CN113292706A

CN113292706A - Fluorine-containing alternating block copolymer reverse-phase nano micelle and preparation method thereof

Info

Publication number: CN113292706A
Application number: CN202110603865.7A
Authority: CN
Inventors: 张丽芬; 王金英; 程振平; 朱秀林
Original assignee: Suzhou University
Current assignee: Suzhou University
Priority date: 2021-05-31
Filing date: 2021-05-31
Publication date: 2021-08-24
Anticipated expiration: 2041-05-31
Also published as: CN113292706B

Abstract

The invention relates to a fluorine-containing alternating block copolymer reversed-phase nano micelle and a preparation method thereof, belonging to the technical field of polymer preparation. The invention discloses a method for obtaining fluorine-containing alternating block copolymer reversed-phase nano-micelle through polymerization-induced self-assembly, which comprises the steps of initiating a hydrophilic monomer and a chain transfer agent to perform polymerization-induced self-assembly reaction in a nonpolar solvent at the temperature of 60-70 ℃ by taking azodiisobutyronitrile as an initiator and a fluorine-containing alternating copolymer macromolecular raft reagent as a chain transfer agent in a protective atmosphere. The reversed-phase nano-micelle with the fluorine-containing component outside and the hydrophilic component nucleated can be obtained by the method. The reversed-phase nano micelle prepared by the method has excellent performances such as corrosion resistance, aging resistance, heat resistance, low surface energy and the like, and the performances enable the fluorine-containing polymer to have great application prospects in the aspects of antifouling paint, hydrophobic material, surfactant and the like.

Description

Fluorine-containing alternating block copolymer reverse-phase nano micelle and preparation method thereof

Technical Field

The invention relates to the technical field of polymer preparation, in particular to a fluorine-containing alternating block copolymer reversed-phase nano micelle and a preparation method thereof.

Background

The fluorine-containing polymer is a polymer in which hydrogen atoms directly covalently bonded to carbon atoms in the main chain or side chain of an organic polymer are completely or partially substituted with fluorine atoms. Because the fluorine atom has low polarizability, strong electronegativity, small atomic radius and strong C-F bond energy, the polymer has excellent performances of corrosion resistance, aging resistance, heat resistance, low surface energy and the like after the fluorine-containing chain segment is introduced, and the performances enable the fluorine-containing polymer to have great application prospects in the aspects of antifouling paint, hydrophobic material, surfactant and the like.

Self-assembly of amphiphilic copolymers in solution can produce copolymer assemblies with tunable size and morphology, including spherical micelles, wormlike micelles, and vesicles. These copolymer assemblies are of great interest for their potential applications in drug delivery, bio-imaging, nanoreactors, cell simulation, and the like. Polymerization-induced self-assembly (PISA) has become a promising technology for conveniently fabricating copolymer components by "living"/controlled dispersion or emulsion polymerization, where synthesis and self-assembly of block copolymers occur simultaneously. Compared to conventional self-assembly schemes, PISA can produce the desired copolymer assembly by easily adjusting copolymer-related parameters, including the hydrophilic/hydrophobic ratio and copolymer concentration. Therefore, PISA has been extensively studied to understand the self-assembly mechanism of amphiphilic copolymers and to develop new drug carriers, dynamic gels, pickering emulsifiers, etc.

The polymerization-induced self-assembly of the fluorine-containing monomer has attracted attention of relevant scholars, but currently, the polymerization-induced self-assembly of the fluorine-containing monomer only stays on small-molecule fluorine-containing monomers (such as vinylidene fluoride, pentafluorostyrene and fluorine-containing acrylate small-molecule monomers).

Disclosure of Invention

In order to solve the technical problems, the invention provides a fluorine-containing alternating block copolymer reverse nano micelle and a preparation method thereof, wherein the reverse nano micelle with fluorine-containing components outside and hydrophilic components nucleated is obtained by adopting a reversible addition-fragmentation chain transfer polymerization (RAFT) method.

The invention aims to provide a fluorine-containing alternating copolymer macromolecular raft reagent, which has the structure shown in formula (1):

wherein o is 4-8; m is 3-5; n is 4-8; x is 6-10; o, n, m and x are integers.

The second purpose of the invention is to provide a preparation method of the fluorine-containing alternating copolymer macromolecular raft reagent.

