl-PDMA)
(i) Under the catalytic action of triethylamine in an inert atmosphere, carrying out esterification reaction on raw materials of absolute tetrahydrofuran or dichloromethane and propiolic alcohol and 2-bromoisobutyryl bromide at the temperature of 60-80 ℃ for 12-24 hours by taking absolute tetrahydrofuran or dichloromethane as a solvent to prepare a bromine compound with a modified alkynyl at the tail end
Figure DEST_PATH_IMAGE020
；
The above reaction formula is as follows:
Figure DEST_PATH_IMAGE022
(ii) taking the bromine compound with the end modified alkynyl as an initiator, cuprous bromide andN, N, N′, N′′, N′′the (E) -pentamethyldiethylenetriamine is used as a catalyst and is anhydrousTetrahydrofuran or isopropanol as solvent to initiate methacrylic acid-N, NPerforming atom transfer radical polymerization on the dimethylaminoethyl ester, and reacting for 6-12 hours at the temperature of 20-40 ℃ to obtain alkynyl-terminated poly (methacrylic acid-)N, N-dimethylaminoethyl ester (propagyl-PDMA);
(6) preparation of alkynyl-terminated poly (tert-butyl methacrylate) (propagyl-PtBMA): under inert atmosphere, taking a bromine compound with a modified alkynyl at the tail end as an initiator, cuprous bromide andN, N, N′, N′′, N′′using pentamethyldiethylenetriamine as a catalyst and anhydrous tetrahydrofuran or isopropanol as a solvent to initiate tert-butyl methacrylate to perform atom transfer radical polymerization, and reacting at 25-40 ℃ for 6-12 hours to obtain alkynyl-terminated tert-butyl polymethacrylate (propagyl-PtBMA);
(7) preparation of eight-arm hetero-arm star polymer: in an inert atmosphere, using the seven-arm star-shaped polystyrene (7 PS-POSS-N) containing the azide group prepared in the step (2)3) Taking the alkynyl-terminated polycaprolactone prepared in the step (3), the alkynyl-terminated polyethylene glycol prepared in the step (4) and the alkynyl-terminated polymethacrylic acid prepared in the step (5) as first raw materialsN, NOne of dimethylamino ethyl ester and alkynyl-terminated poly (tert-butyl methacrylate) prepared in the step (6) is used as a second raw material, and anhydrous tetrahydrofuran is used as a solvent to react for 12-24 hours at 40-60 ℃ in the presence of a cycloaddition click reaction catalyst of terminal alkynyl and azide and a catalyst ligand; the eight-arm hetero-arm star polymer is obtained.
In the above technical scheme, the ratio of each reactant in the steps (1) - (7) is as follows:
the molar ratio of sec-butyl lithium to styrene is 1: 10-50;
the molar ratio of the PSLi to the VPOSS-OH is (8.3-9) to 1;
the molar ratio of the 7PS-POSS-OH to the 2-bromoisobutyryl bromide to the triethylamine is 1: 5-20;
the molar ratio of the 7PS-POSS-Br to the sodium azide is 1: 5-20;
the molar ratio of the propiolic alcohol to the epsilon-caprolactone to the stannous octoate is 1: 50-100: 0.25-0.5;
the molar ratio of the polyethylene glycol monomethyl ether to the potassium hydride to the bromopropyne is 1: 2-5: 3-5;
the molar ratio of the propiolic alcohol to the 2-bromoisobutyryl bromide to the triethylamine is 1: 1-1.5;
the end-modified alkynyl bromide compound and methacrylic acid-N, N-dimethylaminoethyl ester, cuprous bromide andN, N, N′, N′′, N′′the mol ratio of the pentamethyldiethylenetriamine is 1: 10-100: 1;
the bromine compound with the end modified with alkynyl, tert-butyl methacrylate, cuprous bromide andN, N, N′, N′′, N′′the mol ratio of the pentamethyldiethylenetriamine is 1: 10-100: 1;
the molar ratio of the first raw material, the second raw material, the cycloaddition click reaction catalyst of the terminal alkynyl and the azide and the catalyst ligand is 1: 1-1.5: 1-2.
In the above technical scheme, the catalyst in the step (7) is selected from cuprous chloride, cuprous bromide or cuprous iodide; the catalyst ligand is selected from one of bipyridine, pentamethyldiethylenetriamine, tetramethylethylenediamine and hexamethyltriethylenetetramine.
In the above technical scheme, the inert atmosphere is nitrogen or argon.
