阅读说明：本技术 一种单分子链纳米颗粒的制备方法和应用 (Preparation method and application of single molecular chain nano-particles ) 是由 邱东 王嘉玮 于 2020-04-30 设计创作，主要内容包括：本发明介绍了一种大批量制备具有普适性的单分子链纳米颗粒的方法。所述单分子链纳米颗粒为使用活性阳离子聚合制备聚合物链后,用静电保护的方法对聚合物进行分子内交联得到。所述单分子链纳米颗粒可以具有球状、蝌蚪状、链-球-链状、哑铃状等多种形貌,从而普适性地调节纳米颗粒的形貌。所述单分子链纳米颗粒的交联微区内含有大量反应性官能团,可以用于生长无机非金属、金属或金属氧化物；可以用于接枝自由基引发剂,得到大分子引发剂后引发多种带有乙烯双键的单体,从而普适性地调节纳米颗粒的组成和功能。各步聚合反应转化率完全,对后续步骤无干扰,产物分离简单快速,过程简单并可大批量操作,可制备组成普适可调的单分子链纳米颗粒及其复合材料。(The invention discloses a method for preparing single molecular chain nano particles with universality in a large scale. The single-molecular-chain nano-particles are obtained by using an electrostatic protection method to carry out intramolecular cross-linking on a polymer after a polymer chain is prepared by using active cationic polymerization. The single molecular chain nano-particles can have various shapes such as spheres, tadpoles, chain-sphere-chain shapes, dumbbell shapes and the like, so that the shapes of the nano-particles can be universally adjusted. The cross-linking micro-region of the single molecular chain nano-particle contains a large amount of reactive functional groups and can be used for growing inorganic nonmetal, metal or metal oxide; can be used for grafting a free radical initiator to obtain a macromolecular initiator and then initiate various monomers with ethylene double bonds, thereby adjusting the composition and the function of the nano particles universally. The polymerization reaction conversion rate in each step is complete, no interference is caused to the subsequent steps, the product separation is simple and rapid, the process is simple and can be operated in large batch, and the universal and adjustable single molecular chain nano particles and the composite material thereof can be prepared.)

1. A preparation method of single molecular chain nano-particles comprises the following steps:

step A1) synthesizing a polymer having a crosslinkable living segment using a living cationic polymerization method;

step A2) introducing charges into the cross-linked active segments in the polymer;

step A3) carrying out intramolecular crosslinking on the crosslinking active chain segment in the polymer to obtain a single-chain nanoparticle precursor;

step A4) inducing the growth of inorganic matters by using the single-chain nano-particle precursor to obtain single-chain nano-particles compounded with the inorganic matters;

or, a free radical initiator is introduced into the single-chain nanoparticle precursor through further reaction to obtain a single-chain nanoparticle macroinitiator, and the monomer is initiated to polymerize to obtain the single-chain nanoparticle grafted with the polymer.

2. The method according to claim 1, wherein the polymer of step a1) is selected from homopolymers or block copolymers having a crosslinkable living segment;

preferably, the cross-linked active segment of step a1) is selected from at least one of polystyrene, poly-alpha-methylstyrene, poly-p-methylstyrene, poly-benzyl chlorostyrene, polyacrylate based styrene, poly-chloroethyl vinyl ether, poly-phenyl vinyl ether, poly-benzyl chloroethyl vinyl ether, polyacrylate based vinyl ether, poly-epichlorohydrin, poly-phenyl ethylene oxide, polycaprolactone;

preferably, an initiator may be added in step A1), and the initiator may be selected from boron trifluoride, aluminum trichloride, zinc dichloride, titanium tetrachloride, tin tetrachloride, antimony trichloride, chromium tetrachloride, ferric trichloride, alkyl aluminum chloride, trifluoromethanesulfonic acid, HCl, HI/I₂，HI/ZnI₂，HI/ZnBr₂，AlEt₂Cl，EtAlCl₂At least one of/EtOAc; tin tetrachloride and boron trifluoride are preferred;

preferably, the step a1) may be performed in a solvent, which may be selected from at least one of methyl chloride, methylene chloride, chloroform, ethyl chloride, 1, 2-dichloroethane, benzene, toluene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, nitromethane, nitroethane, nitrobenzene, carbon tetrachloride; preferably dichloromethane, trichloromethane and toluene;

preferably, the living cationic polymerizable monomer of step a1) may be selected from at least one of n-Butyl Vinyl Ether (BVE), isobutyl vinyl ether (IBVE), Chloroethyl Vinyl Ether (CVE), methylphenyl vinyl ether (MSVE), benzyl chloride vinyl ether, vinyl ether styrene, vinyl ether alkyl ethylene, vinyl ether acrylate, vinyloxyethoxy benzyl benzoate (BBzVE), styrene (St), p-Methyl Styrene (MS), alpha-methyl styrene, chloromethyl styrene, styrene acrylate.

3. The method according to claim 1, wherein the step a1) further comprises reacting the resulting polymer under acid catalysis to obtain a reactive functional group;

the acid can be at least one of trifluoroacetic acid, acetic acid and formic acid;

the reactive functional group may be carboxyl, fluoro, chloro, bromo or iodo.

4. The preparation method according to claim 1, wherein the charge is introduced in step a2) by adding an imidazole compound or a pyridine compound in the reaction, wherein the imidazole compound may be at least one of methylimidazole, ethylimidazole and 1, 2-dimethylimidazole; the pyridine compound can be at least one of 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 3-ethylpyridine and 2, 4-dimethylpyridine;

preferably, the step a2) may be performed in a solvent, and the solvent may be selected from at least one of N, N-dimethylformamide, methyl chloride, methylene chloride, chloroform, ethyl chloride, 1, 2-dichloroethane, benzene, toluene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, nitromethane, nitroethane, nitrobenzene, carbon tetrachloride;

preferably, the intramolecular crosslinking in the step a3) may be performed by adding a bifunctional crosslinking agent in the reaction, wherein the bifunctional crosslinking agent may be at least one of hexamethylene diisocyanate, 2-bipyridine and 4, 4-bipyridine;

preferably, the step a3) may be performed in a solvent, and the solvent may be at least one selected from N, N-dimethylformamide, methyl chloride, methylene chloride, chloroform, ethyl chloride, 1, 2-dichloroethane, benzene, toluene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, nitromethane, nitroethane, nitrobenzene, carbon tetrachloride.

5. The method according to claim 1, wherein the inorganic material in step a4) is selected from inorganic nonmetal, metal or metal oxide;

preferably, the inorganic nonmetal may be selected from silicon dioxide (SiO)₂)；

Preferably, the metal may be at least one selected from gold (Au), silver (Ag), platinum (Pt), palladium (Pd), iron (Fe), cobalt (Co), nickel (Ni), tin (Sn), indium (In), and alloys thereof;

preferably, the metal oxide may be selected from the group consisting of iron oxide (Fe)₃O₄) Titanium dioxide (TiO)₂) Aluminum oxide (Al)₂O₃) Barium titanate (BaTiO)₃) Strontium titanate (SrTiO)₃) At least one of (1).

