CN112626613A - Brush-shaped hybrid micelle and preparation method thereof - Google Patents

Brush-shaped hybrid micelle and preparation method thereof Download PDF

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CN112626613A
CN112626613A CN202011399326.8A CN202011399326A CN112626613A CN 112626613 A CN112626613 A CN 112626613A CN 202011399326 A CN202011399326 A CN 202011399326A CN 112626613 A CN112626613 A CN 112626613A
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micelle
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童再再
胡崴
苏亚伟
王亚平
陈世昌
江国华
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Zhejiang University of Technology ZJUT
Zhejiang Sci Tech University ZSTU
Zhejiang University of Science and Technology ZUST
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Abstract

The invention relates to a preparation method of brush-shaped hybrid micelles, which comprises the following steps: (1) synthesizing block copolymers PCL-b-P4VP and PCL-b-PDMA; (2) preparing a seed micelle; (3) preparing a template anchoring PCL-b-P4VP seeds on the carbon nano tube; (4) the PCL-b-PDMA monomer can be used for realizing tunable epitaxial growth on a seed micelle. The PCL-b-P4VP rodlike seed micelle prepared by ultrasonic disruption is anchored on the carbon nano tube by utilizing the hydrogen bond effect, the PCL-b-PDMA is added to obtain the brush-shaped hybrid micelle which grows on the PCL-b-P4VP seed by the PCL-b-PDMA, the grafting density of the seed micelle PCL-b-P4VP on the carbon nano tube and the mass ratio of the seed micelle PCL-b-P4VP to the monomer PCL-b-PDMA are adjusted to change the shape of the brush-shaped structure, and the controllable shape of the micelle is realized.

Description

Brush-shaped hybrid micelle and preparation method thereof
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a brush-shaped hybrid micelle and a preparation method thereof.
Background
In recent years, the construction of morphology-controllable and ordered composite structures by active self-assembly has attracted much attention. The biggest characteristic of active self-assembly is that the tail end of the seed structure has activity, and the newly added monomer can continuously grow and prolong at the active tail end of the seed, so that the formation of active sites can be controlled to construct complex structures with different dimensions. The concept of active self-assembly comes from the field of polymer chemistry, and at present, in the field of high molecular polymers, a multi-dimensional complex nano-or micron-scale structure is successfully assembled by combining a block copolymer with different intermolecular forces. For small organic molecule systems, methods for constructing one-dimensional linear composite structures are mature, but the formation and control of two-dimensional or three-dimensional composite structures still pose a huge challenge.
The organic nano self-assembly material with a controllable structure is a hot research problem because the crystalline material with a novel structure has huge potential application in the aspects of catalysis, templating, emulsification, nano-filler and liquid crystal. However, micelles prepared by crystallization-driven self-assembly are generally one-dimensional rod-like structures and two-dimensional sheet-like structures, and great challenges still exist in the aspect of preparation of brush-shaped micelles, particularly in the aspect of shape adjustability, so that intensive research is still needed for how to prepare brush-shaped hybrid micelles with controllable shapes.
Disclosure of Invention
Based on the defects in the prior art, the invention provides a brush-shaped hybrid micelle and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of brush-shaped hybrid micelles comprises the following steps:
(1) synthesizing block copolymers PCL-b-P4VP and PCL-b-PDMA;
(2) preparation of seed micelle solution: dissolving the block copolymer PCL-b-P4VP, heating, cooling to room temperature, and aging to obtain polydisperse micelle solution; placing the micelle solution in an ice water bath for ultrasonic treatment to obtain a seed micelle solution;
(3) preparing a template of anchoring seeds on the carbon nano tube: diluting the seed micelle solution to obtain a seed solution, dripping the seed solution into the carbon nanotube suspension, uniformly mixing, diluting, and aging at room temperature to obtain a template solution containing PCL-b-P4VP short crystals anchored on the carbon nanotubes;
(4) preparation of heteroepitaxially grown brush-like micelles: adding the PCL-b-PDMA monomer dispersed in a good solvent into a template solution, uniformly mixing, and aging at room temperature to obtain the brush-shaped hybrid micelle in which the PCL-b-PDMA monomer grows along the PCL-b-P4VP short crystal epitaxy.