Reacting a micromolecular raft reagent with a terminal double bond and the copolymer A in an organic solvent under the action of a catalyst and a photoinitiator to obtain the fluorine-containing alternating copolymer macromolecule raft reagent; wherein the structure of the small molecular raft reagent with terminal double bonds is shown as formula (2), and the structure of the copolymer A is shown as formula (3):

wherein o is 4-8; m is 3-5; n is 4-8; x is 6-10; o, n, m and x are integers.

The third purpose of the invention is to provide a method for preparing fluorine-containing alternating block copolymer reverse nano-micelle by using the fluorine-containing alternating copolymer macromolecule raft reagent, which comprises the following steps:

in a protective atmosphere, under the action of an initiator, a hydrophilic monomer and a chain transfer agent undergo polymerization-induced self-assembly reaction in a nonpolar solvent to obtain the fluorine-containing alternating block copolymer reverse nano micelle; the chain transfer agent is the fluorine-containing alternating copolymer macromolecular raft reagent.

Further, the hydrophilic monomer is acrylamide or N, N-dimethylacrylamide. Preferably, the hydrophilic monomer is N, N-dimethylacrylamide.

Further, the fluorine-containing alternating copolymer is (AB)_nObtained by polymerization of monomer A and monomer B by START; the monomer A is 1, 4-diiodoperfluorobutaneAn alkane, 1, 6-diiodoperfluorohexane or 1, 8-diiodoperfluorooctane; the monomer B is 1, 7-octadiene. Preferably, monomer A is 1, 6-diiodoperfluorohexane.

Further, the initiator is an azo initiator. Preferably, the initiator is azobisisobutyronitrile.

Further, the nonpolar solvent is toluene or acetone. Preferably, the non-polar solvent is toluene.

Further, the mole ratio of the hydrophilic monomer, the chain transfer agent and the initiator is 100-500: 1: 0.33-0.5. Preferably, the molar ratio is 100: 1: 0.33.

further, the temperature of the reaction is 60-70 ℃. Preferably, the temperature of the reaction is 70 ℃.

Further, the reaction time is 0.5-24 h. Preferably, the reaction time is 6 h.

Preferably, the hydrophilic monomer is N, N-dimethylacrylamide, and the structure of the obtained reversed-phase nano micelle is shown as a formula (5);

preferably, o is 8 in the reversed-phase nano-micelle; m is 4; n is 6; x is 7; and y is 100.

Preferably, the reaction time is 2.5-7h, and within 2.5h, the polymerization reaction is slow, the conversion rate is low, and the obtained copolymer cannot be subjected to micelle nucleation and cannot form copolymer nanoparticles. After 2.5h, the polymerization rate is accelerated, and the copolymer nano-micelle can be formed. When the reaction is carried out for 7 hours, the monomer conversion rate can reach 81.5 percent.

The fourth purpose of the invention is to provide the fluorine-containing alternating block copolymer reversed-phase nano-micelle prepared by the method.

Further, the copolymer structure in the reversed nano micelle is shown as a formula (4):

wherein o is 4-8; m is 3-5; n is 4-8; x is 6-10; y is 10-500; o, n, m, x and y are integers. Preferably, o and n are independently selected from 4,6 and 8.

R is amino or N, N-dimethyl. Preferably, R is N, N-dimethyl.

Furthermore, the particle size of the reversed-phase nano micelle is 20-200 nm.

The fifth purpose of the invention is to provide an application of the fluorine-containing alternating block copolymer reverse nano micelle in antifouling paint, hydrophobic material and surfactant.

The principle of the invention is as follows: azo initiator, fluorine-containing alternating copolymer macromolecule raft reagent as chain transfer agent, and initiating the polymerization of hydrophilic monomer at 60-70 ℃. The fluorine-containing alternating copolymer macromolecule raft agent can be well dissolved in a nonpolar solvent, the hydrophilic monomer is gradually dissolved and dissolved in the nonpolar solvent to form core along with the improvement of polymerization degree, after the core formation of micelle, the monomer is gathered in the micelle to cause the local monomer concentration to increase, the polymerization rate is obviously accelerated, and finally the stable spherical copolymer nano micelle is obtained.