Preferably, the further reaction described in step a4) may be selected from amidation or aminolysis;

preferably, the amidation reaction may be performed by adding a condensing agent, and the condensing agent may be at least one selected from Dicyclohexylcarbodiimide (DCC), 2- (7-azabenzotriazole) -N, N' -tetramethylurea Hexafluorophosphate (HATU), and 1-Hydroxybenzotriazole (HOBT);

preferably, the amidation reaction may be carried out by adding a compound capable of forming an active ester with a carboxylic acid, for example, N-hydroxysuccinimide (NHS);

preferably, a basic catalyst may be added to the ammonolysis reaction, and may be, for example, Triethylamine (TEA);

preferably, the radical initiator in step a4) may be selected from azobisisobutyramidine hydrochloride (AIBA);

preferably, the monomer in step a4) may be an ethylene-based monomer; the vinyl monomer may be selected from n-Butyl Vinyl Ether (BVE), isobutyl vinyl ether (IBVE), Chloroethyl Vinyl Ether (CVE), methylphenyl vinyl ether (MSVE), benzyl chloride vinyl ether, vinyl ether styrene, vinyl ether alkyl ethylene, vinyl ether acrylate, styrene (St), p-Methyl Styrene (MS), alpha-methyl styrene, chloromethyl styrene (VBC), styrene acrylate, p-cyanate styrene, styrene formaldehyde, isoprene, Isobutylene (IB), butadiene, cyclo-conjugated diene, methyl (meth) acrylate (MMA), ethyl (meth) acrylate, n-butyl (meth) acrylate (BA), tert-butyl (meth) acrylate (tBA), methacryloxypropyl trimethoxysilane (KH570), p-cyanate (meth) acrylate, At least one of oligo ethylene glycol (meth) acrylate (OEGMA), N-isopropylacrylamide (NIPAM), dimethyl aminomethyl methacrylate (DMAEMA), dimethyl aminoethyl methacrylate (DEAEMA), and (meth) acrylonitrile.

6. The method for preparing nanoparticles of claim 1, wherein the method for preparing nanoparticles of single molecular chain comprises the following steps:

step a1) adding stannic chloride and vinyloxyethoxy benzyl benzoate into dichloromethane, carrying out polymerization reaction to obtain vinyloxyethoxy benzyl benzoate (PBBzVE), and hydrolyzing the polyvinyloxyethoxy benzyl benzoate (PBBzVE) to obtain the vinyloxyethoxy benzoic acid (PBzVE);

step a2) reacting PBzVE with 1-methylimidazole to introduce charges into the PBzVE;

step a3) adding hexamethylene diisocyanate into the solution obtained in step a2) under the condition of electrostatic protection, and carrying out intramolecular crosslinking reaction on the PBzVE chain to obtain a cPBzVE single-chain nanoparticle precursor;

step a4) inducing the growth of inorganic nonmetal, metal or metal oxide by using a cPBzVE single-chain nano-particle precursor to obtain single-chain nano-particles compounded with inorganic matters;

or reacting the cPBzVE single-chain nanoparticle precursor with dicyclohexylcarbodiimide and N-hydroxysuccinimide, adding azodiisobutyl amidine hydrochloride, introducing a free radical initiator AIBA into the cPBzVE single-chain nanoparticle precursor to obtain the cPBzVE @ AIBA single-chain nanoparticle macroinitiator, and initiating polymerization of various ethylene monomers to obtain the single-chain nanoparticle grafted with the polymer.

7. The method of claim 6, wherein the molecular weight of the PBzVE in step a1) is between 2k and 100k, preferably between 4k and 50 k;

preferably, the temperature of the polymerization reaction of step a1) may be-50 ℃ to 30 ℃; preferably-20 ℃ to 10 ℃;

preferably, the concentration of vinyloxyethoxybenzoic acid benzyl ester in step a1) is 1-40%, preferably 5-30%;

preferably, the overall solids content of the PbzVE polymer after charge introduction in step a2) is in the range of 1-40%, preferably 5-30%;

preferably, the crosslinking reaction temperature of step a3) may be-100 ℃ to 50 ℃; preferably-50 ℃ to 30 ℃;

preferably, the crosslinking reaction time of step a3) may be 1 to 24 hours, preferably 5 to 12 hours;

preferably, the temperature of the reaction in step a4) may be from 0 ℃ to 120 ℃, preferably from 20 ℃ to 90 ℃, for example from 50 ℃ to 70 ℃;

preferably, the reaction time in step a4) may be from 1min to 24h, preferably from 1 to 8 h;

preferably, the temperature of the amidation reaction in step a4) may be-50 ℃ to 100 ℃, preferably-20 ℃ to 50 ℃;

preferably, the amidation reaction time in step a4) may be 1 to 24h, preferably 5 to 12 h.

8. Single-molecular-chain nanoparticles prepared by the preparation method of any one of claims 1 to 7;

preferably, the single-chain nanoparticles comprise various morphologies and compositions, including spherical single-chain nanoparticles, tadpole-shaped single-chain nanoparticles, chain-sphere-chain single-chain nanoparticles, dumbbell-shaped single-chain nanoparticles, and the like; different micro-regions of the single-chain nano-particles are provided with different functional groups.

9. A nanomaterial comprising the single-molecular-chain nanoparticle of claim 8.

10. Use of the preparation method of any one of claims 1 to 7 for the preparation of single-stranded nanoparticles or nanomaterials.

Technical Field

The invention relates to the technical field of inorganic, organic and polymer science and materials, in particular to a preparation method and application of single molecular chain nano particles.

Background

The single molecular chain technology is a brand new technology reflecting the capability of constructing a nanometer soft substance on the level of the single molecular chain. The single molecular chain nano-particles with micro-scale have great advantages in the aspects of synthesizing single molecular reactors and the like due to the characteristics of strong autonomy and the like. One of the most important driving forces for the design of single-stranded nanoparticles is the simulation of biomacromolecular materials and the design of naturally inspired chemical reaction sequences (Anfinsen C. science,1973,181(4096): 223-. By selecting different nano particles and polymer chains, the appearance and performance of the nano particles can be adjusted as required. Therefore, it is very important to precisely design single-chain nanoparticles and develop a new batch preparation method. The currently widely used synthetic single-chain nanoparticles mainly employ the method of intramolecular cross-linking a specific segment of a block polymer (Malvia, Eivgi, Berkovich, Lemcoff. chem. Rev.2016, 116: 878-. However, this method has certain disadvantages, and can be realized only in a solution with a very low solid content (less than or equal to 1%), otherwise, intermolecular crosslinking occurs to generate a gel phenomenon, which results in failure of preparing the composite structure. At present, although studies have shown that crosslinking can be achieved in a highly concentrated solution, the composition of single-molecular-chain nanoparticles obtained by this method is generally limited to a specific range. To produce functionality, the composition of the nanoparticles needs to be universally adjusted. In addition, the limited polymer architecture and composition options affect the microstructural design of single-stranded nanoparticles. The two aspects severely limit the wide application of the materials. Therefore, designing single-chain nanoparticles that can be synthesized in large quantities and adjusting their compositions universally are currently an urgent problem to be solved.