In the above technical solution, in the steps (1) to (7), after the reaction is completed, the products are respectively purified, and the purification process includes the following steps:
1) purification treatment of monohydroxy-containing seven-arm star polystyrene (7 PS-POSS-OH): after the reaction is finished, concentrating the reaction solution by using a rotary evaporator, precipitating twice in methanol or ether, dissolving the obtained product by using cyclohexane or toluene until the solution is transparent, then gradually dropwise adding absolute ethyl alcohol or methanol until the solution is turbid, placing the solution in a water bath at 30-35 ℃ until the solution is transparent, transferring the solution to a separating funnel, standing, layering, taking a lower-layer transparent phase, and repeatedly operating for many times. Removing solvent from the lower transparent phase with rotary evaporator, precipitating the concentrate in methanol or ether, filtering, and oven drying to obtain white solid powder which is monohydroxy-containing seven-arm star polystyrene;
2) purifying the bromine-containing seven-arm star polystyrene (7 PS-POSS-Br): after the reaction is finished, removing the solvent from the reaction solution by using a rotary evaporator, dissolving the concentrated product in a dichloromethane solution, adding a saturated sodium bicarbonate solution, oscillating, standing, separating out a lower organic phase, extracting a water phase by using dichloromethane, combining the organic phases, drying, filtering and concentrating the organic phase solution, precipitating by using methanol or ether to obtain solid powder, and drying the obtained solid powder in a vacuum oven at the temperature of 20-30 ℃ for 12-24 hours to obtain light yellow solid powder which is bromine-containing seven-arm star-shaped polystyrene;
azide group-containing seven-arm star polystyrene (7 PS-POSS-N)3) Purification treatment of (1): after the reaction of the star-shaped polystyrene 7PS-POSS-Br containing bromine at the tail end and sodium azide is finished, filtering and concentrating a reaction product, dissolving a concentrated solution in a dichloromethane solution, adding a saturated sodium chloride solution, oscillating, standing, separating a lower organic phase, extracting a water phase with dichloromethane, combining the organic phases, drying, filtering and concentrating the organic phase solution, precipitating with methanol or ether to obtain light yellow solid powder, and drying the obtained product in a vacuum oven at the temperature of 20-30 ℃ for 12-24 hours to obtain seven-arm star-shaped polystyrene containing an azide group;
3) purification treatment of alkynyl terminated polycaprolactone (propagyl-PCL): after the reaction is finished, concentrating the reaction product by using a rotary evaporator, dripping the concentrated solution into methanol or ether for precipitation twice, carrying out suction filtration, and drying the obtained product in a vacuum oven at the temperature of 20-30 ℃ for 12-24 hours to obtain a white solid which is the alkynyl-terminated polycaprolactone;
4) purification treatment of alkynyl terminated polyethylene glycol (propagyl-PEG): after the reaction is finished, concentrating a reaction product by using a rotary evaporator, adding a saturated sodium bicarbonate solution, oscillating, standing, separating out a lower organic phase, extracting a water phase by using dichloromethane, combining the organic phases, drying, filtering and concentrating an organic phase solution, precipitating twice in n-hexane or diethyl ether, carrying out suction filtration, drying the obtained product in a vacuum oven at the temperature of 20-30 ℃ for 12-24 hours to obtain light yellow solid powder which is alkynyl-terminated polyethylene glycol;
5) alkynyl terminated polymethacrylic acid-N, NPurification treatment of dimethylaminoethyl ester (propagyl-PDMA): after the reaction of propiolic alcohol and 2-bromoisobutyryl bromide is finished, filtering to remove most insoluble substances, adding a saturated sodium bicarbonate solution into the solution obtained by filtering, oscillating, standing, separating out a lower organic phase, extracting a water phase with dichloromethane, combining the organic phases, drying, filtering and concentrating the organic phase solution, and drying in a vacuum oven at the temperature of 20-30 ℃ for 12-24 hours to obtain a colorless and transparent bromine compound with the alkynyl modified at the tail end
Figure 983863DEST_PATH_IMAGE020
(ii) a The small molecule and methacrylic acid-N, NAnd (3) after the reaction of the dimethylaminoethyl ester is finished, allowing the reaction mixture to flow through a silica gel column, concentrating by using a rotary evaporator, precipitating twice in normal hexane or diethyl ether, filtering by suction, and drying the obtained product in a vacuum oven at the temperature of 20-30 ℃ for 12-24 hours to obtain a light yellow transparent sticky solid.
6) Purification treatment of alkynyl-terminated poly (tert-butyl methacrylate) (propagyl-PtBMA):
Figure 429756DEST_PATH_IMAGE020
and (3) after the reaction with tert-butyl methacrylate is finished, allowing the reaction mixture to flow through a silica gel column, concentrating by using a rotary evaporator, precipitating twice in normal hexane or diethyl ether, filtering, and drying the obtained product in a vacuum oven at 20-30 ℃ for 12-24 hours to obtain a white transparent sticky solid.
7) Purification treatment of eight-arm hetero-arm star polymer: and after the reaction is finished, passing the reaction solution through a silica gel column, washing with toluene, concentrating by using a rotary evaporator, precipitating with methanol to obtain light yellow solid powder, and drying the light yellow solid powder in a vacuum oven at the temperature of 20-30 ℃ for 12-24 hours to obtain the eight-arm star polymer.
Preferably, in the step (2), under an inert gas atmosphere, at-5 to 0 ℃, a tetrahydrofuran solution of the monohydroxy-containing seven-arm star polystyrene is dropwise added into a tetrahydrofuran solution of 2-bromoisobutyryl bromide, and then an esterification reaction is carried out at 20 to 50 ℃ to obtain the bromine-containing seven-arm star polystyrene.
The method disclosed by the invention has the advantages of high reaction efficiency, mild reaction conditions, less side reactions and good control on the molecular weight and molecular weight distribution of the polymer, and the obtained eight-arm hetero-arm star polymer has controllable structure and good performance and can be used for multiple purposes; the eight-arm star polymer containing PEG and PDMA chain segments has good amphiphilic property, can be assembled in aqueous solution to form micelles, and has potential application in carrier materials and in-vitro diagnostic reagents, wherein the inner cores of the eight-arm star polymer are used for loading hydrophobic molecules (medicines, dyes and the like); in addition, the eight-arm star polymer has a high thermal decomposition temperature, and can be potentially applied to coating additives. Therefore, the invention also discloses the application of the eight-arm hetero-arm star polymer in carrier materials, in-vitro diagnostic reagents and heat-resistant coatings.