Compared with the prior art, the technical scheme of the invention has the following advantages:

according to the invention, the block copolymer reversed-phase nano micelle with the fluorine-containing alternating component outside and the hydrophilic component nucleated can be obtained by polymerization-induced self-assembly by utilizing the solubility difference of the fluorine-containing alternating copolymer macromolecule raft reagent and the hydrophilic monomer. The copolymer has excellent performances of corrosion resistance, aging resistance, heat resistance, low surface energy and the like after the fluorine-containing chain segment is introduced, so that the fluorine-containing copolymer has great application prospects in the aspects of antifouling paint, hydrophobic material, surfactant and the like, and compared with micelles with the fluorine-containing components wrapped inside, reversed micelles with the fluorine-containing components outside can more fully exert the advantage of fluorine. Using the preparation method of the present invention, ln ([ M ] of monomer]₀/[M]) The molecular weight of the copolymer linearly increases along with the increase of the conversion rate, the molecular weight distribution is narrower, and the copolymer conforms to the free activityThe characteristics of the polymerization.

Drawings

In order that the present disclosure may be more readily and clearly understood, reference is now made to the following detailed description of the embodiments of the present disclosure taken in conjunction with the accompanying drawings, in which

FIG. 1 is a diagram of HPBP in example 1¹H NMR test results.

FIG. 2 is a CTA-OH of example 1¹H NMR test results.

FIG. 3 is CTA-C in example 1₂H₄Is/are as follows¹H NMR test results.

FIG. 4 shows (AB) in example 2_nIs/are as follows¹H NMR test results.

FIG. 5 shows (AB) in example 2_nA of¹H NMR test results.

FIG. 6 is a chart of the fluorine-containing alternating copolymer macromolecular raft reagent of example 2¹H NMR test results.

FIG. 7 is a kinetic graph of monomer concentration [ M ] versus reaction time for the alternating block copolymer containing fluorine of example 4.

FIG. 8 is M of the fluorine-containing alternating block copolymer of example 4_nAnd M_w/M_nCurve with conversion.

FIG. 9 is a GPC outflow curve of the fluorine-containing alternating block copolymer of example 4.

FIG. 10 is a TEM topography of assemblies of different degrees of polymerization in example 4; wherein (a-e) are respectively the topography of the assembly with the polymerization degrees of 16, 39, 63, 76 and 82; (f) is (a-e) the particle size as measured by Dynamic Light Scattering (DLS) for the assembly.

FIG. 11 is a schematic representation of the fluorine-containing alternating block copolymer of example 4¹H NMR test results.

Detailed Description

The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.

Chemical reagents used in the following examples of the invention: n, N-Dimethylacrylamide (DMA) is subjected to polymerization inhibitor removal (passing through a neutral alumina column) before use and is hermetically stored in the upper layer of a refrigerator; the azobisisobutyronitrile is recrystallized and used. Other reagents and starting materials not described were purchased and used as received.

1. Of copolymers¹HNMR spectra were obtained from a Bruker 300MHz Nuclear Magnetic Resonance (NMR) instrument. The test was carried out at room temperature (25 ℃) and was carried out at D₂O or DMSO-d₆As a deuterated reagent, Tetramethylsilane (TMS) was used as an internal standard.

2. Molecular weight (M) of the copolymer_n,GPC) And molecular weight distribution index (M)_w/M_n) Determined using a TOSOH HLC-8320 Gel Permeation Chromatograph (GPC) equipped with a differential refractive index detector (TOSOH). GPC eluting with DMF was equipped with one TSKgel guard column (SuperAW-H) and two test columns (TSKgel SuperAWM-H), and the range of measurable copolymer molecular weights was 1X 10³To 1X 10⁶g/mol. The eluent DMF contained a concentration of LiBr (0.01mol/L) at a flow rate of 0.6mL/min and was calibrated for copolymer molecular weight using linear Polystyrene (PS) from TOSOH as a standard. It has to be mentioned that DMF is not a good solvent for PS at room temperature, but we purchased PS standard solutions of different molecular weights (fully dissolved in DMF) directly from TOSOH and run the GPC instrument at 40 ℃ according to the requirements of TOSOH HLC-8320 GPC.

3. The morphology of the copolymer nanoparticles was obtained by FEI TecnaiG22 Transmission Electron Microscope (TEM) with an acceleration voltage of 120 kV. mu.L of the copolymer mixed solution was taken out into a dry clean ampoule, diluted with 4mL of toluene solvent, and then 10. mu.L of the diluted solution was pipetted onto a 200 mesh carbon-coated copper mesh. After standing for 40 seconds, the excess solvent was sucked away from the underside of the copper mesh with previously cut filter paper and finally dried at room temperature.