Disclosure of Invention

The invention relates to the technical field of polymer science and materials, in particular to single molecular chain nano-particles with various shapes and a large-batch universal preparation method.

In order to improve the technical problem, the invention also provides a preparation method of the single-chain nano-particles, which comprises the following steps:

step A1) synthesizing a polymer with a cross-linked active chain segment by using a living cationic polymerization method;

step A2) introducing charges into the cross-linked active segments in the polymer;

step A3) carrying out intramolecular crosslinking on the crosslinking active chain segment in the polymer to obtain a single-chain nanoparticle precursor;

step A4) inducing the growth of inorganic matters by using the single-chain nano-particle precursor to obtain single-chain nano-particles compounded with the inorganic matters;

or, a free radical initiator is introduced into the single-chain nanoparticle precursor through further reaction to obtain a single-chain nanoparticle macroinitiator, and the monomer is initiated to polymerize to obtain the single-chain nanoparticle grafted with the polymer.

According to an embodiment of the present invention, the polymer of step a1) is selected from homopolymers or block copolymers having a crosslinkable living segment;

according to an embodiment of the present invention, the cross-linked active segment of step a1) is selected from at least one of polystyrene, poly-alpha-methylstyrene, poly-p-methylstyrene, poly-benzyl chlorostyrene, polyacrylate styrene, poly-chloroethyl vinyl ether, poly-phenyl vinyl ether, poly-benzyl chloroethyl vinyl ether, polyacrylate vinyl ether, poly-epichlorohydrin, poly-phenyl ethylene oxide, polycaprolactone.

According to an embodiment of the invention, in step A1) an initiator may be added, said initiator being selected from boron trifluoride, aluminium trichloride, zinc dichloride, titanium tetrachloride, tin tetrachloride, antimony trichloride, chromium tetrachloride, ferric trichloride, alkylaluminium chloride, trifluoromethylsulfonic acid, HCl, HI/I₂，HI/ZnI₂，HI/ZnBr₂，AlEt₂Cl，EtAlCl₂At least one of/EtOAc; preference is given to tetrachloroTin, boron trifluoride.

According to an embodiment of the present invention, step a1) may be performed in a solvent, which may be selected from at least one of methyl chloride, methylene chloride, chloroform, ethyl chloride, 1, 2-dichloroethane, benzene, toluene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, nitromethane, nitroethane, nitrobenzene, carbon tetrachloride; preferably dichloromethane, chloroform or toluene.

According to an embodiment of the present invention, the living cationic polymerizable monomer of step a1) may be selected from at least one of n-Butyl Vinyl Ether (BVE), isobutyl vinyl ether (IBVE), Chloroethyl Vinyl Ether (CVE), methylphenyl vinyl ether (MSVE), benzyl chloride vinyl ether, vinyl ether styrene, vinyl ether alkyl ethylene, vinyl ether acrylate, vinyloxyethoxy benzyl benzoate (BBzVE), styrene (St), p-Methyl Styrene (MS), alpha-methyl styrene, chloromethyl styrene, styrene acrylate.

According to an embodiment of the invention, step a1) further comprises reacting the resulting polymer further under acid catalysis to yield reactive functional groups; the acid can be at least one of trifluoroacetic acid, acetic acid and formic acid; the reactive functional group may be carboxyl, fluoro, chloro, bromo or iodo.

According to an embodiment of the present invention, the charge introduced in step a2) may be introduced by adding an imidazole compound or a pyridine compound in the reaction, where the imidazole compound may be at least one of methylimidazole, ethylimidazole and 1, 2-dimethylimidazole; the pyridine compound can be at least one of 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 3-ethylpyridine and 2, 4-dimethylpyridine.

According to an embodiment of the present invention, step a2) may be performed in a solvent, which may be selected from at least one of N, N-dimethylformamide, methyl chloride, methylene chloride, chloroform, ethyl chloride, 1, 2-dichloroethane, benzene, toluene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, nitromethane, nitroethane, nitrobenzene, carbon tetrachloride; n, N-dimethylformamide is preferred.

According to an embodiment of the present invention, the intramolecular cross-linking in step a3) may be performed by adding a bifunctional cross-linking agent during the reaction, and the bifunctional cross-linking agent may be at least one of hexamethylene diisocyanate, 2-bipyridine and 4, 4-bipyridine.

According to an embodiment of the present invention, step a3) may be performed in a solvent, which may be selected from at least one of N, N-dimethylformamide, methyl chloride, methylene chloride, chloroform, ethyl chloride, 1, 2-dichloroethane, benzene, toluene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, nitromethane, nitroethane, nitrobenzene, carbon tetrachloride; n, N-dimethylformamide is preferred.

According to an embodiment of the present invention, the inorganic substance described in step a4) may be selected from inorganic non-metals, metals or metal oxides;

the inorganic nonmetal may be selected from silicon dioxide (SiO)₂)；

The metal may be at least one selected from gold (Au), silver (Ag), platinum (Pt), palladium (Pd), iron (Fe), cobalt (Co), nickel (Ni), tin (Sn), indium (In), and alloys thereof;

the metal oxide may be selected from the group consisting of iron oxide (Fe)₃O₄) Titanium dioxide (TiO)₂) Aluminum oxide (Al)₂O₃) Barium titanate (BaTiO)₃) Strontium titanate (SrTiO)₃) At least one of (1).

According to an embodiment of the present invention, the further reaction described in step a4) may be selected from amidation or aminolysis;

the amidation reaction may be carried out by adding a condensing agent; the condensing agent may be at least one selected from Dicyclohexylcarbodiimide (DCC), 2- (7-azabenzotriazole) -N, N' -tetramethylurea Hexafluorophosphate (HATU), and 1-Hydroxybenzotriazole (HOBT);

the amidation reaction may be carried out by adding a compound capable of forming an active ester with a carboxylic acid, for example, N-hydroxysuccinimide (NHS);

the ammonolysis reaction may be carried out with the addition of a basic catalyst, which may be triethylamine, for example.