Due to the application of the scheme, compared with the prior art, the invention has the following advantages:
1. the invention adopts an efficient modular combination idea for the first time, combines the living anion polymerization and the cycloaddition reaction (CuAAC) of terminal alkynyl and azide, and synthesizes various eight-arm hetero-arm star polymers.
2. The invention utilizes the active anion polymerization method to prepare the polystyrene active chain which directly generates the addition reaction with the monohydroxy heptavinyl polyhedral oligomeric silsesquioxane, can quickly and efficiently prepare the seven-arm star-shaped polystyrene precursor containing hydroxyl, and can conveniently and efficiently control the molecular weight and the molecular weight distribution of the polymer chain by adopting the active anion polymerization method.
3. The invention converts hydroxyl in the seven-arm star-shaped polystyrene precursor into azide group, and the azide group and various polymers with alkynyl at the tail end undergo cycloaddition reaction (CuAAC) of terminal alkynyl and azide, so that the invention can efficiently synthesize the hetero-arm star-shaped polymer with diversified chemical structures.
Drawings
FIG. 1 is a nuclear magnetic resonance of 7PS-POSS-OH in example IOscillating hydrogen spectrum with deuterated chloroform (CDCl)3）；
FIG. 2 is a gel permeation chromatography elution profile of PS and 7PS-POSS-OH in example one, with Tetrahydrofuran (THF);
FIG. 3 is an IR spectrum of 7PS-POSS-OH in example one;
FIG. 4 is a mass spectrum of macromolecules of propagyl-PCL in example one;
FIG. 5 is a diagram of 7PS-POSS-N in the first embodiment3(A) Nuclear magnetic resonance hydrogen spectrograms of propagyl-PCL (B) and 7PS-POSS-PCL (C), and the solvent is deuterated chloroform (CDCl)3）；
FIG. 6 is a diagram of 7PS-POSS-N in the first embodiment3(A) The IR spectra of propagyl-PCL (B) and 7PS-POSS-PCL (C);
FIG. 7 is a diagram of 7PS-POSS-N in the first embodiment3The effluent curves of gel permeation chromatography of propagyl-PCL and 7PS-POSS-PCL in Tetrahydrofuran (THF);
FIG. 8 is a thermogravimetric plot of 7PS-POSS-PCL in the first example;
FIG. 9 is a mass spectrum of macromolecules of Propargyl-PEG in example two;
FIG. 10 shows the 7PS-POSS-N in example II3(A) Nuclear magnetic resonance hydrogen spectrogram of propagyl-PEG (B), 7PS-POSS-PEG (C), solvent is deuterated chloroform (CDCl)3）；
FIG. 11 is 7PS-POSS-N of example II3(A) The IR spectra of propagyl-PEG (B) and 7PS-POSS-PEG (C);
FIG. 12 is a diagram of 7PS-POSS-N in example II3The elution profiles of the gel permeation chromatography of the Propargyl-PEG and 7PS-POSS-PEG, the solvent being Tetrahydrofuran (THF);
FIG. 13 is a thermogravimetric plot of 7PS-POSS-PEG in example two.
Detailed Description
The invention is further described with reference to the following figures and examples:
the first embodiment is as follows: preparation of eight-arm hetero-arm star polymer (7 PS-POSS-PCL)
(1) Preparation of monohydroxy-containing seven-arm star polystyrene (7 PS-POSS-OH)
Styrene (7.8 mL, 68.1 mmol) was initiated at 30 ℃ for living anionic polymerization using sec-butyllithium (sec-BuLi, 3.8 mL, 4.96 mmol) as initiator and benzene (50 mL) as solvent, and a small amount of the living chain solution was taken out after 8 hours of reaction and terminated with methanol, and the remaining living chain was further subjected to addition reaction with VPOSS-OH (389.3 mg, 0.6 mmol) under vacuum conditions and terminated with methanol after 1 hour of reaction.
And after the reaction is finished, performing rotary evaporation on the product to remove the solvent, precipitating in methanol, filtering and concentrating to obtain white solid powder, drying the obtained solid powder in a vacuum oven at normal temperature for 24 hours to obtain a 7PS-POSS-OH crude product, and performing fractional precipitation by using ethanol/cyclohexane as a solvent to obtain pure 7PS-POSS-OH with the yield of 32%.
By nuclear magnetic resonance hydrogen spectroscopy (1H NMR), Gel Permeation Chromatography (GPC) and infrared spectroscopy (FT-IR). FIG. 1, FIG. 2 and FIG. 3 are nuclear magnetic resonance hydrogen spectra of the above 7PS-POSS-OH1H NMR), Gel Permeation Chromatography (GPC) efflux curves and infrared spectroscopy (FT-IR) confirm the chemical structure of 7 PS-POSS-OH. From1The H NMR spectrum can be found to correspond to the assignment of proton peaks on the polymer structure, from the GPC efflux curve (PS,
Figure DEST_PATH_IMAGE024
= 1460 g•mol-1，
Figure DEST_PATH_IMAGE026
= 1.09；7PS-POSS-OH，
Figure DEST_PATH_IMAGE028
= 14350 g•mol-1，
Figure DEST_PATH_IMAGE030
= 1.11) it can be seen that the peak shape of the purified polymer is relatively symmetrical and the molecular weight distribution is relatively narrow.