Preferably, the structural formula of the block copolymer PCL-b-P4VP is as follows:
Figure BDA0002816488660000021
wherein x is an integer of 320-400, and y is an integer of 40-80.
Preferably, x is 60.
Preferably, the structural formula of the block copolymer PCL-b-PDMA is as follows:
Figure BDA0002816488660000022
wherein m is an integer of 240 to 400, and n is an integer of 40 to 80.
Preferably, m is 320 and n is 60.
Preferably, in the step (1):
the synthesis of the block copolymer PCL-b-P4VP comprises the following steps: sequentially adding RAFT polymerization macroinitiator PCL-CTA, azodiisobutyronitrile, 1, 4-dioxane and 4-vinylpyridine into a reaction bottle, performing multiple liquid nitrogen freezing-vacuumizing-nitrogen introducing-vacuumizing-unfreezing cycles, and reacting in an oil bath under the nitrogen atmosphere; after the reaction is stopped by liquid nitrogen rapid cooling, the solution is precipitated in ice-stored ether, and the segmented copolymer PCL-b-P4VP is obtained after suction filtration and vacuum drying; wherein the molar ratio of the macromolecular initiator PCL-CTA, the 4-vinylpyridine and the azobisisobutyronitrile is 1: 320-400: 0.1 to 0.2;
the synthesis of the block copolymer PCL-b-PDMA comprises the following steps: sequentially adding a RAFT polymerization macroinitiator PCL-CTA, azodiisobutyronitrile, 1, 4-dioxane and a monomer N, N-dimethylacrylamide into a reaction bottle, performing multiple liquid nitrogen freezing-vacuumizing-nitrogen introducing-vacuumizing-unfreezing cycles, and then placing the mixture in an oil bath for reaction under the nitrogen atmosphere; after the reaction is stopped by liquid nitrogen rapid cooling, the solution is precipitated in ice-stored ether, and the segmented copolymer PCL-b-PDMA is obtained after suction filtration and vacuum drying; the molar ratio of the macroinitiator PCL-CTA, N-dimethylacrylamide and azobisisobutyronitrile is 1: 240-400: 0.1 to 0.2.
Preferably, in the step (3), the mass concentration of the carbon nanotube suspension is 0.02-1 mg/mL, and the mass ratio of the seed micelles PCL-b-P4VP in the seed solution to the carbon nanotubes in the carbon nanotube suspension is 0.1-2: 1.
preferably, in the step (4), the mass ratio of the monomer PCL-b-PDMA to the seed micelles in the template solution is 1-20: 1, the good solvent comprises one or more of tetrahydrofuran, trichloromethane, dimethylformamide, 1, 4-dioxane and dimethyl sulfoxide.
Preferably, the N, N-dimethylacrylamide is replaced by 2-dimethylaminoethyl methacrylate and/or the block copolymer PCL-b-PDMA is replaced by the homopolymer PCL.
The invention also provides the brush-shaped hybrid micelle prepared by the preparation method of any one scheme, wherein the length-diameter ratio of the brush-shaped hybrid micelle is 1-20.
Compared with the prior art, the invention has the beneficial effects that:
the invention obtains the rod-shaped seed micelles with different lengths or uniform sizes by controlling the ultrasonic breaking time, anchors the rod-shaped seed micelles on CNT through hydrogen bond acting force to obtain the seed templates with different grafting densities or uniform sizes, adds the monomer PCL-b-PDMA into the template solution, and because the growth space of the monomer is limited, the monomer tends to grow along the extension of the seed micelle PCL-b-P4VP, and the difference of the grafting densities of the seeds causes different degrees of space limitation, thereby influencing the growth process of the monomer PCL-b-PDMA and obtaining the brush-shaped hybrid micelles with different appearances. Meanwhile, the brush-shaped hybrid micelle with different morphologies can be obtained by controlling the mass ratio of the monomer to the seed, so that the controllability of the brush-shaped micelle morphology is realized, a new scheme is provided for the self-assembly process of the crystallization-driven complex structure, and the method is expected to be widely applied to the fields of biomedicine, energy catalysis and the like.