According to an embodiment of the present invention, the radical initiator in step a4) may be selected from azobisisobutyramidine hydrochloride (AIBA); according to an embodiment of the present invention, the monomer in step a4) may be an ethylene-based monomer; the vinyl monomer may be selected from n-Butyl Vinyl Ether (BVE), isobutyl vinyl ether (IBVE), Chloroethyl Vinyl Ether (CVE), methylphenyl vinyl ether (MSVE), benzyl chloride vinyl ether, vinyl ether styrene, vinyl ether alkyl ethylene, vinyl ether acrylate, styrene (St), p-Methyl Styrene (MS), alpha-methyl styrene, chloromethyl styrene (VBC), styrene acrylate, p-cyanate styrene, styrene formaldehyde, isoprene, Isobutylene (IB), butadiene, cyclo-conjugated diene, methyl (meth) acrylate (MMA), ethyl (meth) acrylate, n-butyl (meth) acrylate (BA), tert-butyl (meth) acrylate (tBA), methacryloxypropyl trimethoxysilane (KH570), p-cyanate (meth) acrylate, At least one of oligo ethylene glycol (meth) acrylate (OEGMA), N-isopropylacrylamide (NIPAM), dimethyl aminomethyl methacrylate (DMAEMA), dimethyl aminoethyl methacrylate (DEAEMA), and (meth) acrylonitrile.

According to an embodiment of the present invention, the method for preparing single-molecular-chain nanoparticles comprises the following steps:

step a1) adding stannic chloride and vinyloxyethoxy benzyl benzoate into dichloromethane, carrying out polymerization reaction to obtain vinyloxyethoxy benzyl benzoate (PBBzVE), and hydrolyzing the polyvinyloxyethoxy benzyl benzoate (PBBzVE) to obtain the vinyloxyethoxy benzoic acid (PBzVE);

step a2) reacting PBzVE with 1-methylimidazole to introduce charges into the PBzVE;

step a3) adding hexamethylene diisocyanate into the solution obtained in step a2) under the condition of electrostatic protection, and carrying out intramolecular crosslinking reaction on the PBzVE chain to obtain a cPBzVE single-chain nanoparticle precursor;

step a4) inducing the growth of inorganic nonmetal, metal or metal oxide by using a cPBzVE single-chain nano-particle precursor to obtain single-chain nano-particles compounded with inorganic matters;

or reacting the cPBzVE single-chain nanoparticle precursor with dicyclohexylcarbodiimide and N-hydroxysuccinimide, adding azodiisobutyl amidine hydrochloride, introducing a free radical initiator AIBA into the cPBzVE single-chain nanoparticle precursor to obtain the cPBzVE @ AIBA single-chain nanoparticle macroinitiator, and initiating polymerization of an ethylene monomer to obtain the single-chain nanoparticle grafted with the polymer.

According to an embodiment of the invention, said PBzVE in step a1) has a molecular weight in the range of 2k to 100k, preferably 4k to 50 k;

according to an embodiment of the present invention, the temperature of the polymerization reaction of step a1) may be-50 ℃ to 30 ℃; preferably-20 ℃ to 10 ℃.

According to an embodiment of the invention, the concentration of vinyloxyethoxybenzoic acid benzyl ester of step a1) is 1-40%, preferably 5-30%.

According to an embodiment of the invention, the PbzVE polymer after charge introduction in step a2) has an overall solids content of 1-40%, preferably 5-30%.

According to an embodiment of the present invention, the crosslinking reaction temperature of step a3) may be-100 ℃ to 50 ℃; preferably-50 ℃ to 30 ℃.

According to an embodiment of the present invention, the time of the crosslinking reaction in step a3) may be 1 to 24 hours, preferably 5 to 12 hours.

According to an embodiment of the invention, the temperature of the reaction in step a4) may be in the range of 0 ℃ to 120 ℃, preferably 20 ℃ to 90 ℃, for example 50 ℃ to 70 ℃.

According to an embodiment of the present invention, the time of the reaction in step a4) may be in the range of 1min to 24h, preferably 1 to 8 h.

According to an embodiment of the invention, the temperature of the amidation reaction in step a4) may be between-50 ℃ and 100 ℃, preferably between-20 ℃ and 50 ℃, exemplary 25 ℃;

according to an embodiment of the present invention, the time of the amidation reaction described in step a4) may be 1 to 24h, preferably 5 to 12h, exemplarily 12 h.

The invention also provides the single-chain nano-particles or the composite single-chain nano-particles prepared by the preparation method.

According to embodiments of the present invention, the single-chain nanoparticles comprise a variety of morphologies and compositions, including spherical single-chain nanoparticles, tadpole-like single-chain nanoparticles, chain-sphere-chain single-chain nanoparticles, dumbbell-like single-chain nanoparticles, and the like; different micro-regions of the single-chain nano-particles are provided with different functional groups.

The invention also provides a nano material, which comprises the single-chain nano particle or the composite single-chain nano particle.

The invention also provides application of the preparation method in preparation of the single-chain nano-particles or the nano-materials.

Advantageous effects

The invention provides a method for preparing single molecular chain nano particles, which is simple in reaction and abundant and easily available in raw materials. The polymer with functional blocks can be obtained through active cationic polymerization, the obtained functional micro-region can react with various monomers, inorganic nonmetal, metal or metal oxide to obtain various single-chain nano-particles, and the single-chain nano-particles with universality can be prepared in large batch. The prepared single molecular chain nano-particles are further modified to obtain the multifunctional composite nano-material, and the multifunctional composite nano-material has important significance in the fields of composite material high performance, catalysis, oil-water separation, environmental response, drug controlled release, catalyst carriers and the like.

Drawings

FIG. 1 transmission electron micrograph of cPBzVE single-stranded nanoparticles.

FIG. 2 cPBzVE @ Fe₃O₄Transmission electron microscopy of magnetic composite single-stranded nanoparticles.

FIG. 3 transmission electron micrograph of cPBzVE @ AIBA single-stranded nanoparticles.

FIG. 4 transmission electron micrograph of cPVBC @ AIBA single stranded nanoparticles.

Detailed Description

The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.

Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.

The monomer vinyloxyethoxybenzoic acid benzyl ester (BBzVE) used in the following examples was prepared as follows:

step 1) A100 mL round-bottom flask was charged with 1.4mL CVE, 3.9g potassium carbonate, and 2.7g benzyl 4-hydroxybenzoate, 20mL chromatographically pure DMF, and the reaction stirred at 80 ℃ for 8 h.

Step 2) removing solid matters in the product by using a neutral alumina chromatographic column, and removing the solvent by rotary evaporation.

Step 3), preparing n-hexane: the product was purified by silica gel column chromatography using a solvent mixture of ethyl acetate 5:1 as eluent to give pure BBzVE. The monomer is put into a refrigerator with the temperature of minus 30 ℃ in a glove box for standby after being deoxidized. The hydrogen nuclear magnetic resonance spectrum shows the successful synthesis of the monomer BBzVE.

Example 1

15.0. mu.L of stannic chloride was added to 10.0mL of ultra dry methylene chloride, stirred and cooled to-15 ℃. A solution of BBzVE in methylene chloride (0.4g/mL,5mL) was slowly added dropwise thereto, and the reaction was terminated by adding methanol after 30min of reaction. The PBBzVE polymer chain is obtained.