(2) Containing stackSeven-arm star polystyrene (7 PS-POSS-N) of nitrogen group3) Preparation of
Under an inert gas atmosphere, a certain amount of 2-bromoisobutyryl bromide (0.62 g, 2.68 mmol) was added to a branched flask, and dissolved with a small amount of THF and stirred. 7PS-POSS-OH (1.48 g, 0.134 mmol) was dissolved in THF and added to a constant pressure dropping funnel, followed by a syringe to which an amount of TEA was added. And (3) under the ice-water bath condition (-5-0 ℃), dropwise adding the solution in the constant-pressure dropping funnel into the branch bottle, and after dropwise adding, placing the whole device in an oil bath at 30 ℃ for reaction for 24 hours. After the reaction is finished, the solvent is removed by rotary evaporation, the mixture is continuously dissolved by dichloromethane and is added with saturated NaHCO3Extracting twice, each time about 30 mL, extracting with about 30 mL saturated NaCl until the solution is clear and transparent, and finally using anhydrous Na2SO4Drying, filtering, spin-drying, precipitating with methanol, and drying in a vacuum oven to obtain light yellow powder.
The resulting solid was further dissolved in 10 mL of DMF and taken as NaN3(0.13 g, 2.69 mmol) in the solution, reacting for 24 h at 30 ℃, removing DMF after the reaction is finished, precipitating and drying to obtain light yellow powdery solid 7PS-POSS-N3The yield was 65.5%.
By nuclear magnetic resonance hydrogen spectroscopy (1H NMR), infrared spectroscopy (FT-IR) and Gel Permeation Chromatography (GPC). FIG. 5 (A), FIG. 6 (A) and FIG. 7 are the above 7PS-POSS-N, respectively3Nuclear magnetic resonance hydrogen spectrum of (1H NMR) chart, infrared spectrum (FT-IR) chart and Gel Permeation Chromatography (GPC) outflow curve, and confirmed that 7PS-POSS-N3The chemical structure of (1). From1The proton peak assignment corresponding to the polymer structure can be found in the H NMR spectrum, and the GPC outflow curve (7 PS-POSS-N)3，
Figure 29758DEST_PATH_IMAGE024
= 15130 g•mol-1，
Figure 970032DEST_PATH_IMAGE026
Polymers obtained by purification can be seen in = 1.12)The peak shape of the azide group is symmetrical, the molecular weight distribution is narrow, and a characteristic peak (2105 cm) of the azide group can be seen from an FT-IR spectrum-1）。
(3) Preparation of alkynyl terminated polycaprolactone (propagyl-PCL)
Under inert atmosphere, taking anhydrous Toluene as a solvent, adding propargyl alcohol (100 mg, 1.78 mmol), epsilon-caprolactone (10.17 g, 89.12 mmol) and stannous octoate (0.9 mL, 0.45 mmol, 0.5M solution in Toluene) into a reaction bottle through a dried syringe for ring-opening polymerization, reacting for 6 hours, filtering, concentrating, precipitating with methanol, and drying in a vacuum oven to obtain the alkynyl-terminated polycaprolactone with the yield of 19.7%.
By nuclear magnetic resonance hydrogen spectroscopy (1H NMR), infrared spectroscopy (FT-IR), Gel Permeation Chromatography (GPC), macromolecular mass spectrometry (MALDI-TOF MS) and characterization thereof. FIG. 4, FIG. 5 (B), FIG. 6 (B) and FIG. 7 are the mass spectrum of the macromolecule (MALDI-TOF MS) and the hydrogen nuclear magnetic resonance spectrum (MALDI-TOF MS) of the aforementioned Propargyl-PCL, respectively1H NMR), infrared spectroscopy (FT-IR) and Gel Permeation Chromatography (GPC) efflux curves to verify the chemical structure. From1The H NMR spectrum can be found to correspond to the assignment of proton peaks on the polymer structure, the GPC flow curve (propagyl-PCL,
Figure 945948DEST_PATH_IMAGE024
= 3360 g•mol-1，
Figure 703688DEST_PATH_IMAGE026
= 1.08) the purified polymer had a relatively symmetrical peak profile, a relatively narrow molecular weight distribution, and a distinct alkynyl group (3280 cm) was observed in the FT-IR spectrum-1) And a carbonyl group (1730 cm)-1) Characteristic peak of (2).
(4) Preparation of eight-arm hetero-arm star polymer 7PS-POSS-PCL
Adding 7PS-POSS-N into a round-bottomed bottle in an inert gas atmosphere3(100 mg, 0.009 mmol) and alkynyl terminated polycaprolactone (20.15 mg, 0.011)mmol) and dissolved in 10 mL of THF. CuBr (2.58 mg, 0.018 mmol) and PMDETA (3.12 mg, 0.018 mmol) were added quickly and reacted in a 45 ℃ oil bath for 24 h. After the reaction is finished, the solution flows through a silica gel column, and then is subjected to rotary evaporation, precipitation and drying to obtain light yellow solid powder 7PS-POSS-PCL with the yield of 70%.