The preparation method of the brush-shaped hybrid micelle is simple and convenient to operate, simple in process and mild in preparation conditions, the prepared brush-shaped micelle material is uniform in shape and stable in structure, and a typical brush-shaped structure has a larger specific surface area than other rod-shaped and sheet-shaped structures and also has a larger loading capacity on guest substances such as medicines, dyes, catalysts and the like; when used for in vivo delivery of drugs, have longer in vivo circulation times than the zero-dimensional spherical structure; when the supported metal nanoparticles are used for catalysis, the heterogeneous system is easy to separate, and the reusability is good.
Drawings
FIG. 1 is a transmission electron microscope image of a seed micelle according to a first embodiment of the present invention;
FIG. 2 is a transmission electron micrograph of a CNT-seed template according to a first embodiment of the present invention;
FIG. 3 is a transmission electron microscope image of a brush micelle according to the first embodiment of the present invention;
FIG. 4 is a transmission electron microscope image of a brush micelle according to a second embodiment of the present invention;
FIG. 5 is a transmission electron microscope image of a brush micelle according to a third embodiment of the present invention;
FIG. 6 is a transmission electron micrograph of a brush micelle according to example four of the present invention;
FIG. 7 is a transmission electron micrograph of a brush micelle of example five of the present invention;
FIG. 8 is a transmission electron micrograph of a brush micelle of example six of the present invention;
FIG. 9 is a transmission electron micrograph of a brush micelle of example seven of the present invention;
FIG. 10 is a transmission electron micrograph of a brush micelle of example eight of the present invention;
FIG. 11 is a transmission electron micrograph of a brush micelle of example nine of the present invention.
Detailed Description
The technical solution of the present invention is further described below by specific examples.
The first embodiment is as follows:
the preparation method of the brush-shaped hybrid micelle of the embodiment comprises the following steps:
synthesis of Block copolymer PCL-b-P4VP, PCL-b-PDMA
(1) Synthesis of RAFT reagent modified PCL macroinitiator
In a nitrogen-filled glove box, dried toluene solution (2mL), caprolactone (1.728g,15.12mmol), diphenyl phosphate solution (50.4mg, 0.216mmol) and double-terminal CTA (54mg,0.216mmol) were added to a reaction flask in sequence, stirred at room temperature for 8 hours, the solution was precipitated in glacial ethyl ether three times and collected by suction filtration to obtain PCL-CTA modified by RAFT reagent, which has the following structural formula:
Figure BDA0002816488660000051
(2) synthesis of PCL-b-P4VP Block copolymer
Sequentially adding a PCL macroinitiator PCL-CTA modified by RAFT reagent, an initiator azobisisobutyronitrile, a solvent 1, 4-dioxane and a monomer 4-vinylpyridine into a reaction bottle, performing liquid nitrogen cooling, vacuumizing, nitrogen filling, vacuumizing and unfreezing for three times (not limited to three times, but four times, five times, six times and the like), and then placing the mixture in an oil bath kettle at 70 ℃ under the nitrogen atmosphere for reaction for 24 hours; after the reaction is finished, putting the polymer solution into a large amount of glacial ethyl ether for precipitation, and performing suction filtration and normal-temperature vacuum drying to obtain the PCL-b-P4VP segmented copolymer, wherein the molar ratio of the PCL macroinitiator to the 4-vinylpyridine to the azobisisobutyronitrile is 1: 400: 0.2; the structural formula of the PCL-b-P4VP block copolymer is as follows:
Figure BDA0002816488660000052
(3) synthesis of PCL-b-PDMA Block copolymer
Sequentially adding a PCL macroinitiator PCL-CTA modified by RAFT reagent, an initiator azobisisobutyronitrile, a solvent 1, 4-dioxane and a monomer N, N-dimethylacrylamide into a reaction bottle, performing liquid nitrogen cooling, vacuumizing, nitrogen filling, vacuumizing, unfreezing for three times (not limited to three times, but four times, five times, six times and the like), and then placing the mixture in an oil bath kettle at 70 ℃ under the nitrogen atmosphere for reaction for 24 hours; after the reaction is finished, putting the polymer solution into a large amount of glacial ethyl ether for precipitation, and performing suction filtration and normal-temperature vacuum drying to obtain the PCL-b-PDMA segmented copolymer, wherein the molar ratio of the PCL macroinitiator to the N, N-dimethylacrylamide to the azobisisobutyronitrile is 1: 322: 0.2; the structural formula of the PCL-b-PDMA block copolymer is as follows:
Figure BDA0002816488660000061
secondly, preparation of seed micelle solution
The PCL prepared by the method60-b-P4VP360Dissolving the segmented copolymer in absolute ethyl alcohol at the concentration of 5mg/mL, standing and heating at 70 ℃ for 3h, cooling to room temperature, and aging for 7 days to obtain polydisperse rod-shaped micelles; then the prepared polydisperse rod-shaped micelle is broken by ultrasonic wave for 20min in ice water bath at 0 ℃ by an ultrasonic cell crusher to obtain a short rod-shaped seed micelle with the length of 62nm, as shown in figure 1.
Preparation of template for anchoring seed on Carbon Nanotube (CNT)
(1) Breaking the ultrasonically disrupted PCL60-b-P4VP360Adding absolute ethyl alcohol solution into the absolute ethyl alcohol solution of the block copolymer to dilute the absolute ethyl alcohol solution to 0.1mg/mL to obtain seed solution;
(2) the seed solution was added dropwise to a 0.1mg/mL CNT suspension in the following amounts: seed micelle quality: the mass of CNT is 1: 1, then adding an absolute ethyl alcohol solution into the mixed solution to dilute the seed micelle concentration and the CNT concentration to 0.01mg/mL, and standing and aging the mixed solution at room temperature for 24 hours to obtain PCL60-b-P4VP360The template solution with the short crystals anchored to the CNTs is shown in figure 2. Wherein the mass of the seed micelle is PCL dissolved in absolute ethyl alcohol60-b-P4VP360The mass of the block copolymer.
Preparation of tetra, heteroepitaxially grown brush-like micelles
(1)PCL60-b-PDMA320Dissolving the total amount of the block copolymer in a good solvent tetrahydrofuran at a concentration of 10mg/mL to obtain a monomer solution;
(2) monomer solution in monomer mass: the mass of the seed micelle is 20: 1 is added into the template solution in a dropwise manner, and the mixture is evenly mixed and then stands and ages for 24 hours at room temperature to obtain PCL60-b-PDMA320Monomer along PCL60-b-P4VP360The grafting density of the seed for the seed epitaxial growth is 1, the single polymer feeding ratio is 20, and the brush-shaped hybrid micelle is shown in figure 3, and the length-diameter ratio is 15. Wherein the seed grafting density is seed PCL60-b-P4VP360The single polymer feeding ratio is the single polymer according to the feeding mass ratio of the CNTPCL60-b-PDMA320And seed PCL60-b-P4VP360The mass ratio of the raw materials.
Example two:
the preparation method of the brush-shaped hybrid micelle of the embodiment is different from that of the embodiment one in that:
anchoring PCL in carbon nanotubes60-b-P4VP360In the short-crystallization process, the mass of the seed micelle is as follows: CNT mass 0.5: 1.
the other steps are the same as those in the first embodiment.