1.0g of the synthetically obtained PBBzVE was dissolved in 20.0mL of chromatographically pure DMF. 1.2mL of trifluoroacetic acid and 0.6mL of secondary water were added and stirred overnight. The obtained solution is concentrated by rotary evaporation and then dropped into excessive methanol for precipitation. The precipitate was dried in vacuo to give a polyethyleneoxy ethoxybenzoic acid (PBzVE) chain.

PBzVE was dissolved in ultra dry DMF solvent to make a 50mg/mL solution. Methylimidazole (MI, molar ratio of MI to benzoic acid unit 0.5:1.0) was added and the reaction was stirred at 25 ℃ for 24 h.

Hexamethylene diisocyanate (HDI, molar ratio of HDI to benzoic acid units 0.2:1.0) was added to the solution, and the reaction was stirred at 25 ℃ for 24 hours. After the reaction was completed, the solution was transferred to a dialysis bag (cut-off of 3.5kDa) and dialyzed at 55 ℃ for 24 hours to remove MI. After dialysis, the system was freeze-dried to obtain cPBzVE single-chain nanoparticles, and the transmission electron microscopy image of the stained cPBzVE single-chain nanoparticles is shown in fig. 1.

And dissolving the prepared cPBzVE single-chain nano-particles in an ultra-dry DMF solvent to prepare a solution of 2.0 mg/mL. 5.0mL of the solution was added to a polymerization tube and FeCl was added₃·6H₂DMF solution of O (370.0. mu.L, 50.0mg/mL) and FeSO₄·7H₂DMF solution of O (370.0 μ L, 50.0mg/mL), subjecting the reaction solution to freeze-pump-thaw cycle three times using double calandria, sealing the reaction tube under vacuum, stirring for 2h to fully load iron ions on the carboxyl functional groups, and adding 2mL ammonia water at 50 ℃ to co-precipitate iron ions to obtain Fe₃O₄And (4) crystals. Stirring for 30min, heating to 80 deg.C, reacting for 2h, and performing Fe₃O₄And (4) aging the crystals. After the reaction was completed, the system was cooled to room temperature to terminate the reaction, and the system was centrifuged at 1000rpm at a low speed to remove large particles of Fe₃O₄And (4) crystals. The particles in the centrifuged supernatant were collected using a magnet (0.2T) and dried under vacuum at 25 ℃ to give cPBzVE @ Fe₃O₄Magnetic composite single-stranded nanoparticles. It was characterized using transmission electron microscopy, as shown in FIG. 2.

Example 2

Dicyclohexylcarbodiimide (DCC, molar ratio of DCC to benzoic acid unit in the range of 0.4:1.0) was added to the solution of cPBzVE single-chain nanoparticles obtained above, and after stirring for 20min, N-hydroxysuccinimide (NHS, molar ratio of NHS to DCC of 0.5:1.0) was added, followed by stirring at 25 ℃ overnight to activate carboxyl groups. Azobisisobutyramidine hydrochloride (AIBA, molar ratio of AIBA to DCC 0.25:1.0) was then added to the solution and stirred at 25 ℃ for 12 h. After the reaction was complete, the solution was transferred to a dialysis bag and dialyzed for 24h to remove DCC and NHS. And (4) after dialysis, freezing and drying the system to obtain the cPBzVE @ AIBA single-chain nano-particles. And dissolving the prepared cPBzVE @ AIBA single-chain nano-particles in an ultra-dry DMF solvent to prepare a solution of 2.0 mg/mL. The granules were characterized using transmission electron microscopy after phosphotungstic acid staining and the results are shown in figure 3.

And dissolving the prepared cPBzVE @ AIBA single-chain nano-particles in an ultra-dry DMF solvent to prepare a solution of 2.0 mg/mL. 5.0mL of the above solution was put into a polymerization tube and 200mg of NIPAM was added, the reaction solution was subjected to freeze-pump-thaw cycle three times using a double-row tube, the reaction tube was sealed under vacuum, and heated at 80 ℃ for reaction for 8 hours. After the reaction was complete, the system was cooled to room temperature to terminate the reaction, and dropped into cold ether to precipitate cPBzVE @ NIPAM nanoparticles. The system was centrifuged at 10000rpm, and the supernatant was decanted and redissolved with DMF. And repeating the coprecipitation step twice, and drying the white precipitate in vacuum at 25 ℃ to obtain the cPBzVE @ NIPAM nano-particles.

Example 3

15.0. mu.L of stannic chloride was added to 10.0mL of ultra dry methylene chloride, stirred and cooled to-15 ℃. VBC in methylene chloride (0.4g/mL,5mL) was slowly added dropwise thereto, and the reaction was terminated after 30min by adding methanol. Resulting in PVBC polymer chains.

PVBC was dissolved in ultra-dry DMF to make a 50mg/mL solution. 2-methylpyridine (MP, the mol ratio of MP to chlorine atom is 0.5:1.0) is added firstly, and the mixture is stirred and reacted for 24 hours at the temperature of 80 ℃.

4, 4-bipyridine (BP, mole ratio of BP to chlorine atom: 0.2:1.0) was added to the solution, and the reaction was stirred at 80 ℃ for 24 hours. After the reaction, the solution was transferred to a dialysis bag (cut-off of 3.5kDa) and dialyzed at 55 ℃ for 24 hours to remove MP. And after dialysis, the system is freeze-dried to obtain the cPVB single-chain nano-particles.

The prepared cPVBBC single-chain nano-particles are dissolved in an ultra-dry DMF solvent to prepare a solution of 2.0 mg/mL. To the solution were added triethylamine (TEA, molar ratio of TEA to chlorine atoms 0.5:1.0), and azobisisobutyramidine hydrochloride (AIBA, molar ratio of AIBA to TEA 1.0:1.0), and the mixture was stirred at 50 ℃ for 6 hours. After the reaction was complete, the solution was transferred to a dialysis bag and dialyzed for 24h to remove TEA. And (4) after dialysis, freezing and drying the system to obtain the cPVB @ AIBA single-chain nano-particles. The prepared cPVBC @ AIBA single-chain nano-particles are dissolved in an ultra-dry DMF solvent to prepare a solution of 2.0 mg/mL. The ruthenium tetroxide stained particles were characterized using transmission electron microscopy, and the results are shown in fig. 4.

5.0mL of the solution of the cPVBC @ AIBA particles synthesized above was added to a polymerization tube and 200mg of tBA, the reaction solution was subjected to freeze-pump-thaw cycles three times using a double drain tube, the reaction tube was sealed under vacuum, and the reaction was heated at 80 ℃ for 8 h. After the reaction was completed, the system was cooled to room temperature to terminate the reaction, and dropped into cold methanol to precipitate cPVBC @ PtBA single-chain nanoparticles. The system was centrifuged at 10000rpm, and the supernatant was decanted and redissolved with DMF. And repeating the coprecipitation step twice, and drying the white precipitate in vacuum at 25 ℃ to obtain the cPVB @ PtBA single-chain nano-particles.