FIG. 5 (C), FIG. 6 (C) and FIG. 7 are the NMR spectra of the above 7PS-POSS-PCL, respectively (1H NMR) pattern, infrared spectrum (FT-IR) pattern and Gel Permeation Chromatography (GPC) efflux curve, which confirmed the chemical structure of 7PS-POSS-PCL and the successful synthesis of eight-arm hetero-arm star polymer. From1The proton peak assignment corresponding to the star polymer structure can be found in the H NMR spectrum, and the elution profile from GPC (7 PS-POSS-PCL,
Figure 882997DEST_PATH_IMAGE024
= 16500 g•mol-1，
Figure 348001DEST_PATH_IMAGE026
= 1.13) it can be seen that the peak shape of the purified star polymer is relatively symmetrical and the molecular weight distribution is relatively narrow. FIG. 8 is a thermal weight loss (TGA) curve of the above 7PS-POSS-PCL and its polymer precursors, from which it can be seen that the star polymer has better thermal stability.
Example two: preparation of eight-arm hetero-arm star polymer (7 PS-POSS-PEG)
(1) Preparation of alkynyl-terminated polyethylene glycol (Propargyl-PEG)
A100 mL branched flask was charged with an amount of mPEG-OH (2.00 g, 1 mmol) and 40 mL of anhydrous toluene, and azeotropically removed with water. After completion of the reaction, the purified mPEG-OH was dissolved in anhydrous THF under an inert gas atmosphere, KH (0.24 g, 6 mmol) was slowly added, and the reaction was stirred for 1 h under an oil bath at 25 ℃.
To a constant pressure dropping funnel was added 3-bromopropyne (1.19 g, 10 mmol, 80% in Toluene) with syringe and diluted with about 5 mL of THF. Then dropwise adding the mixture into a branch bottle, and reacting for 20 hours under an oil bath at 45 ℃ after the dropwise adding is finished. After filtration and concentration, 40 mL of CH was added2Cl2With saturated NaHCO3Extracting the solution for three times, collecting organic phase, and extracting with anhydrous Na2SO4Drying for 12 h, filtering, spin-drying, precipitating with n-hexane, and drying in a vacuum oven to obtain light yellow alkynyl terminated PEG with a yield of 91%.
By nuclear magnetic resonance hydrogen spectroscopy (1H NMR), Gel Permeation Chromatography (GPC), macromolecular mass spectrometry (MALDI-TOF MS) and infrared spectroscopy (FT-IR). FIG. 9, FIG. 10B, FIG. 11B and FIG. 12 are the mass spectrum of the aforementioned Propargyl-PEG macromolecule (MALDI-TOF MS), hydrogen nuclear magnetic resonance spectrum (NMR)1H NMR), infrared spectroscopy (FT-IR) and Gel Permeation Chromatography (GPC) efflux curves, validating the chemical structure. From1The H NMR spectrum can be found to correspond to the assignment of proton peaks on the polymer structure, the GPC flow curve (propagyl-PEG,
Figure 929155DEST_PATH_IMAGE024
= 3000 g•mol-1，
Figure 451272DEST_PATH_IMAGE026
= 1.05) the purified polymer had a relatively symmetrical peak profile, the molecular weight distribution was relatively narrow, and significant alkynyl groups (3280 cm) were observed in the FT-IR spectrum-1) Characteristic peak of (2).
(2) Preparation of eight-arm hetero-arm star polymer 7PS-POSS-PEG
Adding the 7PS-POSS-N prepared in the first example into a round-bottomed bottle under the inert gas atmosphere3(100 mg, 0.009 mmol) and Propargyl-PEG (26.5 mg, 0.0126 mol), dissolved in 12 mL of THF. CuBr (2.0 mg, 0.0135 mmol) and PMDETA (2.34 mg, 0.0135 mmol) were added quickly and reacted for 22 h in a 55 ℃ oil bath. After the reaction is finished, the solution flows through a silica gel column, and then is subjected to rotary evaporation, precipitation and drying to obtain light yellow solid powder 7PS-POSS-PEG with the yield of 66%.
FIG. 10 (C), FIG. 11 (C) and FIG. 12 are the NMR spectra of the above 7PS-POSS-PEG, respectively (1H NMR) chart, infrared spectrum (FT-IR) chartAnd gel permeation chromatography efflux curves (GPC, as 7PS-POSS-N3For reference), the chemical structure of 7PS-POSS-PEG and the successful synthesis of an eight-arm hetero-arm star polymer are verified; wherein FIG. 10 (A) and FIG. 11 (A) are 7PS-POSS-N3For reference. From1The proton peak assignment corresponding to the star polymer structure can be found in the H NMR spectrum, the elution curve from GPC (7 PS-POSS-PEG,
Figure 383456DEST_PATH_IMAGE024
= 16170 g•mol-1，
Figure 649221DEST_PATH_IMAGE026
= 1.11) it can be seen that the peak shape of the purified star polymer is relatively symmetrical and the molecular weight distribution is relatively narrow. FIG. 13 is a thermal weight loss (TGA) curve of the above 7PS-POSS-PEG and its polymer precursors, from which it can be seen that the star polymer has better thermal stability.
Example three: preparation of eight-arm hetero-arm star polymer (7 PS-POSS-PDMA)
(1) Preparation of monohydroxy-containing seven-arm star polystyrene (7 PS-POSS-OH)
Sec-butyllithium (sec-BuLi, 3.0 mL, 3.92 mmol) was used as an initiator, benzene (40 mL) was used as a solvent, styrene (8.16 mL, 78.4 mmol) was initiated at 30 ℃ for living anion polymerization, a small amount of the living chain solution was taken after 10 hours of reaction and terminated with methanol, the remaining living chain was further subjected to addition reaction with VPOSS-OH (259.5 mg, 0.4 mmol) under vacuum, and after 1 hour of reaction, terminated with methanol.