This example yielded brush-like hybrid micelles with a seed graft density of 0.5 and a monomer feed ratio of 20, as shown in FIG. 4, with an aspect ratio of 2.
Example three:
the preparation method of the brush-shaped hybrid micelle of the embodiment is different from that of the embodiment one in that:
in the PCL60-b-PDMA320In the heteroepitaxial growth process of the block copolymer, the monomer mass: the mass of the seed micelle is 5: 1.
the other steps are the same as those in the first embodiment.
This example yielded brush-like hybrid micelles with a seed graft density of 1 and a monomer feed ratio of 5, as shown in FIG. 5, with an aspect ratio of 1.
Example four:
the preparation method of the brush-shaped hybrid micelle of the embodiment is different from that of the embodiment one in that:
in the PCL60-b-PDMA320In the heteroepitaxial growth process of the block copolymer, the monomer mass: the mass of the seed micelle is 10: 1.
the other steps are the same as those in the first embodiment.
This example yielded brush-like hybrid micelles with a seed graft density of 1 and a monomer feed ratio of 10, as shown in FIG. 6, with an aspect ratio of 2.
Example five:
the preparation method of the brush-shaped hybrid micelle of the embodiment is different from that of the embodiment one in that:
in the PCL60-b-PDMA320Block co-polymerizationIn the process of polymer heteroepitaxial growth, the monomer mass: the mass of the seed micelle is 15: 1.
the other steps are the same as the first embodiment;
this example yielded brush-like hybrid micelles with a seed graft density of 1 and a monomer feed ratio of 15, as shown in FIG. 7, and an aspect ratio of 3.
Example six:
the preparation method of the brush-shaped hybrid micelle of the embodiment is different from that of the embodiment one in that:
anchoring PCL in carbon nanotubes60-b-P4VP360In the short-crystallization process, the mass of the seed micelle is as follows: the mass of the CNT is 2: 1 in PCL60-b-PDMA320In the heteroepitaxial growth process of the block copolymer, the monomer mass: the mass of the seed micelle is 5: 1.
in this example, a brush-shaped hybrid micelle with a seed graft density of 2 and a monomer feed ratio of 5 was obtained, as shown in FIG. 8, and the aspect ratio was 1.5.
Example seven:
the preparation method of the brush-shaped hybrid micelle of the embodiment is different from that of the embodiment one in that:
anchoring PCL in carbon nanotubes60-b-P4VP360In the short-crystallization process, the mass of the seed micelle is as follows: the mass of the CNT is 2: 1 in PCL60-b-PDMA320In the heteroepitaxial growth process of the block copolymer, the monomer mass: the mass of the seed micelle is 10: 1.
this example yielded brush-like hybrid micelles with a seed graft density of 2 and a monomer feed ratio of 10, as shown in FIG. 9, with an aspect ratio of 4.
Example eight:
the preparation method of the brush-shaped hybrid micelle of the embodiment is different from that of the embodiment one in that:
anchoring PCL in carbon nanotubes60-b-P4VP360In the short-crystallization process, the mass of the seed micelle is as follows: the mass of the CNT is 2: 1 in PCL60-b-PDMA320In the heteroepitaxial growth process of the block copolymer, the monomer mass: the mass of the seed micelle is 15: 1.
this example yielded brush-like hybrid micelles with a seed graft density of 2 and a monomer feed ratio of 15, as shown in FIG. 10, with an aspect ratio of 10.
Example nine:
the preparation method of the brush-shaped hybrid micelle of the embodiment is different from that of the embodiment one in that:
anchoring PCL in carbon nanotubes60-b-P4VP360In the short-crystallization process, the mass of the seed micelle is as follows: the mass of the CNT is 2: 1 in PCL60-b-PDMA320In the heteroepitaxial growth process of the block copolymer, the monomer mass: the mass of the seed micelle is 20: 1.
the other steps are the same as those in the first embodiment.