10.0mg of cPVBC @ PtBA single-stranded nanoparticles were dissolved in 20.0mL of analytically pure DMF, 10.0. mu.L of trifluoroacetic acid and 0.5mL of secondary water were added, and stirred overnight at 25 ℃. After the reaction is finished, the system is dropped into cold ether to precipitate the cPVBC @ PAA single-chain nano-particles. The system was centrifuged at 10000rpm, and the supernatant was decanted and redissolved with DMF. And repeating the coprecipitation step twice, and drying the white precipitate in vacuum at 25 ℃ to obtain the cPVBC @ PAA single-chain nano-particles.

The prepared cPVBC @ PAA single-chain nano-particles are dissolved in an ultra-dry DMF solvent to prepare a solution of 2.0 mg/mL. 5.0mL of the solution was added to a polymerization tube and FeCl was added₃·6H₂DMF solution of O (370.0. mu.L, 50.0mg/mL) and FeSO₄·7H₂DMF solution of O (370.0 μ L, 50.0mg/mL), subjecting the reaction solution to freeze-pump-thaw cycle three times using double calandria, sealing the reaction tube under vacuum, stirring for 2h to fully load iron ions on the carboxyl functional groups, and adding 2mL ammonia water at 50 ℃ to co-precipitate iron ions to obtain Fe₃O₄And (4) crystals. Stirring for 30min, heating to 80 deg.C, reacting for 2h, and performing Fe₃O₄And (4) aging the crystals. After the reaction was completed, the system was cooled to room temperature to terminate the reaction, and the system was centrifuged at 1000rpm at a low speed to remove large particles of Fe₃O₄And (4) crystals. The particles in the centrifuged supernatant were collected with a magnet (0.2T) and dried under vacuum at 25 ℃ to obtain cPVBC @ PAA @ Fe₃O₄Magnetic composite nanoparticles.

Example 4

15.0. mu.L of stannic chloride was added to 10.0mL of ultra dry methylene chloride, stirred and cooled to-15 ℃. A solution of CVE in methylene chloride (0.4g/mL,5mL) was added slowly dropwise thereto, and the reaction was terminated after 30min by adding methanol. PCVE polymer chains are obtained.

PCVE was dissolved in ultra-dry DMF solvent to make a solution with a concentration of 50 mg/mL. 2-methylpyridine (MP, the mol ratio of MP to chlorine atom is 0.5:1.0) is added firstly, and the mixture is stirred and reacted for 24 hours at the temperature of 80 ℃.

4, 4-bipyridine (BP, mole ratio of BP to chlorine atom: 0.2:1.0) was added to the solution, and the reaction was stirred at 80 ℃ for 24 hours. After the reaction, the solution was transferred to a dialysis bag (cut-off of 3.5kDa) and dialyzed at 55 ℃ for 24 hours to remove MP. And (4) after dialysis, freezing and drying the system to obtain the cPCCE single-chain nano-particles.

And dissolving the prepared cPCCE single-chain nano-particles in an ultra-dry DMF solvent to prepare a solution of 2.0 mg/mL. To the solution were added triethylamine (TEA, molar ratio of TEA to chlorine atoms 0.5:1.0), and azobisisobutyramidine hydrochloride (AIBA, molar ratio of AIBA to TEA 1.0:1.0), and the mixture was stirred at 50 ℃ for 6 hours. After the reaction was complete, the solution was transferred to a dialysis bag and dialyzed for 24h to remove TEA. And after dialysis, the system is frozen and dried to obtain the cPCCE @ AIBA single-chain nano-particles. The prepared cPCCE @ AIBA single-chain nano-particles are dissolved in an ultra-dry DMF solvent to prepare a solution of 2.0 mg/mL.

5.0mL of the solution of cPCCE @ AIBA particles synthesized above was added to a polymerization tube and 200mg of acrylic acid was added, the reaction solution was subjected to freeze-pump-thaw cycles three times using a double drain tube, the reaction tube was sealed under vacuum, and heated at 80 ℃ for reaction for 8 hours. After the reaction was completed, the system was cooled to room temperature to terminate the reaction, and dropped into cold methanol to precipitate cPCVE @ PAA single-stranded nanoparticles. The system was centrifuged at 10000rpm, and the supernatant was decanted and redissolved with DMF. And repeating the coprecipitation step twice, and then drying the white precipitate in vacuum at 25 ℃ to obtain the cPCCE @ PAA single-chain nano-particles.

And dissolving the prepared cPCCE @ PAA single-chain nano-particles in an ultra-dry DMF solvent to prepare a solution of 2.0 mg/mL. 5.0mL of the solution was added to a polymerization tube and FeCl was added₃·6H₂DMF solution of O (370.0. mu.L, 50.0mg/mL) and FeSO₄·7H₂DMF solution of O (370.0 μ L, 50.0mg/mL), subjecting the reaction solution to freeze-pump-thaw cycle three times using double calandria, sealing the reaction tube under vacuum, stirring for 2h to fully load iron ions on the carboxyl functional groups, and adding 2mL ammonia water at 50 ℃ to co-precipitate iron ions to obtain Fe₃O₄And (4) crystals. Stirring for 30min, heating to 80 deg.C, reacting for 2h, and performing Fe₃O₄And (4) aging the crystals. After the reaction was completed, the system was cooled to room temperature to terminate the reaction, and the system was centrifuged at 1000rpm at a low speed to remove large particles of Fe₃O₄And (4) crystals. The particles in the centrifuged supernatant were collected with a magnet (0.2T) and dried under vacuum at 25 ℃ to give cPCCE @ PAA @ Fe₃O₄Magnetic composite nanoparticles.

Example 5

15.0. mu.L of stannic chloride was added to 10.0mL of ultra dry methylene chloride, stirred and cooled to-15 ℃. 1.5g of BVE was slowly added dropwise thereto, followed by 30min of reaction, BBzVE was slowly added dropwise thereto in dichloromethane (0.4g/mL,5mL), followed by 30min of reaction, and methanol was added thereto to terminate the reaction. Obtaining the PBVE-PBBzVE polymer chain.

1.0g of synthetically obtained PBVE-PBBzVE was dissolved in 20.0mL of chromatographic DMF. 1.2mL of trifluoroacetic acid and 0.6mL of secondary water were added and stirred overnight. The obtained solution is concentrated by rotary evaporation and then dropped into excessive methanol for precipitation. The precipitate was dried in vacuo to give PBVE-PBzVE chains.

PBVE-PBzVE is dissolved in an ultra-dry DMF solvent to prepare a solution with the concentration of 50 mg/mL. Methylimidazole (MI, molar ratio of MI to benzoic acid unit 0.5:1.0) was added and the reaction was stirred at 25 ℃ for 24 h.