And after the reaction is finished, performing rotary evaporation on the product to remove the solvent, precipitating in methanol, filtering and concentrating to obtain white solid powder, drying the obtained solid powder in a vacuum oven at normal temperature for 24 hours to obtain a 7PS-POSS-OH crude product, and performing fractional precipitation by using ethanol/cyclohexane as a solvent to obtain pure 7PS-POSS-OH with the yield of 35%.
(2) Azide group-containing seven-arm star polystyrene (7 PS-POSS-N)3) Preparation of
Under an inert gas atmosphere, a certain amount of 2-bromoisobutyryl bromide (0.35 g, 1.5 mmol) was added to a branched flask, and dissolved with a small amount of THF and stirred. 7PS-POSS-OH (1.60 g, 0.1 mmol) was dissolved in THF and added to a constant pressure dropping funnel, followed by a syringe to which an amount of TEA was added. And (3) under the ice-water bath condition (-5-0 ℃), dropwise adding the solution in the constant-pressure dropping funnel into the branch bottle, and after dropwise adding, placing the whole device in an oil bath at 35 ℃ for reaction for 20 hours. After the reaction is finished, the solvent is removed by rotary evaporation, the mixture is continuously dissolved by dichloromethane and is added with saturated NaHCO3Extracting twice, each time about 35 mL, extracting with about 35 mL saturated NaCl until the solution is clear and transparent, and finally using anhydrous Na2SO4Drying, filtering, spin-drying, precipitating with methanol, and drying in a vacuum oven to obtain light yellow powder.
The resulting solid was further dissolved in 10 mL of DMF and taken as NaN3(0.097 g, 2.0 mmol) in the solution, reacting at 30 ℃ for 24 h, removing DMF after the reaction is finished, precipitating and drying to obtain light yellow powdery solid 7PS-POSS-N3The yield was 70%.
(3) Alkynyl terminated polymethacrylic acid-N, NPreparation of (meth) acrylic acid dimethyl ester (Propargyl-PDMA)
CuBr (21.5 mg, 0.15 mmol) was added to a vial under an inert gas atmosphere, vacuum was applied, and then a bromine compound having a terminal modified alkynyl group (30.8 mg, 0.15 mmol), DMA monomer (0.943 g, 6.0 mmol), PMDETA (26 mg, 0.15 mmol) and 10 mL of THF were sequentially injected from a syringe, and the reaction was stirred at 35 ℃ for 6 hours. After the reaction is finished, the solution flows through a silica gel column, and is subjected to rotary evaporation, n-hexane precipitation and vacuum oven drying at 30 ℃ for 12 hours to obtain a light yellow sticky solid propagyl-PDMA with the yield of 65%.
(4) Preparation of eight-arm hetero-arm star polymer 7PS-POSS-PDMA
Adding 7PS-POSS-N into a round-bottomed bottle in an inert gas atmosphere3(160 mg, 0.01 mmol) and Propargyl-PDMA (52.5 mg, 0.015 mmol), and dissolved in 15 mL of THF. CuCl (2.985 mg, 0.03 mmol) and PMDETA (5.2 mg, 0.03 mmol) were added quickly in oil at 50 deg.CThe reaction is carried out for 24 hours under a bath. After the reaction is finished, the solution flows through a silica gel column, and then is subjected to rotary evaporation, precipitation and drying to obtain light yellow solid powder 7PS-POSS-PDMA with the yield of 64%.
Example four: preparation of eight-arm hetero-arm star polymer (7 PS-POSS-PtBMA)
(1) Preparation of alkynyl-terminated Poly (tert-butyl methacrylate) (Propargyl-PtBMA)
CuBr (21.5 mg, 0.15 mmol) was added to a vial under an inert gas atmosphere, vacuum was applied, and then a terminal-modified alkynyl bromide compound (30.8 mg, 0.15 mmol), a tBMA monomer (0.853 g, 6.0 mmol), PMDETA (26 mg, 0.15 mmol) and 10 mL of THF were sequentially injected from a syringe, and the reaction was stirred at 35 ℃ for 6 hours. After the reaction is finished, the solution flows through a silica gel column, and is subjected to rotary evaporation, n-hexane precipitation and vacuum oven drying at 30 ℃ for 12 hours to obtain a light yellow sticky solid propagyl-PDMA with the yield of 70%.
(2) Preparation of eight-arm hetero-arm star polymer 7PS-POSS-PtBMA
Adding the 7PS-POSS-N prepared in the first example into a round-bottomed bottle under the inert gas atmosphere3(100 mg, 0.009 mmol) and Propargyl-PtBMA (54.6 mg, 0.013 mmol) were dissolved in 10 mL of THF. CuBr (1.94 mg, 0.0135 mmol) and PMDETA (2.34 mg, 0.0135 mmol) were added quickly and reacted for 20 h in a 50 ℃ oil bath. After the reaction is finished, the solution flows through a silica gel column, and then is subjected to rotary evaporation, precipitation and drying to obtain light yellow solid powder 7PS-POSS-PtBMA with the yield of 60%.