This example yielded brush-like hybrid micelles with a seed graft density of 2 and a monomer feed ratio of 20, as shown in FIG. 11, with an aspect ratio of 20.
In the above examples and their alternatives, the molar ratio of macroinitiator PCL-CTA, 4-vinylpyridine, azobisisobutyronitrile was 1: 320-400: any value between 0.1 and 0.2; the molar ratio of the macroinitiator PCL-CTA, N-dimethylacrylamide and azobisisobutyronitrile is 1: 240-400: any value between 0.1 and 0.2.
In the above embodiment and the alternative, x in the structural formula of the PCL-b-P4VP block copolymer can be any integer between 320 and 400, and y can be any integer between 40 and 80.
In the above embodiment and the alternative scheme, m in the structural formula of the PCL-b-PDMA block copolymer can be an integer between 240 and 400, and n can be an integer between 40 and 80.
In the embodiment and the alternative scheme thereof, the ultrasonic time can be any value between 3-40 min.
In the embodiment and the alternative scheme, the mass ratio of the seed micelle PCL-b-P4VP to the CNT can also be 0.1-2: 1 is arbitrarily chosen.
In the embodiment and the alternative scheme, the mass ratio of the monomer PCL-b-PDMA to the seed micelles in the template solution is 0.5-20: 1, obtaining the brush-shaped hybrid micelle with gradually plump brush shape along with the increase of the mass ratio.
In the above embodiment and its alternatives, the good solvent may also be one or a combination of tetrahydrofuran, chloroform, dimethylformamide, 1, 4-dioxane, and dimethyl sulfoxide, all of which can obtain brush-like hybrid micelles with the same or similar structures.
In the above examples and alternatives, it is also possible to replace the monomer N, N-dimethylacrylamide with 2-dimethylaminoethyl methacrylate (DMAEMA) or the like and/or the homopolymer block copolymer PCL-b-PDMA with homopolymer PCL or the like. Accordingly, the block copolymers PCL-b-PDMAEMA and PCL were synthesized by reversible addition fragmentation chain transfer polymerization (RAFT), respectively. Specifically, the structural formula of the synthesized PCL block copolymer is as follows:
Figure BDA0002816488660000111
from the comparison between the above examples, it is known that the brush density and length of the brush-shaped hybrid micelle are related to the grafting density of the seed micelle on the Carbon Nanotube (CNT) and the mass ratio of the unimer to the seed micelle in the template, and the larger the grafting density of the seed micelle on the CNT is, the denser the brush structure is, and the larger the mass ratio of the unimer to the seed micelle in the template is, the larger the brush length is, and the overall brush shape is, the fuller. Different PCL block copolymers embody the same rule in the CNT-seed template epitaxial growth process, and the preparation method of the tunable brush-shaped hybrid micelle provided by the invention has certain universality and can be used for preparing brush-shaped micelles with controllable structural morphology by using various PCL block copolymers and other similar crystallizable homopolymer/block copolymer systems.
The foregoing has outlined rather broadly the preferred embodiments and principles of the present invention and it will be appreciated that those skilled in the art may devise variations of the present invention that are within the spirit and scope of the appended claims.

Claims (10)

1. The preparation method of the brush-shaped hybrid micelle is characterized by comprising the following steps of:
(1) synthesizing block copolymers PCL-b-P4VP and PCL-b-PDMA;
(2) preparation of seed micelle solution: dissolving the block copolymer PCL-b-P4VP, heating, cooling to room temperature, and aging to obtain polydisperse micelle solution; placing the micelle solution in an ice water bath for ultrasonic treatment to obtain a seed micelle solution;
(3) preparing a template of anchoring seeds on the carbon nano tube: diluting the seed micelle solution to obtain a seed solution, dripping the seed solution into the carbon nanotube suspension, uniformly mixing, diluting, and aging at room temperature to obtain a template solution containing PCL-b-P4VP short crystals anchored on the carbon nanotubes;
(4) preparation of heteroepitaxially grown brush-like micelles: adding the PCL-b-PDMA monomer dispersed in a good solvent into a template solution, uniformly mixing, and aging at room temperature to obtain the brush-shaped hybrid micelle in which the PCL-b-PDMA monomer grows along the PCL-b-P4VP short crystal epitaxy.