Example 1 Synthesis of Small molecule raft reagent with terminal double bond

(1) Synthesis of HPBP: 4.75g of hydroquinone and 100mL of anhydrous Tetrahydrofuran (THF) were sequentially charged into a 250mL three-necked flask and stirred. Then 8mL of triethylamine was added to the solution and the flask was placed in an ice water bath for precooling. Then, a 50mL constant pressure dropping funnel was connected to the flask, and 20mL of anhydrous THF and 4mL of 2-bromopropionyl bromide were sequentially added to the funnel, and the above solution was slowly added dropwise to the flask under ice bath conditions under an argon atmosphere. The reaction was carried out in ice bath for 2h and at room temperature for 12 h. After the reaction, the reaction solution was filtered with suction, the filter cake was washed with a small amount of THF, and the THF was removed from the filtrate by rotary evaporation. And (3) carrying out column chromatography on the concentrated solution after rotary evaporation by using petroleum ether/ethyl acetate (volume ratio) 4/1 as an eluent to obtain a pure intermediate HPBP. The reaction route is as follows:

FIG. 1 is of HPBP¹H NMR test results.

(2) Synthesis of CTA-OH: 3.65g of potassium ethylxanthate and 25mL of acetone were sequentially added to a 100mL three-necked flask and stirred. Then 4.00g of HPBP was dissolved in 25mL of acetone, added to a constant pressure dropping funnel, and the solution was slowly added dropwise under the protection of argon atmosphere and reacted at room temperature for 16 h. After the reaction is finished, the reaction solution is filtered, a filter cake is washed by proper amount of acetone, all filtrate is collected, and the acetone is removed by rotary evaporation. The concentrate was dissolved in 100mL of dichloromethane, poured into a 250mL separatory funnel, and then 75mL of deionized water was added and washed 3 times with water. Adding appropriate amount of anhydrous Na into organic phase₂SO₄And dried overnight. Finally filtering to remove Na₂SO₄And (3) carrying out rotary evaporation on the filtrate to remove dichloromethane, and purifying the obtained concentrated solution by column chromatography to obtain a yellow viscous liquid CTA-OH. The reaction route is as follows:

FIG. 2 is of CTA-OH¹H NMR test results.

(3) Synthesis of CTA-C₂H₄: 3.21mL of undecylenoyl chloride, 2.08mL of triethylamine, and 25mL of dichloromethane were sequentially added to a 100mL three-necked flask and stirred. 2.85g of CTA-OH was then dissolved in 20mL of dichloromethane and added to a constant pressure dropping funnel under argonSlowly adding the solution dropwise under the protection of the atmosphere, and reacting for 16h at room temperature. After the reaction, the reaction solution was filtered, a filter cake was washed with an appropriate amount of dichloromethane, and the whole filtrate was collected and poured into a 250mL separatory funnel, followed by addition of 75mL deionized water and washing with water for 3 times. Adding appropriate amount of anhydrous Na into organic phase₂SO₄And dried overnight. Finally filtering to remove Na₂SO₄The dichloromethane is removed by rotary evaporation of the filtrate, and the obtained concentrated solution is purified by column chromatography to obtain CTA-C₂H₄. The reaction route is as follows:

FIG. 3 is CTA-C₂H₄Is/are as follows¹H NMR test results.

EXAMPLE 2 Synthesis of fluorine-containing alternating copolymer macromolecular raft reagent

(1) Synthesis (AB)_n(ii) a Initial charge molar ratio [ C ]₆F₁₂I₂]₀：[C₈H₁₄]₀：[TPP⁺BF₄ ^-]₀：[AsAc-Na]₀1: 1: 0.1: 0.5, to a clean 5mL ampoule was added dodecafluoro-1, 6-diiodohexane (0.2769g), sodium ascorbate (0.0496g), 2,4, 6-tris (p-methoxyphenyl) pyran tetrafluoroborate (0.0243g), acetonitrile (1mL), dimethyl carbonate (3mL), 1, 7-octadiene (74 μ L), and a clean magnetic stir bar, respectively, and flame-sealed by three freeze-pump-argon operations. And (3) placing the ampoule bottle under the irradiation of a blue light LED, stirring, reacting for a preset time, and taking out. Adding 1-2 mL of tetrahydrofuran for dilution, and passing through a neutral alumina column to remove metal salts while precipitating in a large amount of methanol. Standing in refrigerator overnight, vacuum filtering, drying in 40 deg.C constant temperature vacuum oven, weighing to obtain fluorine-containing alternating copolymer (AB)_n. The reaction route is as follows:

FIG. 4 is (AB)_nIs/are as follows¹H NMR test results.