Claims (8)

1. A preparation method of an eight-arm hetero-arm star polymer is characterized by comprising the following steps:
(1) preparation of monohydroxy-containing seven-arm star polystyrene: taking styrene as a monomer, sec-butyl lithium as an initiator, and anhydrous benzene or cyclohexane as a solvent, and carrying out an anionic polymerization reaction at 20-30 ℃ to obtain a polystyrene lithium compound; then, performing addition reaction on a polystyrene lithium compound and monohydroxy heptavinyl polyhedral oligomeric silsesquioxane to obtain monohydroxy-containing seven-arm star polystyrene;
(2) preparation of azide group-containing seven-arm star polystyrene: under the catalytic action of triethylamine in an inert atmosphere, taking anhydrous tetrahydrofuran or dichloromethane as a solvent, and carrying out esterification reaction on monohydroxy-containing seven-arm star polystyrene and 2-bromoisobutyryl bromide at 20-50 ℃ to obtain bromine-containing seven-arm star polystyrene; then the bromine-containing seven-arm star polystyrene is mixed with sodium azideN, NCarrying out azide reaction in dimethylformamide at 40-80 ℃ to obtain seven-arm star polystyrene containing azide groups;
(3) preparation of alkynyl terminated polycaprolactone: in an inert atmosphere, under the catalytic action of stannous octoate, initiating an epsilon-caprolactone ring-opening polymerization reaction by taking absolute toluene as a solvent and propiolic alcohol as an initiator at the temperature of 60-80 ℃ to obtain alkynyl-terminated polycaprolactone;
(4) preparation of alkynyl terminated polyethylene glycol: in an inert atmosphere, taking polyethylene glycol monomethyl ether as a raw material, taking anhydrous tetrahydrofuran as a solvent, taking potassium hydride as a catalyst, reacting for 0.5-2 hours at 20-30 ℃, then dropwise adding a tetrahydrofuran solution of bromopropyne, and reacting for 12-24 hours at 30-50 ℃ to obtain alkynyl-terminated polyethylene glycol;
(5) preparation of alkynyl-terminated polymethacrylic acid-N, N-dimethylaminoethyl ester: under the catalytic action of triethylamine in an inert atmosphere, carrying out esterification reaction on propargyl alcohol and 2-bromoisobutyryl bromide serving as raw materials under the condition of 60-80 ℃ by taking anhydrous tetrahydrofuran or dichloromethane as a solvent and preparing a bromine compound with a modified alkynyl at the tail end; taking a bromine compound with a modified alkynyl at the tail end as an initiator, cuprous bromide andN, N, N′, N′′, N′′pentamethyldiethylenetriamine as catalyst, anhydrous tetrahydrofuran or isopropanol as solvent, and at 20-40 deg.c to initiate methacrylic acid-N, NAtom transfer radical polymerization of dimethylaminoethyl ester to obtain alkynyl-terminated polymethacrylic acid-N, N-dimethylaminoethyl ester;
(6) preparation of alkynyl-terminated poly (tert-butyl methacrylate): in an inert atmosphere, taking the bromine compound with the end modified alkynyl prepared in the step (5) as an initiator and bromineCuprous oxide andN, N, N′, N′′, N′′initiating tert-butyl methacrylate to carry out atom transfer radical polymerization reaction at 25-40 ℃ by taking pentamethyl diethylenetriamine as a catalyst and anhydrous tetrahydrofuran or isopropanol as a solvent to obtain alkynyl-terminated tert-butyl methacrylate;
(7) preparation of eight-arm hetero-arm star polymer: in an inert atmosphere, taking the seven-arm star-shaped polystyrene containing the azide group prepared in the step (2) as a first raw material, taking the alkynyl-terminated polycaprolactone prepared in the step (3), the alkynyl-terminated polyethylene glycol prepared in the step (4) and the alkynyl-terminated polymethacrylic acid-doped polystyrene prepared in the step (5)N, NOne of dimethylamino ethyl ester and alkynyl-terminated poly (tert-butyl methacrylate) prepared in the step (6) is used as a second raw material, and anhydrous tetrahydrofuran is used as a solvent to react for 12-24 hours at 40-60 ℃ in the presence of a cycloaddition click reaction catalyst of terminal alkynyl and azide and a catalyst ligand; the eight-arm hetero-arm star polymer is obtained.
2. The method for producing an eight-arm hetero-arm star polymer according to claim 1, wherein: the chemical structural formula of the eight-arm hetero-arm star polymer is as follows:
Figure DEST_PATH_IMAGE001
in the formula, R1Is composed of
Figure 530523DEST_PATH_IMAGE002
；R2Is selected from
Figure DEST_PATH_IMAGE003
、
Figure 50366DEST_PATH_IMAGE004
、
Figure DEST_PATH_IMAGE005
Or
Figure 296363DEST_PATH_IMAGE006
；m = 10～40，n = 10～60。
3. The method for producing an eight-arm hetero-arm star polymer according to claim 2, wherein: r2Is selected from
Figure 479345DEST_PATH_IMAGE003
Or
Figure 543116DEST_PATH_IMAGE004
。
4. The method for producing an eight-arm hetero-arm star polymer according to claim 1, wherein: the inert atmosphere is nitrogen or argon atmosphere.