2. The preparation method of the brush-shaped hybrid micelle of claim 1, wherein the structural formula of the block copolymer PCL-b-P4VP is:
Figure FDA0002816488650000011
wherein x is an integer of 320-400, and y is an integer of 40-80.
3. The method for preparing brush-like hybrid micelles of claim 2, wherein x is 60.
4. The preparation method of the brush-shaped hybrid micelle according to claim 1, wherein the structural formula of the block copolymer PCL-b-PDMA is as follows:
Figure FDA0002816488650000012
wherein m is an integer of 240 to 400, and n is an integer of 40 to 80.
5. The method for preparing brush-like hybrid micelle according to claim 4, wherein m is 320 and n is 60.
6. The method for preparing brush-like hybrid micelles according to claim 1, wherein in the step (1):
the synthesis of the block copolymer PCL-b-P4VP comprises the following steps: sequentially adding RAFT polymerization macroinitiator PCL-CTA, azodiisobutyronitrile, 1, 4-dioxane and 4-vinylpyridine into a reaction bottle, performing multiple liquid nitrogen freezing-vacuumizing-nitrogen introducing-vacuumizing-unfreezing cycles, and reacting in an oil bath under the nitrogen atmosphere; after the reaction is stopped by liquid nitrogen rapid cooling, the solution is precipitated in ice-stored ether, and the segmented copolymer PCL-b-P4VP is obtained after suction filtration and vacuum drying; wherein the molar ratio of the macromolecular initiator PCL-CTA, the 4-vinylpyridine and the azobisisobutyronitrile is 1: 320-400: 0.1 to 0.2;
the synthesis of the block copolymer PCL-b-PDMA comprises the following steps: sequentially adding RAFT polymerization macroinitiator PCL-CTA, azodiisobutyronitrile, 1, 4-dioxane and N, N-dimethylacrylamide into a reaction bottle, performing multiple liquid nitrogen freezing-vacuumizing-nitrogen introducing-vacuumizing-unfreezing cycles, and placing the mixture in an oil bath for reaction under the nitrogen atmosphere; after the reaction is stopped by liquid nitrogen rapid cooling, the solution is precipitated in ice-stored ether, and the segmented copolymer PCL-b-PDMA is obtained after suction filtration and vacuum drying; the molar ratio of the macroinitiator PCL-CTA, N-dimethylacrylamide and azobisisobutyronitrile is 1: 240-400: 0.1 to 0.2.
7. The preparation method of brush-shaped hybrid micelle according to claim 1, wherein in the step (3), the mass concentration of the carbon nanotube suspension is 0.02-1 mg/mL, and the mass ratio of the seed micelle PCL-b-P4VP in the seed solution to the carbon nanotube in the carbon nanotube suspension is 0.1-2: 1.
8. the preparation method of the brush-shaped hybrid micelle according to claim 1, wherein in the step (4), the mass ratio of the monomer PCL-b-PDMA to the seed micelle in the template solution is 1-20: 1, the good solvent comprises one or more of tetrahydrofuran, trichloromethane, dimethylformamide, 1, 4-dioxane and dimethyl sulfoxide.
9. The method for preparing brush-like hybrid micelle according to claim 1, wherein the N, N-dimethylacrylamide is replaced by 2-dimethylaminoethyl methacrylate, and/or the block copolymer PCL-b-PDMA is replaced by homopolymer PCL.
10. The brush-shaped hybrid micelle prepared by the preparation method according to any one of claims 1 to 9, wherein the aspect ratio of the brush-shaped hybrid micelle is 1-20.
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