(2) Synthesis (AB)_nA; initial feed molar ratio [ (AB)_n]₀：[C₈F₁₇I]₀：[Ru(bpy)₃Cl₂]₀：[AsAc-Na]₀1: 10: 0.02: 0.5, Adding (AB) to a clean 5mL ampoule_n]₀、C₈F₁₇I、Ru(bpy)₃Cl₂AsAc-Na, acetonitrile, dimethyl carbonate and a clean magnetic stirrer followed by example 2 (1). The reaction route is as follows:

FIG. 5 is (AB)_nA of¹H NMR test results.

(3) Synthesizing a fluorine-containing alternating copolymer macromolecular raft reagent; initial feed molar ratio [ (AB)_nA]₀：[CTA-C₂H₄]₀：[Ru(bpy)₃Cl₂]₀：[AsAc-Na]₀1: 2: 0.02: 0.5, Adding (AB) to a clean 5mL ampoule_nA、CTA-C₂H₄、Ru(bpy)₃Cl₂AsAc-Na, acetonitrile, dimethyl carbonate and a clean magnetic stirrer followed by example 2 (1). The reaction route is as follows:

FIG. 6 is a schematic representation of a fluorine containing alternating copolymer macromolecular raft reagent¹H NMR test results.

Example 3 preparation of fluorine-containing alternating block copolymer reverse nanomicelle

Initial charge molar ratio [ macro-CTA]₀：[DMA]₀：[AIBN]₀1: 100: 0.33, to a 2mL ampoule was added macro-CTA (50mg), DMA (110. mu.L), AIBN (0.6mg), Toluene (1.0mL) and oneClean stirring bar. And (2) putting the ampoule bottle in liquid nitrogen to freeze the solution, then exhausting for 50 seconds, then unfreezing and dissolving the ampoule bottle at room temperature, simultaneously introducing argon protective gas, then refreezing, exhausting, unfreezing and inflating, and sequentially carrying out three circulation processes to remove oxygen in the ampoule bottle. After deoxidization, move the ampoule to spray gun mouth department fast and carry out flame seal pipe. Placing the ampoule bottle in a stirrer at 70 deg.C for reaction for 6h, transferring the ampoule bottle to dark place, breaking the tube, and transferring about 50 μ L of the copolymer stock solution in deuterated chloroform by using a liquid transfer gun¹H NMR measurement to calculate monomer conversion, about 100. mu.L of the copolymer stock solution was transferred by a pipette gun, dissolved in an appropriate amount of tetrahydrofuran, precipitated in petroleum ether, suction filtered, and the resulting copolymer was oven-dried at 30 ℃ to obtain 4mg of copolymer stock solution as GPC data for measurement, and about 10. mu.L of the copolymer stock solution was transferred by a pipette gun as 0.5mg/mL solution for TEM and DLS measurements.

Example 4 polymerization kinetics study of DMA

At the initial feed molar ratio [ macro-CTA ] of inventive example 3]₀：[DMA]₀：[AIBN]₀1: 100: 0.33 was taken as an example and the polymerization kinetics of DMA was examined. To a 2mL Toluene ampoule was added macro-CTA (50mg), DMA (110. mu.L), AIBN (0.6mg), Toluene (1.0mL) and a clean magnetic stirrer, the mixture was reacted at 70 ℃ for 6 hours, the ampoule was removed to the dark, the tube was broken, and 20. mu.L of the copolymer solution was removed by a pipette and dissolved in CDCl₃To carry out¹H NMR measurement, calculation of M_n,NMRAnd conversion. The results of the experiment are shown in table 1, consistent with the "living" polymerization characteristics. As can be seen from FIG. 7, in 0 to 2.5 hours, ln ([ M)]₀/[M]) The increase with time was very slow, indicating that the increase in the polymerization degree of DMA was not sufficient to achieve micelle nucleation before 2.5 hours, but after 2.5 hours ln ([ M)]₀/[M]) The growth is significantly faster with time, since the polymerization rate is significantly faster as the viscosity increases after the formation of the micelle nucleation, and the monomer is encapsulated inside the micelle, resulting in an increase in the local monomer concentration. As can be seen from FIG. 8, the molecular weight of the copolymer shows a substantially linear growth tendency with increasing conversion, and the molecular weight distribution is also narrower. Beginning of the reactionThe incomplete opening of the chain transfer agent results in a large deviation of the actual molecular weight from the theoretical molecular weight, the closer the GPC molecular weight is to the theoretical molecular weight as the reaction proceeds. As can be seen from FIG. 9, the change in molecular weight of the copolymer from a longer run-out time to a shorter run-out time indicates a process in which the molecular weight of the copolymer increases from small to large. The kinetics of polymerization showed that the alternating copolymer (AB) containing fluorine was produced using azobisisobutyronitrile as initiator_nThe macromolecular raft reagent is a chain transfer agent, and the polymerization of N, N-dimethylacrylamide is initiated under the condition of 70 ℃ to meet the characteristic of 'active' polymerization.