Hexamethylene diisocyanate (HDI, molar ratio of HDI to benzoic acid units 0.2:1.0) was added to the solution, and the reaction was stirred at 25 ℃ for 24 hours. After the reaction was completed, the solution was transferred to a dialysis bag (cut-off of 3.5kDa) and dialyzed at 55 ℃ for 24 hours to remove MI. And (4) after dialysis, freezing and drying the system to obtain the PBVE-cPbzVE tadpole-shaped single-chain nano-particles.

And dissolving the prepared PBVE-cPBzVE mono-tadpole-shaped nano-particles in an ultra-dry DMF solvent to prepare a solution of 2.0 mg/mL. 5.0mL of the solution was added to a polymerization tube and FeCl was added₃·6H₂DMF solution of O (370.0. mu.L, 50.0mg/mL) and FeSO₄·7H₂DMF solution of O (370.0 μ L, 50.0mg/mL), subjecting the reaction solution to freeze-pump-thaw cycle three times using double calandria, sealing the reaction tube under vacuum, stirring for 2h to fully load iron ions on the carboxyl functional groups, and adding 2mL ammonia water at 50 ℃ to co-precipitate iron ions to obtain Fe₃O₄And (4) crystals. Stirring for 30min, heating to 80 deg.C, reacting for 2h, and performing Fe₃O₄And (4) aging the crystals. After the reaction was completed, the system was cooled to room temperature to terminate the reaction, and the system was centrifuged at 1000rpm at a low speed to remove large particles of Fe₃O₄And (4) crystals. Collecting the particles in the supernatant after centrifugation with a magnet (0.2T), and vacuum drying at 25 deg.C to obtain PBVE-cPBzVE @ Fe₃O₄Magnetic composite tadpole-shaped nanoparticles.

Example 6

15.0. mu.L of stannic chloride was added to 10.0mL of ultra dry methylene chloride, stirred and cooled to-15 ℃. 1.2mL of MS was slowly added dropwise thereto, after reacting for 30min, a dichloromethane solution of VBC (0.4g/mL,5mL) was slowly added dropwise thereto, and after reacting for 30min, methanol was added to terminate the reaction. Obtaining PMS-PVBC polymer chain.

PMS-PVBC is dissolved in super-dry DMF solvent to prepare solution with the concentration of 50 mg/mL. 2-methylpyridine (MP, the mol ratio of MP to chlorine atom is 0.5:1.0) is added firstly, and the mixture is stirred and reacted for 24 hours at the temperature of 80 ℃.

4, 4-bipyridine (BP, mole ratio of BP to chlorine atom: 0.2:1.0) was added to the solution, and the reaction was stirred at 80 ℃ for 24 hours. After the reaction, the solution was transferred to a dialysis bag (cut-off of 3.5kDa) and dialyzed at 55 ℃ for 24 hours to remove MP. And (4) after dialysis, freezing and drying the system to obtain PMS-cPPVBC tadpole-shaped nano particles.

And dissolving the prepared PMS-cPVBBC single-chain nano-particles in an ultra-dry DMF solvent to prepare a solution of 2.0 mg/mL. To the solution were added triethylamine (TEA, molar ratio of TEA to chlorine atoms 0.5:1.0), and azobisisobutyramidine hydrochloride (AIBA, molar ratio of AIBA to TEA 1.0:1.0), and the mixture was stirred at 50 ℃ for 6 hours. After the reaction was complete, the solution was transferred to a dialysis bag and dialyzed for 24h to remove TEA. And after dialysis, the system is freeze-dried to obtain PMS-cPVB @ AIBA tadpole-shaped nanoparticles. And dissolving the prepared PMS-cPVBC @ AIBA tadpole-shaped nano particles in an ultra-dry DMF solvent to prepare a solution of 2.0 mg/mL.

And dissolving the prepared PMS-cPVBC @ AIBA tadpole-shaped nano particles in an ultra-dry DMF solvent to prepare a solution of 2.0 mg/mL. 5.0mL of the above solution was put into a polymerization tube and 200mg of OEGMA was added, the reaction solution was subjected to freeze-pump-thaw cycle three times using a double drain tube, the reaction tube was sealed under vacuum, and the reaction was heated at 80 ℃ for 8 hours. After the reaction was completed, the system was cooled to room temperature to terminate the reaction, and PMS-cPVBC @ OEGMA nanoparticles were precipitated by dropping into cold ether. The system was centrifuged at 10000rpm, and the supernatant was decanted and redissolved with DMF. And repeating the coprecipitation step twice, and then drying the white precipitate in vacuum at 25 ℃ to obtain the amphiphilic PMS-cPVB @ OEGMA tadpole-shaped nanoparticles.

Example 7

15.0. mu.L of stannic chloride was added to 10.0mL of ultra dry methylene chloride, stirred and cooled to-15 ℃. Firstly, 1.2mLBVE is slowly dropped into the mixture, a dichloromethane solution (0.4g/mL,5mL) of CVE is slowly dropped after stirring for reaction for 30min, a dichloromethane solution (0.4g/mL,5mL) of MSVE is slowly dropped after stirring for reaction for 30min, and methanol is added after stirring for reaction for 30min to stop the reaction. Obtaining the PBVE-PCVE-PMSM polymer chain.

PBVE-PCVE-PMSCVE is dissolved in ultra-dry DMF solvent to prepare solution with the concentration of 50 mg/mL. 2-methylpyridine (MP, the mol ratio of MP to chlorine atom is 0.5:1.0) is added firstly, and the mixture is stirred and reacted for 24 hours at the temperature of 80 ℃.

4, 4-bipyridine (BP, mole ratio of BP to chlorine atom: 0.2:1.0) was added to the solution, and the reaction was stirred at 80 ℃ for 24 hours. After the reaction, the solution was transferred to a dialysis bag (cut-off of 3.5kDa) and dialyzed at 55 ℃ for 24 hours to remove MP. And after the dialysis is finished, freezing and drying the system to obtain the PBVE-cPCCVE-PMSVE chain-sphere-chain nano-particles.

Dissolving the prepared PBVE-cPCCE-PMSVE chain-sphere-chain nano-particles in an ultra-dry DMF solvent to prepare a solution of 2.0 mg/mL. To the solution were added triethylamine (TEA, molar ratio of TEA to chlorine atoms 0.5:1.0), and azobisisobutyramidine hydrochloride (AIBA, molar ratio of AIBA to TEA 1.0:1.0), and the mixture was stirred at 50 ℃ for 6 hours. After the reaction was complete, the solution was transferred to a dialysis bag and dialyzed for 24h to remove TEA. And after the dialysis is finished, freezing and drying the system to obtain the PBVE-cPCCE @ AIBA-PMSVE chain-sphere-chain nano-particles. Dissolving the prepared PBVE-cPCCE @ AIBA-PMSVE chain-sphere-chain nano-particles in an ultra-dry DMF solvent to prepare a solution with the concentration of 2.0 mg/mL.