5. The method for producing an eight-arm hetero-arm star polymer according to claim 1, wherein: after the reactions of the steps (1) to (7), respectively purifying products, comprising the following steps:
1) purification treatment of monohydroxy-containing seven-arm star polystyrene: after the reaction is finished, concentrating the reaction liquid by using a rotary evaporator, precipitating twice in methanol or ether, dissolving the precipitate with cyclohexane or toluene until the precipitate is transparent, then dropwise adding absolute ethyl alcohol or methanol until the solution is turbid, then treating at 30-35 ℃ until the solution is transparent, transferring to a separating funnel, standing for layering, removing the solvent from a lower transparent phase, precipitating in methanol or ether, and filtering and drying the precipitate to obtain the monohydroxy-containing seven-arm star-shaped polystyrene;
2) purifying the bromine-containing seven-arm star polystyrene: after the reaction is finished, removing the solvent from the reaction solution by using a rotary evaporator, dissolving the concentrated product in a dichloromethane solution, adding a saturated sodium bicarbonate solution, oscillating, standing, separating out a lower organic phase, extracting a water phase by using dichloromethane, combining the organic phases, drying, filtering and concentrating the organic phase, precipitating by using methanol or ether to obtain solid powder, and drying the solid powder in a vacuum oven at the temperature of 20-30 ℃ for 12-24 hours to obtain the bromine-containing seven-arm star-shaped polystyrene;
purifying seven-arm star polystyrene containing azide groups: after the reaction is finished, filtering and concentrating a reaction product, dissolving a concentrated solution into a dichloromethane solution, adding a saturated sodium chloride solution, oscillating and standing, separating out a lower organic phase, extracting a water phase with dichloromethane, combining the organic phases, drying, filtering, concentrating the organic phase solution, precipitating with methanol or diethyl ether to obtain light yellow solid powder, and drying the light yellow solid powder in a vacuum oven at the temperature of 20-30 ℃ for 12-24 hours to obtain the seven-arm star-shaped polystyrene containing the azide groups;
3) purification treatment of alkynyl terminated polycaprolactone: after the reaction is finished, concentrating the reaction product by using a rotary evaporator, dripping the concentrated solution into methanol or ether for precipitation and suction filtration, and drying the filter cake in a vacuum oven at the temperature of 20-30 ℃ for 12-24 hours to obtain alkynyl-terminated polycaprolactone;
4) and (3) purifying and processing the alkynyl-terminated polyethylene glycol: after the reaction is finished, concentrating the reaction solution by using a rotary evaporator, adding a saturated sodium bicarbonate solution, oscillating, standing, separating out a lower organic phase, extracting a water phase by using dichloromethane, combining the organic phases, drying, filtering and concentrating the organic phase solution, precipitating and filtering in n-hexane or diethyl ether, drying a filter cake in a vacuum oven at 20-30 ℃ for 12-24 hours to obtain alkynyl-terminated polyethylene glycol;
5) purification treatment of the terminal-modified alkynyl bromine compound: after the reaction is finished, filtering to remove most insoluble substances, adding a saturated sodium bicarbonate solution into the solution obtained by filtering, oscillating, standing, separating out a lower organic phase, extracting a water phase with dichloromethane, combining the organic phases, drying, filtering and concentrating the organic phase solution, and drying the organic phase solution in a vacuum oven at the temperature of 20-30 ℃ for 12-24 hours to obtain a bromine compound with the alkynyl modified at the tail end;
alkynyl terminated polymethacrylic acid-N, N-purification treatment of dimethylaminoethyl ester: after the reaction is finished, concentrating the reaction solution by using a rotary evaporator, precipitating in normal hexane or ether,drying the precipitate in a vacuum oven at 20-30 ℃ for 12-24 hours to obtain alkynyl-terminated polymethacrylic acid-N, N-dimethylaminoethyl ester;
6) and (3) purifying alkynyl-terminated poly (tert-butyl methacrylate): after the reaction is finished, concentrating the reaction product by using a rotary evaporator, precipitating in normal hexane or ether, and drying the precipitate in a vacuum oven at the temperature of 20-30 ℃ for 12-24 hours to obtain alkynyl-terminated poly (tert-butyl methacrylate);
7) purification treatment of eight-arm hetero-arm star polymer: and after the reaction is finished, passing the reaction solution through a silica gel column, washing with toluene, concentrating by using a rotary evaporator, precipitating with methanol to obtain light yellow solid powder, and drying the light yellow solid powder in a vacuum oven at the temperature of 20-30 ℃ for 12-24 hours to obtain the eight-arm hetero-arm star polymer.
6. The method for producing an eight-arm hetero-arm star polymer according to claim 1, wherein: in the step (7), the catalyst is selected from cuprous chloride, cuprous bromide or cuprous iodide; the catalyst ligand is selected from bipyridine, pentamethyldiethylenetriamine, tetramethylethylenediamine or hexamethyltriethylenetetramine.
7. The method for producing an eight-arm hetero-arm star polymer according to claim 1, wherein: in the step (1), anionic polymerization is carried out for 6-12 hours, and addition reaction is carried out for 0.5-2 hours; in the step (2), esterification reaction is carried out for 12-24 hours, and azide reaction is carried out for 12-24 hours; in the step (3), ring-opening polymerization is carried out for 5-8 hours; in the step (5), esterification reaction is carried out for 12-24 hours, and atom transfer radical polymerization reaction is carried out for 6-12 hours; in the step (6), the atom transfer radical polymerization is carried out for 6-12 hours.
8. The method for producing an eight-arm hetero-arm star polymer according to claim 1, wherein: in the step (2), under the atmosphere of inert gas, dripping a tetrahydrofuran solution of the monohydroxy-containing seven-arm star-shaped polystyrene into a tetrahydrofuran solution of 2-bromoisobutyryl bromide at the temperature of-5-0 ℃, and then carrying out an esterification reaction at the temperature of 20-50 ℃ to obtain the bromine-containing seven-arm star-shaped polystyrene.
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