TABLE 1 kinetics study of the polymerization of DMA

FIG. 10 is a graph of the morphology of the assemblies at different degrees of polymerization in Table 1, as observed by TEM. In FIGS. 10(a-e), the morphology of the assemblies at polymerization degrees of 16, 39, 63, 76, and 82, respectively, shows that the micelle diameter increases with the increase in polymerization degree, and the micelles are spherical. FIG. 10(f) is a measurement of DLS particle size for the assemblies of FIG. 10 (a-e). The micelle is relatively stretched in a solvent during DLS test, so that the particle size measured by the dry micelle is larger compared with that measured by a TEM, and the trend of increasing the particle size along with the increase of the polymerization degree is consistent. Due to the insufficient proportion of hydrophilic segments, higher order morphologies cannot be formed. FIG. 11 is a drawing of a copolymer¹HNMR test chart proves the successful obtaining of the amphiphilic block copolymer.

In conclusion, the invention utilizes the solubility difference of the fluorine-containing alternating copolymer macromolecule raft reagent and the hydrophilic monomer, and obtains the block copolymer reverse-phase nano micelle with the fluorine-containing alternating component outside and the hydrophilic component nucleated by polymerization-induced self-assembly.

It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims

1. A fluorine-containing alternating copolymer macromolecule raft reagent is characterized in that the structure is shown as formula (1):

wherein o is 4-8; m is 3-5; n is 4-8; x is 6-10; o, n, m and x are integers.

2. A method for preparing a fluorine-containing alternating copolymer macromolecular raft reagent as recited in claim 1, comprising the steps of:

wherein o is 4-8; m is 3-5; n is 4-8; x is 6-10; o, n, m and x are integers.

3. A preparation method of fluorine-containing alternating block copolymer reversed-phase nano-micelle is characterized by comprising the following steps:

in a protective atmosphere, under the action of an initiator, a hydrophilic monomer and a chain transfer agent undergo polymerization-induced self-assembly reaction in a nonpolar solvent to obtain the fluorine-containing alternating block copolymer reverse nano micelle; the chain transfer agent is the fluorine-containing alternating copolymer macromolecular raft reagent of claim 1.

4. The method for preparing fluorine-containing alternating block copolymer reversed-phase nanomicelle according to claim 3, characterized in that: the hydrophilic monomer is acrylamide or N, N-dimethylacrylamide.

5. The method for preparing fluorine-containing alternating block copolymer reversed-phase nanomicelle according to claim 3, characterized in that: the initiator is an azo initiator.

6. The method for preparing fluorine-containing alternating block copolymer reversed-phase nanomicelle according to claim 3, characterized in that: the nonpolar solvent is toluene or acetone.

7. The method for preparing fluorine-containing alternating block copolymer reversed-phase nanomicelle according to claim 3, characterized in that: the molar ratio of the hydrophilic monomer, the chain transfer agent and the initiator is 100-500: 1: 0.33-0.5.

8. The method for preparing fluorine-containing alternating block copolymer reversed-phase nanomicelle according to claim 3, characterized in that: the temperature of the reaction is 60-70 ℃.

9. The fluorine-containing alternating block copolymer reversed nanomicelle prepared by the method of any one of claims 3 to 8, wherein the copolymer structure in the reversed nanomicelle is represented by the formula (4):

wherein o is 4-8; m is 3-5; n is 4-8; x is 6-10; y is 10-500; o, n, m, x and y are integers;

r is amino or N, N-dimethyl.

10. The fluorine-containing alternating block copolymer reverse nano-micelle of claim 9 is applied to antifouling paint, hydrophobic material and surfactant.