5.0mL of the PBVE-cPCCE @ AIBA-PMSVE chain-sphere-chain particle solution obtained by the synthesis is added into a polymerization tube, 200mg of KH570 is added, the reaction solution is subjected to freezing-air suction-unfreezing circulation three times by using a double-row tube, the reaction tube is sealed under the vacuum condition, and the reaction is heated at 80 ℃ for 8 hours. After the reaction was completed, the system was cooled to room temperature to terminate the reaction, and dropped into cold ether to precipitate PBVE-cPCVE @ PKH570-PMSVE chain-sphere-chain particles. The system was centrifuged at 10000rpm, and the supernatant was decanted and redissolved with DMF. And repeating the coprecipitation step twice, and drying the white precipitate in vacuum at 25 ℃ to obtain the PBVE-cPCCE @ PKH570-PMSVE chain-sphere-chain particles.

10.0mg of PBVE-cPCCE @ PKH570-PMSVE chain-sphere-chain particles were dissolved in 20.0mL of analytically pure DMF, 10.0. mu.L of acetic acid was added, and stirred overnight at 25 ℃. After the reaction is finished, the system is dropped into cold ether to lead PBVE-cPCCVE @ SiO₂-precipitation of PMSVE chain-sphere-chain composite nanoparticles. The system was centrifuged at 10000rpm, and the supernatant was decanted and redissolved with DMF. Repeating the coprecipitation step twice, and drying the white precipitate in vacuum at 25 ℃ to obtain PBVE-cPCCVE @ SiO₂-PMSVE chain-sphere-chain composite nanoparticles.

Example 8

15.0. mu.L of stannic chloride was added to 10.0mL of ultra dry methylene chloride, stirred and cooled to-15 ℃. BBzVE solution (0.4g/mL,5mL) was slowly added dropwise thereto, after 30min of reaction, 1.5g BVE was slowly added dropwise thereto, VBC solution (0.4g/mL,5mL) was slowly added dropwise thereto after 30min of reaction, and after 30min of reaction, methanol was added to terminate the reaction. Obtaining the PBBzVE-PBVE-PVBC polymer chain.

PBBzVE-PBVE-PVBC is dissolved in super-dry DMF solvent to prepare a solution with the concentration of 50 mg/mL. 2-methylpyridine (MP, the mol ratio of MP to chlorine atom is 0.5:1.0) is added firstly, and the mixture is stirred and reacted for 24 hours at the temperature of 80 ℃.

4, 4-bipyridine (BP, mole ratio of BP to chlorine atom: 0.2:1.0) was added to the solution, and the reaction was stirred at 80 ℃ for 24 hours. After the reaction, the solution was transferred to a dialysis bag (cut-off of 3.5kDa) and dialyzed at 55 ℃ for 24 hours to remove MP. And (4) after dialysis, freezing and drying the system to obtain the PBBzVE-PBVE-cPPVBC tadpole-shaped nano particles.

1.0g of the synthesized PBBzVE-PBVE-cPPVBC tadpole-like nanoparticles were dissolved in 20.0mL of chromatographic DMF. 1.2mL of trifluoroacetic acid and 0.6mL of secondary water were added and stirred overnight. The obtained solution is concentrated by rotary evaporation and then dropped into excessive methanol for precipitation. And (3) drying the precipitate in vacuum to obtain the PBzVE-PBVE-cPVBC tadpole-shaped nano particles.

Dissolving the PBzVE-PBVE-cPPVBC tadpole-shaped nano particles in an ultra-dry DMF solvent to prepare a solution with the concentration of 50 mg/mL. Methylimidazole (MI, molar ratio of MI to benzoic acid unit 0.5:1.0) was added and the reaction was stirred at 25 ℃ for 24 h.

Hexamethylene diisocyanate (HDI, molar ratio of HDI to benzoic acid units 0.2:1.0) was added to the solution, and the reaction was stirred at 25 ℃ for 24 hours. After the reaction was completed, the solution was transferred to a dialysis bag (cut-off of 3.5kDa) and dialyzed at 55 ℃ for 24 hours to remove MI. And after dialysis, the system is frozen and dried to obtain the cPBzVE-PBVE-cPVBB dumbbell-shaped single-chain nano-particles.

Example 9

5.0mL of the solution of PBVE-cPBzVE @ AIBA particles synthesized above was added to a polymerization tube and Ni (NO) was added₃)₂·6H₂DMF solution of O (370.0. mu.L, 50.0mg/mL) was subjected to freeze-pump-thaw cycles three times using a double drain tube, the reaction tube was sealed under vacuum, and stirred for 24h to fully load the nickel ions on the carboxyl functional groups. Dropwise adding BH into the system₄After the reaction solution was stirred for 24 hours in DMF (2.2mL, 5.0mg/mL), the metallic nickel was sufficiently reduced. After the reaction is finished, centrifuging at 1000rpm at low speed to remove large-particle nickel crystals, collecting particles in the centrifuged supernatant by using a magnet (0.2T), and drying in vacuum at 25 ℃ to obtain the PBVE-cPBzVE @ Ni magnetic composite tadpole-shaped nano particlesAnd (3) granules.

Example 10

5.0mL of the solution of PBVE-cPbzVE @ AIBA particles synthesized above was added to a polymerization tube and HAuCl was added₄The reaction solution was subjected to freeze-pump-thaw cycle three times using a double drain tube, the reaction tube was sealed under vacuum, stirred for 2 hours to fully load gold ions on the carboxyl functional groups, and then BH was added dropwise₄After the reaction solution (2.2mL, 5.0mg/mL), the reaction mixture was stirred for 24 hours to fully reduce the gold. After the reaction was completed, the system was centrifuged at 1000rpm at a low speed to remove large-particle crystals. The system is dropped into cold ether to precipitate the PBVE-cPbzVE @ (Au-AIBA) composite tadpole-shaped nano particles. The system was centrifuged at 10000rpm, and the supernatant was decanted and redissolved with DMF. And repeating the coprecipitation step twice, and then drying the pink precipitate in vacuum at 25 ℃ to obtain the PBVE-cPBzVE @ (Au-AIBA) tadpole-shaped nano particles.

Adding PBVE-cPBzVE @ (Au-AIBA) composite tadpole-shaped nanoparticles into 200mg DEAEMA, performing freezing-air extraction-unfreezing circulation on the reaction solution for three times by using a double-row pipe, sealing the reaction pipe under a vacuum condition, and heating and reacting for 8 hours at 80 ℃. After the reaction, the system was cooled to room temperature to terminate the reaction, and was dropped into cold methanol to precipitate PBVE-cPBzVE @ (Au-PDEAEMA) tadpole-like nanoparticles. The system was centrifuged at 10000rpm, and the supernatant was decanted and redissolved with DMF. And repeating the coprecipitation step twice, and then drying the pink precipitate in vacuum at 25 ℃ to obtain the PBVE-cPBzVE @ (Au-PDEAEMA) pH response composite tadpole-shaped nano particles.

The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.